A photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device

Abstract

The present invention provides a desensitizing or radiation-sensitive resin composition having excellent resolution, LWR performance, and PED stability, a desensitizing or radiation-sensitive film using the desensitizing or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. A desensitized photoreactive or radiation-reduced resin composition comprising a resin (P) having repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups, a compound (A) that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation, and an acid diffusion control agent (B), wherein at least one of the compound (A) and the acid diffusion control agent (B) is a specific compound, and the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A); a desensitized photoreactive or radiation-reduced film using the desensitized photoreactive or radiation-reduced resin composition; a method for forming a pattern; and a method for manufacturing an electronic device.

Description

Technology Field

[0001] The present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device that can be suitably utilized in an ultra-microlithography process applicable to manufacturing processes for ultra-Large Scale Integration (LSI) and high-capacity microchips, mold-making processes for nanoimprinting, and manufacturing processes for high-density information recording media, as well as other photofabrication processes. Background Technology

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication by lithography using a resist composition is performed. Recently, with the high integration of integrated circuits, the formation of ultra-fine patterns in the sub-micron or quarter-micron range is required. Accordingly, there is a trend toward shorter wavelengths, such as from the g-line to the i-line and further to KrF excimer laser light, and currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source is being developed. In addition, as a technology to further increase resolution, the so-called immersion method, which involves filling the space between the projection lens and the sample with a high refractive index liquid (hereinafter also referred to as "immersion liquid"), has been under development.

[0003] In addition, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) is currently being developed in addition to excimer laser light. Accordingly, resist compositions that are effectively responsive to various active light or radiation are being developed.

[0004] For example, patent documents 1 and 2 describe a resist composition containing a resin having a specific structure, a photogenerative agent, and an acid diffusion control agent. Prior art literature

[0005] Patent Document 1: International Publication No. 2017 / 115629 Patent Document 2: International Publication No. 2021 / 220851 The problem to be solved

[0006] Recently, the performance requirements for resist compositions have been steadily increasing. In particular, there is a demand to improve resolution and Line Width Roughness (LWR) performance when forming fine patterns. LWR performance refers to the ability to reduce the LWR of a pattern.

[0007] In addition, for the sensitizing light-sensitive or radiation-sensitive resin composition, it is desired that the performance be less affected by the passage of time from exposure to post-exposure baking (PEB) due to manufacturing process requirements, that is, that the Post-Exposure Time Delay (PED) stability is excellent.

[0008] Accordingly, the present invention aims to provide a desensitizing photoreactive or radiation-reducing resin composition having excellent resolution, LWR performance, and PED stability.

[0009] In addition, the present invention aims to provide a photosensitive or radiation-sensitive film formed using the photosensitive or radiation-sensitive resin composition, a method for forming a pattern using the photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. means of solving the problem

[0010] The inventors have found that the above problem can be solved by the following configuration.

[0011] [1]

[0012] A resin (P) comprising repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups,

[0013] Compounds (A) that produce acids with a pKa of less than 0 upon irradiation with active light or radiation, and

[0014] A photosensitive or radiation-sensitive resin composition containing at least one acid diffusion control agent (B),

[0015] At least one of the above compound (A) and the above acid diffusion control agent (B) is a compound represented by the following formula (Z-1), and

[0016] A light-sensitive or radiation-sensitive resin composition in which the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).

[0017] [Chemical Formula 1]

[0018]

[0019] In formula (Z-1), Ar 1 , Ar 2 and Ar 3 Each represents an aryl group or a heteroaryl group independently. Ar 1 , Ar 2 and Ar 3 At least two of them may be joined to each other by a single joint or through a connector. X - represents an anion.

[0020] However, the sulfonium cation in formula (Z-1) satisfies the following condition (i).

[0021] Condition (i): Salt (a) is formed by a sulfonium cation in formula (Z-1) and an anion represented by formula (a1) below, and salt (b) is formed by a cation represented by formula (b1) below and an anion represented by formula (a1) below. Using salt (a) and salt (b) respectively, a solution with a solid content concentration of 2.7 mass% is prepared, comprising each salt, the resin (P), and a solvent containing propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethyl lactate in a mass ratio of 20 / 20 / 60, such that the "moles of added salt / (total mass of the resin (P) and the added salt)" is 0.4 mmol / g. The dissolution rate of the film obtained by applying the solution is measured against an alkaline developer, which is a 2.38 mass% aqueous tetramethylammonium hydroxide solution. The dissolution rate of the membrane formed by adding salt (a) to the alkaline developer is DR a Let , and the dissolution rate of the membrane formed by adding salt (b) with respect to the alkaline developer is DR b In the case of , DR a and DR b satisfies the following equation (i-1).

[0022] DR a / DR b≤ 0.5… (i-1)

[0023] [Chemical Formula 2]

[0024]

[0025] [2]

[0026] A light-sensitive or radiation-sensitive resin composition described in [1], wherein the total amount of compounds that generate acid upon irradiation with active light or radiation is 0.3 mmol / g or more relative to the total solid content.

[0027] [3]

[0028] The above acid diffusion control agent (B) is a compound that generates an acid with a pKa of 0 or higher upon irradiation with active light or radiation, as described in [1] or [2], a photosensitive or radiation-sensitive resin composition.

[0029] [4]

[0030] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [3], wherein the above acid diffusion control agent (B) is a compound represented by the above formula (Z-1).

[0031] [5]

[0032] The above acid diffusion control agent (B) comprises an anion represented by the following formula (xa1), a desensitizing photo- or radiation-reducing resin composition described in any one of [1] to [4].

[0033] [Chemical Formula 3]

[0034]

[0035] In equation (xa1), Ar a1 represents a direction ring. R a1 represents a substituent. k1 represents an integer from 0 to 7. If k1 is 2 or greater, multiple R a1 They may be identical or different. If k1 is 2 or greater, multiple R a1 Silver may combine with each other to form rings.

[0036] [6]

[0037] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [5], wherein the pKa of the acid generated from the above compound (A) is -1.5 or higher.

[0038] [7]

[0039] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [6], wherein the above compound (A) comprises an anion represented by the following formula (ca1).

[0040] [Chemical Formula 4]

[0041]

[0042] In formula (ca1), Ar a2 represents a direction ring. R a2 represents a substituent. k2 represents an integer from 0 to 7. If k2 is 2 or greater, multiple R a2 They may be identical or different. If k2 is 2 or greater, multiple R a2 They may combine with each other to form a ring.

[0043] [8]

[0044] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [7], wherein the ratio of the compound represented by the formula (Z-1) to the total amount of compounds that generate acid upon irradiation with active light or radiation is 50 mol% or more.

[0045] [9]

[0046] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [8], wherein the above resin (P) comprises repeating units represented by the following formula (Pa1).

[0047] [Chemical Formula 5]

[0048]

[0049] In equation (Pa1), R P1 R represents a hydrogen atom or an alkyl group. P2 represents the energy that is dehydrated by the action of acid.

[0050]

[10]

[0051] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [9], wherein the above resin (P) comprises repeating units represented by the following formula (Pa2).

[0052] [Chemical Formula 6]

[0053]

[0054] In equation (Pa2), R P3 R represents a hydrogen atom or an alkyl group. P4 represents the energy that is dehydrated by the action of acid.

[0055]

[11]

[0056] A photosensitive or radiation-sensitive resin composition described in any one of [1] to

[10] , wherein the compound represented by the above formula (Z-1) is the compound represented by the following formula (Z-2).

[0057] [Chemical Formula 7]

[0058]

[0059] In equation (Z-2), R Z1 , R Z2 and R Z3 Each represents an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, an acylamino group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or an arylsulfonyl group. n1 represents an integer from 1 to 5. n2 and n3 each represent an integer from 0 to 5. R Z1 , R Z2 and R Z3 In cases where each exists in multiple instances, multiple R Z1 , R Z2 and R Z3 They may be identical or different. R Z1 , R Z2 and R Z3 At least two of them may be joined to each other by single bonds or via linkers. Also, the benzene rings in formula (Z-2) may be joined to each other by single bonds or via linkers. X - represents an anion.

[0060]

[12]

[0061] The above DR a and the above DR b A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to

[11] that satisfies the following formula (i-2).

[0062] DR a / DR b≤ 0.10… (i-2)

[0063]

[13]

[0064] A photosensitive or radiation-sensitive resin composition described in any one of [1] to

[12] , wherein the ClogP of the sulfonium cation in the above formula (Z-1) is 3 or more and 8 or less.

[0065]

[14]

[0066] A photosensitive or radiation-sensitive resin composition described in any one of [1] to

[13] , wherein the ratio of the compound represented by the formula (Z-1) to the total amount of compounds that generate acid upon irradiation with active light or radiation is 100 mol%.

[0067]

[15]

[0068] [1] to

[14] A desensitizing photoreceptive or desensitizing radioreceptive film formed by a desensitizing photoreceptive or desensitizing radioreceptive resin composition.

[0069]

[16]

[0070] A pattern forming method comprising: a process of forming a photosensitive or photosensitive film on a substrate using a photosensitive or photosensitive resin composition described in any one of [1] to

[14] ; a process of exposing the photosensitive or photosensitive film to light; and a process of developing the exposed photosensitive or photosensitive film using a developer.

[0071]

[17]

[0072] A method for manufacturing an electronic device comprising the pattern forming method described in

[16] .

[0073]

[18]

[0074] A resin (P) comprising repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups,

[0075] Compounds (A) that produce acids with a pKa of less than 0 upon irradiation with active light or radiation, and

[0076] A desensitizing photoreactive or radiation-reducing resin composition containing an acid diffusion control agent (B),

[0077] The above resin (P) includes a repeating unit represented by the following formula (Pa2), and

[0078] At least one of the above compound (A) and the above acid diffusion control agent (B) is a compound represented by the following formula (Z-2), and

[0079] A light-sensitive or radiation-sensitive resin composition in which the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).

[0080] [Chemical Formula 8]

[0081]

[0082] In equation (Pa2), R P3 R represents a hydrogen atom or an alkyl group. P4 represents the energy that is dehydrated by the action of acid.

[0083] [Chemical Formula 9]

[0084]

[0085] In equation (Z-2), R Z1 , R Z2 and R Z3Each represents an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, an acylamino group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or an arylsulfonyl group. n1 represents an integer from 1 to 5. n2 and n3 each represent an integer from 0 to 5. R Z1 If this plural exists, the plural R Z1 They may be identical or different from each other, and may combine to form a ring. R Z2 If there are multiple instances of , multiple R Z2 They may be identical or different from each other, and may combine to form a ring. R Z3 If this plural exists, the plural R Z3 They may be identical or different, and may be combined with each other. Also, the benzene rings in formula (Z-2) may be connected to each other by single bonds or through linkers. X - represents an anion represented by the following formula (xa1).

[0086] [Chemical Formula 10]

[0087]

[0088] In equation (xa1), Ar a1 represents a direction ring. R a1 represents a substituent. k1 represents an integer from 0 to 7. If k1 is 2 or greater, multiple R a1 They may be identical or different. If k1 is 2 or greater, multiple R a1 Silver may combine with each other to form rings. Effects of the invention

[0089] The present invention provides a desensitizing photoreactive or radiation-reducing resin composition having excellent resolution, LWR performance, and PED stability.

[0090] In addition, the present invention may provide a photosensitive or radiation-sensitive film using the photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device. Specific details for implementing the invention

[0091] The present invention will be described in detail below.

[0092] The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0093] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB).

[0094] In this specification, "light" means active light or radiation.

[0095] In this specification, "exposure" includes, unless specifically explained otherwise, exposure by emission spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, as well as drawing by particle beams such as electron beams and ion beams.

[0096] In this specification, "~" is used to mean including the values ​​described before and after it as lower and upper limits.

[0097] In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Also, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0098] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (also called molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene equivalent values ​​obtained by GPC measurement using a Gel Permeation Chromatography (GPC) device (HLC-8120GPC manufactured by Tosho Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10μL, column: TSK gel Multipore HXL-M manufactured by Tosho Corporation, column temperature: 40℃, flow rate: 1.0mL / min, detector: differential refractive index detector).

[0099] Regarding the notation of a group (atomic group) in this specification, unless contrary to the spirit of the present invention, notations that do not specify substitution or non-substitution include groups that include substituents along with groups that do not have substituents. For example, the term "alkyl group" includes not only alkyl groups that do not have substituents (non-substituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group comprising at least one carbon atom.

[0100] As for the substituents, monovalent substituents are preferred unless otherwise specified. Examples of substituents include monovalent nonmetal groups excluding hydrogen atoms, and, for example, can be selected from the following substituents T.

[0101] (Substituent T)

[0102] As substituent T, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and tert-butoxy groups; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy groups; acyl groups such as acetyl, benzoyl, isobutyryl, acrylyl, methacryloyl, and methoxalyl groups; sulfaneyl groups; alkylsulfaneyl groups such as methylsulfaneyl and tert-butylsulfaneyl groups; arylsulfaneyl groups such as phenylsulfaneyl and p-tolylsulfaneyl groups; alkyl groups; alkenyl groups; Examples include cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups, etc. In addition, if these substituents may have one or more additional substituents, a group having one or more substituents selected from the above substituents as additional substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.) is also included as an example of substituent T.

[0103] In this specification, the bonding direction of the divalent groups indicated is not limited unless specifically explained. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may be -CO-O- or -O-CO-. The compound may be "X-CO-OZ" or "XO-CO-Z".

[0104] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, it is a value obtained by calculation based on the database of Hamette's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification represent values ​​obtained by calculation using this software package.

[0105] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0106] In addition, pKa is also determined by molecular orbital calculations. Specifically, this method involves H in an aqueous solution based on thermodynamic cycles. + One method is to calculate it by calculating the dissociation free energy. H + Regarding the method for calculating the dissociation free energy, it can be calculated, for example, by the Density Functional Path (DFT); however, various other methods have been reported in the literature and are not limited to this. Furthermore, while there are multiple software programs capable of performing DFT, Gaussian 16 can be cited as an example.

[0107] In this specification, pKa refers to a value obtained by calculation based on a database of Hammett's substituent constants and known literature values ​​using software package 1 as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on the DFT (density functional method) is adopted.

[0108] In this specification, pKa refers to "pKa in an aqueous solution" as described above; however, if pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0109] In this specification, "solid content" refers to a component that forms a photosensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered a solid content even if its nature is in a liquid state.

[0110] <Resin composition that is sensitive to light or radiation>

[0111] The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as the "composition of the present invention") is,

[0112] A resin (P) comprising repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups,

[0113] Compounds (A) that produce acids with a pKa of less than 0 upon irradiation with active light or radiation, and

[0114] A photosensitive or radiation-sensitive resin composition containing at least one acid diffusion control agent (B),

[0115] At least one of the above compound (A) and the above acid diffusion control agent (B) is a compound represented by the following formula (Z-1), and

[0116] A light-sensitive or radiation-sensitive resin composition in which the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).

[0117] [Chemical Formula 11]

[0118]

[0119] In formula (Z-1), Ar 1 , Ar 2 and Ar 3Each represents an aryl group or a heteroaryl group independently. Ar 1 , Ar 2 and Ar 3 At least two of them may be joined to each other by a single joint or through a connector. X - represents an anion.

[0120] However, the sulfonium cation in formula (Z-1) satisfies the following condition (i).

[0121] Condition (i): Salt (a) is formed by a sulfonium cation in formula (Z-1) and an anion represented by formula (a1) below, and salt (b) is formed by a cation represented by formula (b1) below and an anion represented by formula (a1) below. Using salt (a) and salt (b) respectively, a solution with a solid content concentration of 2.7 mass% is prepared, comprising each salt, the resin (P), and a solvent containing propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethyl lactate in a mass ratio of 20 / 20 / 60, such that the "moles of added salt / (total mass of the resin (P) and the added salt)" is 0.4 mmol / g. The dissolution rate of the film obtained by applying the solution is measured against an alkaline developer, which is a 2.38 mass% aqueous tetramethylammonium hydroxide solution. The dissolution rate of the membrane formed by adding salt (a) to the alkaline developer is DR a Let , and the dissolution rate of the membrane formed by adding salt (b) with respect to the alkaline developer is DR b In the case of , DR a and DR b satisfies the following equation (i-1).

[0122] DR a / DR b≤ 0.5… (i-1)

[0123] [Chemical Formula 12]

[0124]

[0125] Although the mechanism by which the above-mentioned effect is obtained by the composition of the present invention is not entirely clear, the inventors estimate as follows.

[0126] Since the resin (P) contains repeating units having phenolic hydroxyl groups as hydrophilic sites and repeating units having acid-degradable groups as hydrophobic sites, there is non-uniformity in the dissolution rate with respect to the developer. By adding a compound represented by formula (Z-1) to the resin (P), the dissolution rate of the resin (P) (especially the dissolution rate of the hydrophilic sites) can be reduced (this action is also called "inhibition"), and the non-uniformity in the dissolution rate is suppressed, and as a result, it is believed that the resolution, LWR performance, and PED stability have improved. In addition, it is believed that the resolution, LWR performance, and PED stability have improved further because the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of compound (A).

[0127] The composition of the present invention is typically a resist composition, and may be a positive-type resist composition or a negative-type resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.

[0128] The composition of the present invention may be a chemically amplified type resist composition or a non-chemically amplified type resist composition. Typically, the composition of the present invention is a chemically amplified type resist composition.

[0129] A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. The photosensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film.

[0130] First, the various components of the composition of the present invention will be described in detail below.

[0131] [Suzy (P)]

[0132] The resin (P) included in the composition of the present invention is a resin comprising repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups.

[0133] The resin (P) is an acid-degradable resin, and in a pattern forming method using the composition of the present invention, typically, when an alkaline developer is used as the developer, a positive type pattern is suitably formed, and when an organic developer is used as the developer, a negative type pattern is suitably formed.

[0134] (Repeating unit having an acid-degrading group)

[0135] The acid-decomposing group is a group that is decomposed by the action of acid and whose polarity increases.

[0136] The acid-degradable group is typically a group that decomposes upon the action of an acid to generate a polar group. It is desirable for the acid-degradable group to have a structure in which the polar group is protected by the action of the acid (detachable group). Typically, the polarity of the resin (P) increases upon the action of the acid, thereby increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.

[0137] As the above polar group, an alkali-soluble group is preferred, and examples include an acidic group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group.

[0138] Examples of groups that are removed by the action of acid include the groups represented by equations (Y1) to (Y4).

[0139] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0140] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0141] Equation (Y3): -C(R 36 )(R 37 )(OR 38 )

[0142] Equation (Y4): -C(Rn)(H)(Ar)

[0143] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (straight or branched), or an alkeneyl group (straight or branched). Additionally, when all of Rx1 to Rx3 are alkyl groups (straight or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0144] Among these, it is preferable that Rx1 to Rx3 each independently represent a straight-chain or branched-chain alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a straight-chain alkyl group.

[0145] Two of Rx1 to Rx3 may combine to form a ring (either a monoring or a polyring).

[0146] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0147] As for the cycloalkyl groups of Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0148] As for the aryl groups of Rx1 to Rx3, aryl groups having 6 to 10 carbon atoms are preferred, and examples include phenyl groups, naphthyl groups, and anthryl groups.

[0149] As for the aralkyl groups of Rx1 to Rx3, it is preferable to have a group in which one hydrogen atom of the alkyl groups of Rx1 to Rx3 described above is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples include a benzyl group.

[0150] As for the alkene groups of Rx1~Rx3, a vinyl group is preferred.

[0151] As for the ring formed by combining two of Rx1 to Rx3, a cycloalkyl group is preferred. As for the cycloalkyl group formed by combining two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0152] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0153] The group represented by formula (Y1) or formula (Y2) is preferably, for example, in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are combined to form the cycloalkyl group described above.

[0154] In equation (Y3), R 36 ~R 38 Each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 Silver may combine with each other to form rings. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. R 36 It is also desirable that it be a hydrogen atom.

[0155] In addition, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with, for example, one or more methylene groups having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group.

[0156] Also, R 38 It may combine with other substituents on the main chain of the repeating unit to form a ring. R 38 The group formed by the bonding of other substituents on the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0157] In formula (Y4), Ar represents an aromatic group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. More preferably, Ar is an aryl group.

[0158] It is preferable that the resin (P) includes a repeating unit represented by the following formula (Pa1). The repeating unit represented by the following formula (Pa1) is a repeating unit having an acid-degradable group.

[0159] [Chemical Formula 13]

[0160]

[0161] In equation (Pa1), R P1 R represents a hydrogen atom or an alkyl group. P2 represents the energy that is dehydrated by the action of acid.

[0162] R P1The alkyl group represented here may be straight-chain or branched-chain. As for the alkyl group, alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred. The alkyl group may have substituents.

[0163] R P2 As for the groups detached by the action of the acid represented by, examples include the groups represented by the above-described equations (Y1) to (Y4). R P2 As is detached, a hydroxyl group (phenolic hydroxyl group) is generated in formula (Pa1).

[0164] It is also desirable for the resin (P) to include a repeating unit represented by the following formula (Pa2). The repeating unit represented by the following formula (Pa2) is a repeating unit having an acid-degradable group.

[0165] [Chemical Formula 14]

[0166]

[0167] In equation (Pa2), R P3 R represents a hydrogen atom or an alkyl group. P4 represents the energy that is dehydrated by the action of acid.

[0168] R P3 The alkyl group represented here may be straight-chain or branched-chain. As for the alkyl group, alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred. The alkyl group may have substituents.

[0169] R P4 As for the groups detached by the action of the acid represented by, examples include the groups represented by the above-described equations (Y1) to (Y4). R P4 As is detached, a carboxyl group is generated in formula (Pa2).

[0170] The content of repeating units having acid-degradable groups is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 15 mol% or more, with respect to the total repeating units in the resin (P). In addition, the content of repeating units having acid-degradable groups is preferably 70 mol% or less, more preferably 60 mol% or less, and more preferably 50 mol% or less, with respect to the total repeating units in the resin (P).

[0171] The repeating unit having an acid-degradable group included in the resin (P) may be one type or two or more types. When the resin (P) includes two or more repeating units having an acid-degradable group, it is preferable that the total content thereof is within the range of the above suitable content.

[0172] (Repeating unit having a phenolic hydroxyl group)

[0173] A repeating unit having a phenolic hydroxyl group containing resin (P) is described.

[0174] It is preferable that the repeating unit having a phenolic hydroxyl group is a repeating unit different from the repeating unit having an acid-degrading group described above.

[0175] The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following formula (Pa3).

[0176] [Chemical Formula 15]

[0177]

[0178] In equation (Pa3), R 101 , R 102 and R 103 Each represents, independently, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 102 is Ar A It may combine with to form a ring, and in that case, R 102 represents a single bond or an alkylene group.

[0179] L Arepresents a single link or a divalent link.

[0180] Ar A represents directional ventilation.

[0181] k represents an integer from 1 to 5.

[0182] R in equation (Pa3) 101 , R 102 and R 103 Each represents, independently, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0183] R 101 , R 102 and R 103 As for the alkyl group, it may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, 1 to 5 is more preferred, and 1 to 3 is particularly preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.

[0184] R 101 , R 102 and R 103 The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. R 101 , R 102 and R 103 As for the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0185] R 101 , R 102 and R 103 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0186] R 101, R 102 and R 103 The alkyl group included in the alkoxycarbonyl group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0187] Ar in formula (Pa3) A represents an aromatization, and more specifically, represents an aromatization of (k+1). In the case where k is 1, the divalent aromatization is preferably a divalent aromatization comprising, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, tolylene group, naphthylene group, or anthraceneylene group, or a heterocyclic ring such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, or thiazole ring. The above aromatization may have a substituent.

[0188] As a specific example of a (k+1)-valent directional ventilation in the case where k is an integer greater than or equal to 2, a group formed by removing (k-1) arbitrary hydrogen atoms from the above-described specific example of a divalent directional ventilation can be cited.

[0189] The (k+1) directional ventilation may have additional substituents.

[0190] The substituents that may have a (k+1) valence aromatic group are not particularly limited, but examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl groups.

[0191] Ar AIt is preferable that it represents an aromatic group having 6 to 18 carbon atoms, and more preferable that it represents a benzene group, a naphthalene group, or a biphenylene group.

[0192] L in equation (Pa3) A represents a single bond or a divalent linker.

[0193] L A The divalent connector represented by is not particularly limited, but for example, -COO-, -CONR 104 Examples include -, alkylene groups, or groups formed by combining two or more of these groups. The above R 104 represents a hydrogen atom or an alkyl group.

[0194] The above alkylene group is not particularly limited, but an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, is preferred.

[0195] R 104 As for the alkyl group in which α represents an alkyl group, examples include alkyl groups having 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups having 8 or fewer carbon atoms are preferred.

[0196] The repeating unit represented by formula (Pa3) preferably has a hydroxystyrene structure. That is, Ar A It is desirable to represent a benzene ring.

[0197] It is preferable that k represents an integer from 1 to 3, and more preferable that it represents 1 or 2.

[0198] The content of repeating units having phenolic hydroxyl groups in the resin (P) is not particularly limited, but is preferably 20 mol% or more with respect to the total repeating units in the resin (P), more preferably 30 mol% or more, and even more preferably 40 mol% or more. In addition, the content of repeating units having phenolic hydroxyl groups is preferably 90 mol% or less with respect to the total repeating units in the resin (P), more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0199] The repeating unit having a phenolic hydroxyl group included in the resin (P) may be one type or two or more types. When the resin (P) includes two or more repeating units having a phenolic hydroxyl group, it is preferable that the total content thereof is within the range of the above suitable content.

[0200] The resin (P) may include other repeating units in addition to repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups.

[0201] For other repeating units, the contents of

[0112] –

[0172] of International Publication No. 2022 / 024928 are taken into account.

[0202] The resin (P) can be synthesized by a conventional method (e.g., radical polymerization).

[0203] As a polystyrene equivalent value by the GPC method, the weight average molecular weight (Mw) of the resin (P) is preferably 30,000 or less, more preferably 1,000 to 30,000, more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000.

[0204] The dispersion (molecular weight distribution, Pd, Mw / Mn) of the resin (P) is preferably 1 to 5, more preferably 1 to 3, more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. The smaller the dispersion, the better the resolution and resist shape, and also the smoother the sidewalls of the resist pattern and the better the roughness.

[0205] In the composition of the present invention, the content of resin (P) is preferably 40.0 to 99.9 mass% with respect to the total solid content of the composition of the present invention, and more preferably 60.0 to 90.0 mass%.

[0206] The resin (P) may be used as a single type or as two or more types. When two or more types of resin (P) are used, it is preferable that their total content be within the range of the above suitable content.

[0207] [Compounds represented by formula (Z-1)]

[0208] The compound represented by formula (Z-1) may be a compound (A) that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation, or an acid diffusion control agent (B). Also, both the compound (A) and the acid diffusion control agent (B) may be compounds represented by formula (Z-1). Furthermore, a compound that generates an acid with a pKa of 0 or more upon irradiation with active light or radiation is an acid diffusion control agent (B). Also, regarding a compound containing two or more acid-generating sites upon irradiation with active light or radiation, if the pKa of the acid with the smallest pKa among the generated acids is less than 0, it is designated as compound (A), and if the pKa of the acid with the smallest pKa among the generated acids is 0 or more, it is designated as an acid diffusion control agent (B).

[0209] The compound represented by formula (Z-1) is preferably an acid diffusion control agent (B). The pKa of the acid generated from the compound represented by formula (Z-1) is preferably 0 or higher, more preferably 1 or higher, and more preferably 2 or higher. In addition, the pKa of the acid generated from the compound represented by formula (Z-1) is preferably 10 or lower, and more preferably 9 or lower.

[0210] [Chemical Formula 16]

[0211]

[0212] In formula (Z-1), Ar 1 , Ar 2 and Ar 3 Each represents an aryl group or a heteroaryl group independently. Ar 1 , Ar 2 and Ar 3 At least two of them may be joined to each other by a single joint or through a connector. X - represents an anion.

[0213] Ar 1 , Ar 2 and Ar 3 The aryl group represented therein is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

[0214] Ar 1 , Ar 2 and Ar 3The heteroaryl group represented here is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably comprises at least one heteroatom selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroaryl groups include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, etc. The heteroaryl group may have a substituent.

[0215] Ar 1 , Ar 2 and Ar 3 It is desirable for it to represent an aryl group.

[0216] Ar 1 , Ar 2 and Ar 3 At least two of them may be joined to each other by a single bond or by interposing a linker. Examples of linkers include -O-, -S-, -CO-, -CO2-, -SO-, -SO2-, alkylene groups (preferably 1 to 5 carbon atoms), alkenylene groups (preferably 2 to 5 carbon atoms), and groups formed by combining two or more of these.

[0217] X in equation (Z-1) - represents an anion. Examples of anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkylcarboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, etc.

[0218] The aliphatic portion of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be a straight-chain or branched-chain alkyl group or a cycloalkyl group, and a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms is preferred.

[0219] The above alkyl group may be, for example, a fluoroalkyl group (it may have a substituent other than a fluorine atom. It may also be a perfluoroalkyl group).

[0220] As for the aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a tolyl group, and a naphthyl group.

[0221] The alkyl groups, cycloalkyl groups, and aryl groups mentioned above may have substituents. Substituents are not particularly limited, but examples include halogen atoms such as nitro groups, fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably 1 to 15 carbon atoms), alkyl groups (preferably 1 to 10 carbon atoms), cycloalkyl groups (preferably 3 to 15 carbon atoms), aryl groups (preferably 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably 2 to 7 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably 2 to 7 carbon atoms), alkylthio groups (preferably 1 to 15 carbon atoms), alkylsulfonyl groups (preferably 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably 6 to 20 carbon atoms).

[0222] As for the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferred.

[0223] Examples of aryl-kil groups having 7 to 14 carbon atoms include benzyl groups, phenethyl groups, naphthylmethyl groups, naphthylethyl groups, and naphthylbutyl groups.

[0224] Examples of sulfonylimide anions include saccharin anions.

[0225] As the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferred. As substituents of these alkyl groups, examples include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

[0226] In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond with each other to form a ring structure. This increases the acid strength.

[0227] Other anions include, for example, phosphorus fluoride (e.g., PF6) - ), boron fluoride (e.g., BF4 - ), and, antimony fluoride (e.g., SbF6 - ...can be cited.

[0228] X - It is preferable that it be represented by the following equation (xa1).

[0229] [Chemical Formula 17]

[0230]

[0231] In equation (xa1), Ar a1 represents a direction ring. R a1 represents a substituent. k1 represents an integer from 0 to 7. If k1 is 2 or greater, multiple R a1 They may be identical or different. If k1 is 2 or greater, multiple R a1 Silver may combine with each other to form rings.

[0232] Ar a1The aromatic ring represented here may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of reduced carbon atoms of the aromatic hydrocarbon ring is preferably 6 to 20, and more preferably 6 to 15. As the aromatic hydrocarbon ring, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The number of reduced atoms of the aromatic heterocyclic ring is preferably 4 to 20, and more preferably 5 to 10. As the aromatic heterocyclic ring, it is preferable to include at least one of a sulfur atom, a nitrogen atom, and an oxygen atom. Examples of aromatic heterocyclic rings include, for instance, five-membered aromatic heterocyclic rings such as pyrrole rings, imidazole rings, pyrazol rings, oxazole rings, iso-oxazole rings, thiazole rings, isothiazol rings, triazole rings, furan rings, and thiophene rings; six-membered aromatic heterocyclic rings such as pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, thiazine rings, and oxazine rings.

[0233] R a1 The substituents represented here are not particularly limited, but examples include the above substituent T, and hydroxyl groups, carboxyl groups, alkyl groups, alkoxy groups, and halogen atoms are preferred.

[0234] k1 represents an integer from 0 to 7, preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.

[0235] The compound represented by formula (Z-1) is preferably a compound represented by the following formula (Z-2).

[0236] [Chemical Formula 18]

[0237]

[0238] In equation (Z-2), R Z1 , R Z2 and R Z3Each represents an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, an acylamino group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or an arylsulfonyl group. n1 represents an integer from 1 to 5. n2 and n3 each represent an integer from 0 to 5. R Z1 , R Z2 and R Z3 In cases where each exists in multiple instances, multiple R Z1 , R Z2 and R Z3 They may be identical or different. R Z1 , R Z2 and R Z3 At least two of them may be joined to each other by single bonds or via linkers. Also, the benzene rings in formula (Z-2) may be joined to each other by single bonds or via linkers. X - represents an anion.

[0239] R Z1 , R Z2 and R Z3 The alkyl group may be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, 1 to 5 is more preferred, and 1 to 3 is particularly preferred. The alkyl group may have a substituent. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, trifluoromethyl, etc.

[0240] R Z1 , R Z2 and R Z3The description, specific examples, and preferred ranges regarding the alkyl group included in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylaminocarbonyl group, and alkylsulfonyl group of, the alkyl group when the acyloxy group is an alkylcarbonyloxy group, and the alkyl group when the acylamino group is an alkylcarbonylamino group are, wherein R Z1 , R Z2 and R Z3 It is identical to the alkyl group of.

[0241] R Z1 , R Z2 and R Z3 The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, adamantyl groups, etc. The cycloalkyl group may have substituents. One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be substituted with vinylene groups.

[0242] R Z1 , R Z2 and R Z3 The description, specific examples, and preferred ranges regarding the cycloalkyl group included in the cycloalkyloxy group, cycloalkylthio group, cycloalkyloxycarbonyl group, cycloalkylaminocarbonyl group, and cycloalkylsulfonyl group of the cycloalkyl group when the acyloxy group is a cycloalkylcarbonyloxy group, and the cycloalkyl group when the acylamino group is a cycloalkylcarbonylamino group are the cycloalkyl group, are as follows: the above R Z1 , R Z2 and R Z3 It is identical to the cycloalkyl group of.

[0243] R Z1 , R Z2 and RZ3 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

[0244] R Z1 , R Z2 and R Z3 The description, specific examples, and preferred ranges regarding the aryl group included in the aryloxy group, arylthio group, aryloxycarbonyl group, arylaminocarbonyl group, and arylsulfonyl group, the aryl group when the acyloxy group is an arylcarbonyloxy group, and the aryl group when the acylamino group is an arylcarbonylamino group, are as follows: R Z1 , R Z2 and R Z3 It is identical to the aryl group.

[0245] R Z1 , R Z2 and R Z3 The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably comprises at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of heteroaryl groups include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, etc. The heteroaryl group may have a substituent.

[0246] R Z1 , R Z2 and R Z3 At least two of them may be joined to each other by a single bond or through a linker. Also, the benzene ring (R in formula (Z-2) Z1 , R Z2 and R Z3The benzene rings that are bonded together may be bonded to each other by a single bond or by interposing a linker. Examples of linkers include -O-, -S-, -CO-, -CO2-, -SO-, -SO2-, alkylene groups (preferably 1 to 5 carbon atoms), alkenylene groups (preferably 2 to 5 carbon atoms), and groups formed by combining two or more of these.

[0247] X in equation (Z-2) - represents an anion. X - The description, specific examples, and preferred ranges of X in the above-described formula (Z-1) are - It is the same as.

[0248] (Regarding condition (i))

[0249] The sulfonium cation in formula (Z-1) (the sulfonium cation represented by the following formula (Z-1c)) satisfies the following condition (i).

[0250] Condition (i): Salt (a) is formed by a salt consisting of a sulfonium cation in formula (Z-1) and an anion represented by formula (a1) below (salt represented by formula (a) below), and salt (b) is formed by a salt consisting of a cation represented by formula (b1) below and an anion represented by formula (a1) below (salt represented by formula (b) below). Using salt (a) and salt (b) respectively, a solution with a solid content concentration of 2.7 mass% is prepared, comprising each salt, the resin (P), and a solvent containing propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethyl lactate in a mass ratio of 20 / 20 / 60, such that the "moles of added salt / (total mass of the resin (P) and the added salt)" is 0.4 mmol / g. The dissolution rate of the film obtained by applying the above solution with respect to an alkaline developer, which is a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, is measured. The dissolution rate of the film formed by adding salt (a) with respect to the alkaline developer is DR aLet , and the dissolution rate of the membrane formed by adding salt (b) with respect to the alkaline developer is DR b In the case of , DR a and DR b satisfies the following equation (i-1).

[0251] DR a / DR b≤ 0.5… (i-1)

[0252] [Chemical Formula 19]

[0253]

[0254] By satisfying condition (i) with the sulfonium cation represented by formula (Z-1c), the composition of the present invention has stronger inhibition than when using salt (b), and the non-uniformity of the dissolution rate of the resin (P) is suppressed, thereby improving the resolution, LWR performance, and PED stability.

[0255] DR a and DR b More specifically, it is measured as follows.

[0256] (DR a (Measurement of)

[0257] A solution (Sa) with a solid content of 2.7 mass% is prepared, comprising a salt (a), a resin (P), and a solvent (a mixed solvent consisting of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethyl lactate in a mass ratio of 20 / 20 / 60). In the solution (Sa), the “moles of salt (a) / (total mass of resin (P) and salt (a)” is 0.4 mmol / g.

[0258] Solution (Sa) is applied onto a silicon wafer at 1500 rpm (rotations per minute) and baked at 130°C for 300 seconds to form a film (La) with a thickness of 80 nm. The film (La) is developed (dissolved) with an alkaline developer (an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38 mass%) for 600 seconds, followed by rinsing with pure water for 30 seconds. The film thickness after development is measured using a spectroscopic ellipsometer (e.g., M-2000D (manufactured by J.A. Uram Japan Co., Ltd.)), and the difference between the film thickness before development and the film thickness after development is defined as the developed film thickness. The value obtained by dividing the developed film thickness by the development time (600 seconds) is DR. a ...does as.

[0259] (DR b (Measurement of)

[0260] A solution (Sb) with a solid content of 2.7 mass% is prepared, comprising a salt (b), a resin (P), and a solvent (a mixed solvent consisting of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethyl lactate in a mass ratio of 20 / 20 / 60). In the solution (Sb), the moles of salt (b) / (total mass of resin (P) and salt (b)) is 0.4 mmol / g.

[0261] Solution (Sb) is applied onto a silicon wafer at 1500 rpm and baked at 130°C for 300 seconds to form a film (Lb) with a thickness of 80 nm. The film (Lb) is developed (dissolved) in an alkaline developer (an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38 mass%) for 600 seconds, followed by rinsing with pure water for 30 seconds. The film thickness after development is measured using a spectroscopic ellipsometer (e.g., M-2000D (manufactured by J.A. Uram Japan Co., Ltd.)), and the difference between the film thickness before development and the film thickness after development is defined as the developed film thickness. The value obtained by dividing the developed film thickness by the development time (600 seconds) is DR. b ...does as.

[0262] DR a and DR bThe resin (P) and solvent used in the measurement are each the same.

[0263] DR a / DR b is 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, and even more preferably 0.2 or less. Also, DR a / DR b It is preferable that it be 0.01 or higher, and more preferable that it be 0.02 or higher.

[0264] On the grounds that superior resolution, LWR performance, and PED stability are obtained through stronger inhibition, DR a and DR b It is particularly desirable that the following equation (i-2) is satisfied.

[0265] DR a / DR b≤ 0.10… (i-2)

[0266] The ClogP of the sulfonium cation (sulfonium cation represented by formula (Z-1c)) in formula (Z-1) is preferably 3 or more and 11 or less, more preferably 3 or more and 8 or less, and particularly preferably 4 or more and 8 or less.

[0267] ClogP is a value obtained by calculating the common logarithm logP of the partition coefficient P for 1-octanol and water. While known methods and software may be used for calculating ClogP, unless specifically described otherwise, the present invention uses the ClogP program introduced in Cambridge Soft's ChemBioDraw Ultra 12.0.

[0268] [Compound (A)]

[0269] Compound (A) is a compound that produces an acid with a pKa of less than 0 upon irradiation with active light or radiation.

[0270] The pKa of the acid generated from compound (A) upon irradiation with active light or radiation is preferably -0.1 or less, and more preferably -0.5 or less. Additionally, the pKa of the acid generated from compound (A) upon irradiation with active light or radiation is preferably -1.5 or more, and more preferably -1.0 or more.

[0271] Compound (A) may be a compound represented by formula (Z-1), or a compound different from the compound represented by formula (Z-1).

[0272] Compound (A) may be in the form of a low-molecular-weight compound or in a form introduced into a part of a polymer. In addition, the form of a low-molecular-weight compound and the form introduced into a part of a polymer may be used in combination.

[0273] When compound (A) is in the form of a low molecular weight compound, the molecular weight of compound (A) is preferably 3000 or less, more preferably 2000 or less, and more preferably 1000 or less. The lower limit is not particularly restricted, but 100 or more is preferred.

[0274] When compound (A) is in a form introduced into a part of a polymer, it may be introduced into a part of a resin (P), or it may be introduced into a resin different from resin (P).

[0275] It is preferable that the compound (A) be in the form of a low-molecular-weight compound.

[0276] As for compound (A), for example, "M + X - Examples include compounds (onium salts) that appear as such, and it is preferable that they be compounds that generate organic acids upon exposure to light.

[0277] Examples of the above organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide.

[0278] "M + X - In compounds represented as ", M + The organic cation is represented by the formula (ZaI) (hereinafter also referred to as "cation (ZaI)"), or the cation represented by the formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0279] [Chemical Formula 20]

[0280]

[0281] In formula (ZaI), R 201 , R 202 , and R 203 Each independently represents an organic group.

[0282] R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 Two of them may combine 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. R 201 ~R 203 Examples of groups formed by the combination of two of them include, for instance, alkylene groups (e.g., butylene and pentylene groups), and -CH2-CH2-O-CH2-CH2-.

[0283] R 201 , R 202 , and R 203 The organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0284] As for the alkyl group, it may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 5 is more preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.

[0285] The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. As for the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0286] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

[0287] The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably comprises at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of heteroaryl groups include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, etc.

[0288] The cation represented by formula (ZaI) may be a sulfonium cation represented by formula (Z-1c).

[0289] In formula (ZaII), R 204 and R 205 Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group.

[0290] R 204 and R 205 As the aryl group, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. R 204 and R205 The aryl group may be an aryl group having a heterocyclic group having an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of the backbone of an aryl group having a heterocyclic group include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0291] R 204 and R 205 As for the alkyl group and cycloalkyl group, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group) is preferred.

[0292] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group of may each independently have a substituent. R 204 and R 205 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include, for example, an alkyl group (e.g., C1 to C15), a cycloalkyl group (e.g., C3 to C15), an aryl group (e.g., C6 to C15), an alkoxy group (e.g., C1 to C15), a halogen atom, a hydroxyl group, and a phenylthione group. Also, R 204 and R 205 It is also desirable for the substituents to independently form acid-degradable groups by any combination of substituents.

[0293] "M + X - In compounds represented as ", X - represents an anion. X - A specific example of is X in the above-described formula (Z-1). - Same as, but X -It is preferable that is an anion represented by the following formula (ca1). That is, compound (A) is preferable to contain an anion represented by the following formula (ca1).

[0294] [Chemical Formula 21]

[0295]

[0296] In formula (ca1), Ar a2 represents a direction ring. R a2 represents a substituent. k2 represents an integer from 0 to 7. If k2 is 2 or greater, multiple R a2 They may be identical or different. If k2 is 2 or greater, multiple R a2 They may combine with each other to form a ring.

[0297] Ar a2 The aromatic ring represented by α may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of reduced carbon atoms of the aromatic hydrocarbon ring is preferably 6 to 20, and more preferably 6 to 15. As an aromatic hydrocarbon ring, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The number of reduced atoms of the aromatic heterocyclic ring is preferably 4 to 20, and more preferably 5 to 10. As an aromatic heterocyclic ring, it is preferable to include at least one of a nitrogen atom and an oxygen atom. Examples of aromatic heterocyclic rings include, for instance, five-membered aromatic heterocyclic rings such as pyrrole rings, imidazole rings, pyrazol rings, oxazol rings, isooxazol rings, thiazole rings, isothiazol rings, and triazol rings; and six-membered aromatic heterocyclic rings such as pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, thiazine rings, and oxazine rings.

[0298] Ar a2 The aromatic ring represented by is preferably an aromatic hydrocarbon ring.

[0299] R a2The substituents represented by are not particularly limited, but examples include the above substituent T, and hydroxyl groups, carboxyl groups, alkyl groups, alkoxy groups, and halogen atoms are preferred.

[0300] k2 represents an integer from 0 to 7, preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.

[0301] Compound (A) may be at least one selected from the group consisting of compounds (I) to (II) below.

[0302] (Compound (I))

[0303] Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, and is a compound that generates an acid comprising a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation.

[0304] Structural site X: Anion site A1 - and cation site M1 + A structural region composed of, and also forming a first acidic region appearing as HA1 upon irradiation with active light or radiation.

[0305] Structural site Y: Anion site A2 - and cation site M2 + A structural region composed of, and also forming a second acidic region appearing as HA2 upon irradiation with active light or radiation.

[0306] The above compound (I) satisfies the following condition I.

[0307] Condition I: In the above compound (I), the above cation site M1 in the above structural site X + and the cation site M2 in the above structural site Y + ul H +A compound PI formed by substitution, wherein the cation site M1 in the structural site X + ul H + The acid dissociation constant a1 derived from the acidic region represented by HA1 formed by substitution, and the cation region M2 in the structural region Y. + ul H + It has an acid dissociation constant a2 derived from an acidic region represented by HA2 formed by substitution, and furthermore, the acid dissociation constant a2 is greater than the acid dissociation constant a1. At least one of the acid dissociation constants a1 is less than 0.

[0308] Condition I is explained in more detail below.

[0309] If compound (I) is an acid-generating compound having, for example, one first acidic site derived from the structural site X and one second acidic site derived from the structural site Y, then compound PI corresponds to a “compound having HA1 and HA2”.

[0310] The acid dissociation constants a1 and a2 of compound PI, to explain more specifically, in the case where the acid dissociation constants of compound PI are calculated, compound PI is "A1 - The pKa when it becomes a "compound having HA2" is the acid dissociation constant a1, and the above "A1 - "Compound having HA2" is "A1 - Department A2 - The pKa when it becomes a compound having “ is the acid dissociation constant a2.

[0311] If compound (I) is an acid-generating compound having, for example, two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y, then compound PI corresponds to "a compound having two HA1 and one HA2".

[0312] When the acid dissociation constant of compound PI is calculated, compound PI is "1 A1 - and the acid dissociation constant when it becomes a compound having 1 HA1 and 1 HA2, and "1 A1 - and a compound having one HA1 and one HA2 is "2 A1 - The acid dissociation constant when it becomes a "compound having 1 HA2" corresponds to the aforementioned acid dissociation constant a1. "2 A1 - and a compound having 1 HA2 is "2 A1 - Department A2 - The acid dissociation constant when it becomes a "compound having" corresponds to the acid dissociation constant a2. That is, in the case of compound PI, the cation site M1 in the structural site X + ul H + In the case where there are multiple acid dissociation constants derived from the acidic site represented by HA1 formed by substitution, the value of the acid dissociation constant a2 is greater than the largest value among the multiple acid dissociation constants a1. In addition, compound PI is "1 A1 - Let aa be the acid dissociation constant when it becomes a compound having 1 HA1 and 1 HA2, and "1 A1 - and a compound having one HA1 and one HA2 is "2 A1 - When the acid dissociation constant is denoted as ab when it becomes a "compound having one HA2 group," the relationship between aa and ab is aa <ab를 충족시킨다.

[0313] The acid dissociation constants a1 and a2 are obtained by the acid dissociation constant measurement method described above.

[0314] The above compound PI corresponds to the acid that is generated when compound (I) is irradiated with active light or radiation.

[0315] If compound (I) has two or more structural sites X, the structural sites X may each be the same or different. Also, two or more of the above A1- , and two or more of the above M1 + Each may be the same or different.

[0316] Among compound (I), the above A1 - and the above A2 - , and, the above M1 + and the above M2 + They may be the same or different, respectively, but the above A1 - and the above A2 - It is desirable that each be different.

[0317] (Compound (II))

[0318] Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, and is a compound that generates an acid comprising two or more of the above-mentioned first acidic sites originating from the above-mentioned structural site X and the above-mentioned structural site Z upon irradiation with active light or radiation.

[0319] Structural region Z: Non-ionic region capable of neutralizing acid

[0320] If compound (II) is, for example, an acid-generating compound having the two first acidic sites originating from the structural site X and the structural site Z, then compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, compound PII corresponds to a "compound having one A1 - and the acid dissociation constant when it becomes a compound having 1 HA1, and "1 A1 - and a compound having 1 HA1 is "2 A1 - The acid dissociation constant when it becomes a compound having “ is the acid dissociation constant a1.

[0321] The acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above. At least one of the acid dissociation constants a1 is less than 0.

[0322] The above compound PII corresponds to the acid that is generated when compound (II) is irradiated with active light or radiation.

[0323] In addition, the two or more structural parts X mentioned above may each be identical or different. Two or more of the above A1 - , and two or more of the above M1 + Each may be the same or different.

[0324] The nonionic site capable of neutralizing acid in structural site Z is not particularly limited, and, for example, it is preferable to be a site containing a group capable of electrostatically interacting with a proton, or a functional group having an electron.

[0325] As functional groups capable of electrostatically interacting with protons, or having electrons, examples include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having nitrogen atoms having non-covalent electron pairs that do not contribute to π-conjugation. A nitrogen atom having non-covalent electron pairs that do not contribute to π-conjugation is, for example, a nitrogen atom having a substructure shown in the following formula.

[0326] [Chemical Formula 22]

[0327] non-shared electron pairs

[0328] Examples of partial structures of functional groups having a group or electron capable of electrostatically interacting with protons include crown ether structures, aza crown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0329] For the cation, compound (I) and compound (II), reference may be made to

[0207] –

[0278] of International Publication No. 2022 / 024928.

[0330] The content of compound (A) in the composition of the present invention is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and more preferably 5.0 mass% or more, with respect to the total solid content of the composition of the present invention. The content of compound (A) is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and more preferably 20.0 mass% or less, with respect to the total solid content of the composition of the present invention.

[0331] Compound (A) may be used as a single type or as two or more types. If two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0332] [Acid Diffusion Control Agent (B)]

[0333] The acid diffusion control agent (B) acts as a quencher that traps acid generated from, for example, compound (A) during exposure, thereby suppressing the reaction of acid-degradable resin in the unexposed area caused by excess generated acid.

[0334] The type of acid diffusion control agent (B) is not particularly limited and may include, for example, a basic compound (BA), a low molecular weight compound (BB) having a nitrogen atom and a group that is removed by the action of acid, and a compound (BC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation.

[0335] Examples of compounds (BC) include, for instance, an onium salt compound (BD) of an acid that is relatively weak acid with respect to the acid generated from compounds (A), and a basic compound (BE) whose basicity is reduced or lost upon irradiation with active light or radiation.

[0336] Specific examples of basic compounds (BA) include, for instance, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (BE) whose basicity is reduced or lost upon irradiation with active light or radiation include those described in paragraphs

[0137] to

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

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

[0156] to

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

[0337] For example, specific examples of onium salt compounds (BD) that are relatively weak acids with respect to acids generated from compounds (A), etc., include those described in paragraphs

[0305] to

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

[0338] In addition to the above, known compounds disclosed in, for example, paragraphs

[0627] –

[0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] –

[0187] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] –

[0423] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] –

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 may be suitably used as acid diffusion control agents.

[0339] The acid diffusion control agent (B) is preferably a compound that generates an acid with a pKa of 0 or higher upon irradiation with active light or radiation.

[0340] The acid diffusion control agent (B) may be a compound represented by formula (Z-1) or a compound different from the compound represented by formula (Z-1), but it is preferable that it be a compound represented by formula (Z-1).

[0341] The acid diffusion control agent (B) preferably includes an anion represented by the formula (xa1) described above.

[0342] The content of acid diffusion control agent (B) in the composition of the present invention is preferably 3.0 mass% or more, more preferably 5.0 mass% or more, and more preferably 10.0 mass% or more, based on the total solid content of the composition of the present invention. The content of compound (A) is preferably 50.0 mass% or less, more preferably 40.0 mass% or less, and more preferably 30.0 mass% or less, based on the total solid content of the composition of the present invention.

[0343] Acid diffusion control agent (B) may be used as a single type or as two or more types. If two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0344] (Regarding the content of acid diffusion control agent (B) relative to the content of compound (A))

[0345] The content of acid diffusion control agent (B) is 80 mol% or more relative to the content of compound (A).

[0346] If the ratio (mol%) of the content of acid diffusion control agent (B) to the content of compound (A) is denoted as "(B) / (A)", then (B) / (A) = {content of acid diffusion control agent (B) / content of compound (A)} × 100.

[0347] The ratio of the acid diffusion control agent (B) to the content of compound (A) is preferably 100 mol% or more, more preferably 130 mol% or more, and particularly preferably 150 mol% or more. In addition, the ratio of the acid diffusion control agent (B) to the content of compound (A) is preferably 450 mol% or less, more preferably 400 mol% or less, and particularly preferably 350 mol% or less.

[0348] In the composition of the present invention, the total amount of the acid-generating compound upon irradiation with active light or radiation is preferably 0.3 mmol / g or more with respect to the total solid content, more preferably 0.35 mmol / g or more, and particularly preferably 0.40 mmol / g or more. Furthermore, the total amount of the acid-generating compound upon irradiation with active light or radiation is preferably 1.5 mmol / g or less with respect to the total solid content, more preferably 1.2 mmol / g or less, and particularly preferably 1.0 mmol / g or less.

[0349] In the composition of the present invention, the ratio of the compound represented by formula (Z-1) to the total amount of compounds that generate acid upon irradiation with active light or radiation is preferably 50 mol% or more, more preferably 75 mol% or more, and particularly preferably 100 mol% (where all compounds that generate acid upon irradiation with active light or radiation in the composition of the present invention are compounds represented by formula (Z-1).

[0350] [Hypohydrophobic resin (resin (T))]

[0351] The composition of the present invention may further include a hydrophobic resin (also referred to as "resin (T)") that is different from resin (P).

[0352] It is desirable for hydrophobic resins to be designed to be localized on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and non-polar substances.

[0353] In terms of localization to the film surface layer, it is preferable for the hydrophobic resin to have one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures included in the side chain portion of the resin, and it is more preferable for it to have two or more. It is preferable for the hydrophobic resin to have hydrocarbon groups with five or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

[0354] Examples of hydrophobic resins include compounds described in paragraphs

[0275] to

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

[0355] When the composition of the present invention includes a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% with respect to the total solid content of the composition of the present invention, and more preferably 0.1 to 15.0 mass%.

[0356] Hydrophobic resins may be used as a single type or as two or more types. When two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0357] [Surfactant]

[0358] The composition of the present invention may include a surfactant. If a surfactant is included, a pattern with better adhesion and fewer development defects can be formed.

[0359] Fluorine-based and / or silicone-based surfactants are preferred.

[0360] Examples of fluorine-based and / or silicone-based surfactants include the surfactants disclosed in paragraphs

[0218] and

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

[0361] When the composition of the present invention includes a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass% with respect to the total solid content of the composition of the present invention, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%.

[0362] One type of surfactant may be used, or two or more types may be used. If two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0363] [solvent]

[0364] The composition of the present invention preferably includes a solvent.

[0365] Preferably, the solvent comprises at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Additionally, the solvent may further comprise components other than components (M1) and (M2).

[0366] Combining the aforementioned solvent with the aforementioned resin is desirable from the perspective of improving the coating properties of the composition of the present invention and reducing the number of defects in the pattern development. Since the aforementioned solvent provides a good balance of the solubility, boiling point, and viscosity of the aforementioned resin, it can suppress non-uniformity in the film thickness of the resist film and the occurrence of precipitates during spin coating.

[0367] Details of component (M1) and component (M2) are described in paragraphs

[0218] –

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

[0368] If the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30 mass% with respect to the total amount of the solvent.

[0369] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30 mass%, and more preferably set so that it is 1 to 20 mass%. By doing so, the coating properties of the composition of the present invention can be further improved.

[0370] [Other additives]

[0371] The composition of the present invention may further include a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (e.g., a phenol compound with a molecular weight of 1000 or less, or a cycloaliphatic or aliphatic compound containing a carboxyl group).

[0372] The above "dissolution-inhibiting compound" is a compound with a molecular weight of 3,000 or less that decomposes due to the action of acid and reduces its solubility in an organic developer.

[0373] <Other embodiments of photosensitive or radiation-sensitive resin compositions>

[0374] The present invention also relates to a light-sensitive or radiation-sensitive resin composition having the following composition.

[0375] A resin (P) comprising repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups,

[0376] A photosensitive or radiation-sensitive resin composition containing a compound (A) that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation, and an acid diffusion control agent (B).

[0377] The above resin (P) includes a repeating unit represented by the following formula (Pa2), and

[0378] At least one of the above compound (A) and the above acid diffusion control agent (B) is a compound represented by the following formula (Z-2), and

[0379] A light-sensitive or radiation-sensitive resin composition in which the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).

[0380] [Chemical Formula 23]

[0381]

[0382] In equation (Pa2), R P3 R represents a hydrogen atom or an alkyl group. P4 represents the energy that is dehydrated by the action of acid.

[0383] [Chemical Formula 24]

[0384]

[0385] In equation (Z-2), R Z1 , R Z2 and R Z3 Each represents an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, an acylamino group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or an arylsulfonyl group. n1 represents an integer from 1 to 5. n2 and n3 each represent an integer from 0 to 5. R Z1 If this plural exists, the plural R Z1 They may be identical or different from each other, and may combine to form a ring. R Z2 If there are multiple instances of , multiple R Z2 They may be identical or different from each other, and may combine to form a ring. R Z3 If this plural exists, the plural R Z3They may be identical or different, and may be combined with each other. Also, the benzene rings in formula (Z-2) may be connected to each other by single bonds or through linkers. X - represents an anion represented by the following formula (xa1).

[0386] [Chemical Formula 25]

[0387]

[0388] In equation (xa1), Ar a1 represents a direction ring. R a1 represents a substituent. k1 represents an integer from 0 to 7. If k1 is 2 or greater, multiple R a1 They may be identical or different. If k1 is 2 or greater, multiple R a1 Silver may combine with each other to form rings.

[0389] The explanation for each of the above formulas and the content of each component are the same as those described above.

[0390] <Desensitizing photoreactive or radiation-sensitive film, pattern formation method>

[0391] The present invention also relates to a photosensitive or radiation-sensitive film formed by the composition of the present invention. The photosensitive or radiation-sensitive film of the present invention is preferably a resist film.

[0392] The present invention also relates to a pattern forming method. The pattern forming method of the present invention preferably comprises a step of forming a photosensitive or photosensitive film (typically a resist film) on a substrate using a composition of the present invention, a step of exposing the photosensitive or photosensitive film to light, and a step of developing the exposed photosensitive or photosensitive film using a developer.

[0393] The steps of the pattern formation method using the composition of the present invention are not particularly limited, but it is preferable to have the following process.

[0394] Process 1: A process of forming a resist film on a substrate using the composition of the present invention.

[0395] Process 2: Process of exposing the resist film

[0396] Process 3: Process of developing the exposed resist film using a developer.

[0397] Below, the sequence of each of the above processes will be explained in detail.

[0398] (Process 1: Resist film formation process)

[0399] Process 1 is a process of forming a resist film on a substrate using the composition of the present invention.

[0400] As a method for forming a resist film on a substrate using the composition of the present invention, for example, a method of applying the composition of the present invention onto a substrate may be used.

[0401] In addition, it is preferable to filter the composition of the present invention as needed before application. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0402] The composition of the present invention can be applied by a suitable application method, such as a spinner or a coater, onto a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit devices. Spin coating using a spinner is preferred as the application method. When performing spin coating using a spinner, the rotation speed is preferably 1,000 to 3,000 rpm (rotations per minute).

[0403] After applying the composition of the present invention, the substrate may be dried to form a resist film. Additionally, if necessary, various underlayers (inorganic film, organic film, anti-reflective film) may be formed on the lower layer of the resist film.

[0404] As a drying method, for example, a method of drying by heating may be used. Heating can be performed using means equipped in a conventional exposure machine and / or a developer, or it may be performed using a hot plate, etc. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0405] The film thickness of the resist film is not particularly limited, but 10 to 120 nm is preferred in that it allows for the formation of fine patterns with higher precision. Among these, when using EUV exposure, the film thickness of the resist film is more preferably 10 to 65 nm, and 15 to 50 nm is more preferred. When using ArF immersion exposure, the film thickness of the resist film is more preferably 10 to 120 nm, and 15 to 90 nm is more preferred.

[0406] In addition, a top coat may be formed on the upper layer of the resist film using a top coat composition.

[0407] It is preferable that the top coat composition be applied uniformly to the upper layer of the resist film without mixing with the resist film. The top coat is not particularly limited and can be formed by conventionally known top coats by conventionally known methods, for example, a top coat can be formed based on the description in paragraphs

[0072] to

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

[0408] For example, it is preferable to form a top coat containing a basic compound as described in Japanese Patent Publication No. 2013-61648 on the resist film. Specific examples of basic compounds that the top coat may contain include basic compounds that may be included in the composition of the present invention.

[0409] It is also preferable that the top coat comprises a compound having at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0410] (Process 2: Photolithography Process)

[0411] Process 2 is a process of exposing the resist film.

[0412] As a method of exposure, an active light or radiation can be irradiated onto the formed resist film through a predetermined mask.

[0413] Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and far ultraviolet light with a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams are particularly preferred.

[0414] It is desirable to perform baking (heating) after exposure and before developing. Baking promotes the reaction of the exposed area, and improves sensitivity and pattern shape.

[0415] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0416] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0417] Heating can be performed using means provided in a conventional exposure machine and / or developer, or by using a hot plate, etc.

[0418] This process is also called post-exposure baking.

[0419] (Process 3: Development Process)

[0420] Process 3 is a process of developing the exposed resist film using a developer and forming a pattern.

[0421] The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0422] Examples of development methods include a method of immersing a substrate in a tank filled with a developer solution for a certain period of time (dip method), a method of developing by raising the developer solution on the surface of the substrate by surface tension and letting it stand for a certain period of time (puddle method), a method of spraying the developer solution onto the surface of the substrate (spray method), and a method of continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a certain speed onto a substrate rotating at a certain speed (dynamic dispensing method).

[0423] In addition, after the process of performing the development, a process of stopping the development may be carried out while replacing it with another solvent.

[0424] There is no particular limit to the development time as long as it is the time for the resin in the unexposed area to sufficiently dissolve, and 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred.

[0425] The temperature of the developer solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0426] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include an alkaline aqueous solution containing a quaternary ammonium salt represented by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, or a cyclic amine. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is typically preferably 0.1 to 20 mass%. The pH of the alkaline developer is typically preferably 10.0 to 15.0.

[0427] 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.

[0428] The above solvents may be mixed in multiple quantities, or mixed with solvents other than those mentioned above or with water. The water content of the entire developer solution is preferably less than 50 mass%, more preferably less than 20 mass%, more preferably less than 10 mass%, and is particularly preferably not substantially water-free.

[0429] The content of the organic solvent in the organic developer is preferably 50 mass% or more and 100 mass% or less with respect to the total amount of the developer, more preferably 80 mass% or more and 100 mass% or less, more preferably 90 mass% or more and 100 mass% or less, and particularly preferably 95 mass% or more and 100 mass% or less.

[0430] (Other processes)

[0431] The above pattern forming method preferably includes a process of cleaning using a rinse solution after process 3.

[0432] As a rinsing solution used in the rinsing process after the development process using an alkaline developer, pure water can be used, for example. In addition, an appropriate amount of surfactant may be added to the pure water.

[0433] An appropriate amount of surfactant may be added to the rinse solution.

[0434] The rinsing solution used in the rinsing process after the development process using an organic developer is not particularly limited as long as the pattern is not dissolved, and a solution containing a general organic solvent may be used. It is preferable to use a rinsing solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0435] The method of the rinsing process is not particularly limited, and examples include a method of continuously dispensing a rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with rinsing liquid for a certain period of time (dip method), and a method of spraying a rinsing liquid onto the surface of the substrate (spray method).

[0436] In addition, the pattern forming method may include a heating process (Post Bake) after the rinsing process. Through this process, the developer and rinsing solution remaining between and inside the patterns are removed by baking. In addition, through this process, the resist pattern is annealed, and the surface roughness of the pattern is improved. The heating process after the rinsing process is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0437] In addition, the formed pattern may be used as a mask to perform an etching treatment on the substrate. That is, the pattern formed in process 3 may be used as a mask to process the substrate (or the lower layer film and the substrate) to form a pattern on the substrate.

[0438] The processing method of the substrate (or the lower layer and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by performing dry etching on the substrate (or the lower layer and the substrate) using the pattern formed in process 3 as a mask is preferred. Oxygen plasma etching is preferred for the dry etching.

[0439] Various materials used in the composition and pattern forming method of the present invention (e.g., solvent, developer, rinsing solution, composition for forming an anti-reflective film, composition for forming a top coat, 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, 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. The lower limit is not particularly restricted, but 0 mass ppt or more is preferred. 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.

[0440] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited, for example. Details of filtration using a filter are described in paragraph

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

[0441] 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 constituting various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible by lining the inside of the device with Teflon (registered trademark).

[0442] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, known adsorbents may be used; for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used. In order to reduce impurities such as metals contained in the various materials mentioned above, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be verified by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing apparatus. The content of metal components contained in the cleaning solution after use is preferably 100 mass ppt or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less. The lower limit is not particularly restricted, but 0 mass ppt or more is preferred.

[0443] In organic treatment solutions such as rinse solutions, a conductive compound may be added to prevent failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity accumulation and continuous electrostatic discharge. The conductive compound is not particularly limited, but methanol may be cited as an example. The amount added is not particularly limited, but to maintain desirable developing or rinsing characteristics, it is preferable to have 10 mass% or less, and more preferable to have 5 mass% or less. The lower limit is not particularly limited, but 0.01 mass% or more is preferred.

[0444] As for the chemical piping, various types of piping can be used, for example, made of SUS (stainless steel), or coated with antistatic-treated polyethylene, polypropylene, or fluoropolymer (polytetrafluoroethylene, or perfluoroalkoxy resin, etc.). Likewise, regarding the filter and O-ring, antistatic-treated polyethylene, polypropylene, or fluoropolymer (polytetrafluoroethylene, or perfluoroalkoxy resin, etc.) can be used.

[0445] Method for manufacturing an electronic device

[0446] The present specification relates to a method for manufacturing an electronic device comprising the pattern forming method described above, and to an electronic device manufactured by the method.

[0447] Suitable embodiments of the electronic device of this specification include embodiments mounted in electrical and electronic devices (home appliances, OA (Office Automation), media-related devices, optical devices and communication devices, etc.).

[0448] Examples

[0449] The present invention will be described in more detail below based on the examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0450] The various components used in the resist compositions of the examples and comparative examples are described below.

[0451] Suzy (P)

[0452] P-1 to P-9 were used as resins (P). The types and contents of repeating units included in P-1 to P-9 are shown in Table 1 below. The contents of repeating units are the molar ratio to the total repeating units in the resin.

[0453] The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). In addition, the content of repeating units is, 13 It was measured by C-NMR (nuclear magnetic resonance).

[0454] [Table 1]

[0455]

[0456] The structural formula for each iteration unit is shown below.

[0457] [Chemical Formula 26]

[0458]

[0459] <Hypohydrophobic resin (resin (T))>

[0460] T-1 was used as the hydrophobic resin (Resin (T)). The structural formula, repeating unit content, Mw, and Mw / Mn of T-1 are shown below. The repeating unit content in T-1 is the molar ratio to the total repeating units in the resin. Mw and Mw / Mn were measured by GPC (Carrier: Tetrahydrofuran (THF)) (these are polystyrene equivalents). The repeating unit content is, 13 It was measured by C-NMR.

[0461] [Chemical Formula 27]

[0462]

[0463] <Compound (A)>

[0464] A-1 to A-18 and AR-1 were used as compounds (A) that generate acids with a pKa of less than 0 upon irradiation with active light or radiation. A-1 to A-18 and AR-1 are compounds containing cations and anions as shown in Tables 2 and 3 below, respectively. Tables 2 and 3 below also list the pKa of the acid (generated product) generated from each compound upon irradiation with active light or radiation.

[0465] [Table 2]

[0466]

[0467] [Table 3]

[0468]

[0469] <Acid Diffusion Control Agent (B)>

[0470] B-1 to B-31 and BR-1 were used as acid diffusion control agents (B). B-1 to B-26 and BR-1 are compounds containing cations and anions, respectively, as shown in Table 4 below. B-28 to B-31 are compounds containing cations and anions, respectively, as shown in Table 5 below. Tables 4 and 5 below also list the pKa of the acid (exudative product) generated from each compound upon irradiation with active light or radiation. B-27 is a compound represented by the following structural formula.

[0471] [Table 4]

[0472]

[0473] [Table 5]

[0474]

[0475] [Chemical Formula 28]

[0476]

[0477] The structural formula of the cation is shown below. Me represents a methyl group.

[0478] [Chemical Formula 29]

[0479]

[0480] [Chemical Formula 30]

[0481]

[0482] [Chemical Formula 31]

[0483]

[0484] The structural formula of the anion is shown below.

[0485] [Chemical Formula 32]

[0486]

[0487] Solvent

[0488] The solvents used are shown below.

[0489] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0490] S-2: Propylene glycol monomethyl etherpropionate

[0491] S-3: Ethyl lactate

[0492] <Preparation of Resist Composition>

[0493] Each component other than the solvent shown in Tables 6 and 7 was used in the content (mass%) shown in Tables 6 and 7, and mixed with the solvent shown in Tables 6 and 7 to obtain a solution. The content of each component is the mass ratio to the total solid content of the resist composition. The obtained solution was filtered through a polyethylene filter having a pore size of 0.02 μm to obtain resist compositions R-1 to R-38, XR-1, and XR-2. The solid content concentration of the resist composition was adjusted to 3.0 mass%. Solid content refers to all components other than the solvent. The obtained resist compositions were used in the examples and comparative examples. Tables 6 and 7 list the types of solvents used and their mass ratios.

[0494] In Tables 6 and 7, when two or more types of each component are used, the type and content of each are indicated by separating them with " / ". For example, in resist composition R-30, "B-9 / BR-1" indicates that two types of acid diffusion control agents (B), B-9 and BR-1, are used, and "2.3 / 7.6" indicates that the content of B-9 is 2.3 mass% and the content of BR-1 is 7.6 mass%.

[0495] [Table 6]

[0496]

[0497] [Table 7]

[0498]

[0499] For each resist composition, it was investigated whether the above-described condition (i) is satisfied with respect to the cation contained in compound (A) or acid diffusion control agent (B). In the column "Cation contained in (A) or (B)" of Tables 8 and 9 below, the type of cation targeted, DR a / DR b The values ​​of and ClogP were recorded respectively. DR a / DR b and ClogP were calculated using the methods described above, respectively. In addition, DR a and DR b In measuring the film thickness after development, the film thickness was measured using the M-2000D (manufactured by J.A. Uram Japan Co., Ltd.).

[0500] The ratio (mol%) of the content of acid diffusion control agent (B) to the content of compound (A) was indicated in the column "(B) / (A)".

[0501] The ratio (mmol / g) of the acid-generating compound (total amount) upon irradiation with active light or radiation to the total solid content of the resist composition was indicated in the "PAG Total Amount" column.

[0502] The ratio (mol%) of the compound represented by formula (Z-1) to the total amount of compounds that generate acid upon irradiation with active light or radiation was recorded in the column "Ratio of (Z-1) to total amount of PAG".

[0503] [Table 8]

[0504]

[0505] [Table 9]

[0506]

[0507] <Diagram of the Resist Composition>

[0508] The prepared resist composition was applied using a Tokyo Electron spin coater Mark 8 on a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilasein (HMDS), and dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm.

[0509] In addition, the same result is obtained even if the above Si wafer is changed to a chromium substrate.

[0510] (Examples 1-1 to 1-38, Comparative Examples 1-1 to 1-2)

[0511] <Pattern Formation Method (1): EB Exposure, Alkaline Development (Positive)>

[0512] The wafer coated with the resist film obtained above was patterned using an electron beam lithography device (Advantest Inc.; F7000S, acceleration voltage 50 keV). At this time, lithography was performed to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then dried by rinsing with water for 30 seconds. After that, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds, and then dried by baking at 95°C for 60 seconds.

[0513] [evaluation]

[0514] [Seaworthiness]

[0515] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi Seisakusho S-9380II). The exposure amount (electron beam irradiation amount) when resolving a 1:1 line-and-space resist pattern with a line width of 50 nm was set as the sensitivity (Eop).

[0516] The limiting resolution (the minimum line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure amount representing the sensitivity mentioned above was defined as resolution (nm). The smaller this value, the higher the resolution.

[0517] [LWR Performance]

[0518] For a line-and-space pattern with a line width of 50 nm (1:1) resolved with an exposure amount representing the sensitivity (Eop) above, the pattern was observed from the top using a scanning electron microscope (SEM (S-9380II manufactured by Hitachi Seisakusho Inc.). The line width of the pattern was observed at an arbitrary point, and its standard deviation (σ) was calculated. The measurement non-uniformity of the line width was evaluated as 3σ, and the value of 3σ was defined as LWR (nm). The smaller the value of LWR, the better the LWR performance.

[0519] [PED Safety]

[0520] For an exposure amount at which the line width dimension of a 1:1 line and space pattern with a line width of 50 nm and a space width of 50 nm becomes 50 nm, the line width dimension (L0h) when PEB treatment is performed quickly after exposure and the line width dimension (L2h) when PEB treatment is performed 1 hour after exposure were measured, and the line width change rate was calculated by the following formula. In addition, for PEB treatment, heating at 100°C for 60 seconds was performed.

[0521] Linewidth change rate (%) = 100 × (L2h - L0h) nm / 50 nm

[0522] A smaller value indicates better performance and was used as an indicator of PED stability. Furthermore, in practical terms, a value of B or higher is desirable, and A is more desirable.

[0523] A: Linewidth change rate less than 2%

[0524] B: Linewidth change rate is 2% or more and less than 5%

[0525] C: Linewidth change rate is 5% or more and less than 10%

[0526] D: Linewidth change rate of 10% or more

[0527] Tables 10 and 11 below show the resist compositions used and the results.

[0528] [Table 10]

[0529]

[0530] [Table 11]

[0531]

[0532] (Examples 2-1 to 2-38, Comparative Examples 2-1 to 2-2)

[0533] <Pattern Formation Method (2): EUV Exposure, Alkaline Development (Positive)>

[0534] Except for using an EUV exposure device (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) instead of an electron beam lithography device, the same process as the above pattern formation method (1) was performed.

[0535] In the same manner as described above, the resolution, LWR performance, and PED stability were evaluated.

[0536] Tables 12 and 13 below show the resist compositions used and the results.

[0537] [Table 12]

[0538]

[0539] [Table 13]

[0540]

[0541] From the results of Tables 10 to 13, it was found that the resist composition used in the examples had excellent resolution, LWR performance, and PED stability.

[0542] Industrial applicability

[0543] The present invention provides a desensitizing photoreactive or radiation-reducing resin composition having excellent resolution, LWR performance, and PED stability.

[0544] In addition, the present invention may provide a photosensitive or radiation-sensitive film using the photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device.

[0545] Although the present invention has been described in detail with reference to specific embodiments, it is clear to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0546] This application is based on Japanese patent application filed on August 31, 2022 (Japanese patent application 2022-138115) and Japanese patent application filed on August 16, 2023 (Japanese patent application 2023-132614), the contents of which are incorporated herein by reference.

Claims

Claim 1 A photosensitive or radiation-sensitive resin composition comprising at least a resin (P) having repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups, a compound (A) that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation, and an acid diffusion control agent (B), wherein at least one of the compound (A) and the acid diffusion control agent (B) is a compound represented by the following formula (Z-2), and the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A). [Chemical Formula 1] In equation (Z-2), R Z1 , R Z2 and R Z3 Each represents an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, an acylamino group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or an arylsulfonyl group. n1 represents an integer from 1 to 5. n2 and n3 each represent an integer from 0 to 5. R Z1 , R Z2 and R Z3 In cases where each exists in multiple instances, multiple R Z1 , R Z2 and R Z3 They may be identical or different. R Z1 , R Z2 and R Z3 At least two of them may be joined to each other by single bonds or via linkers. Also, the benzene rings in formula (Z-2) may be joined to each other by single bonds or via linkers. X - represents an anion. However, the sulfonium cation in formula (Z-2) satisfies the following condition (i). Condition (i): A salt consisting of the sulfonium cation in formula (Z-2) and the anion represented by the following formula (a1) is designated as salt (a), and a salt consisting of the cation represented by the following formula (b1) and the anion represented by the following formula (a1) is designated as salt (b). Using salt (a) and salt (b) respectively, a solution having a solid content concentration of 2.7 mass% is prepared, comprising each salt, the resin (P), and a solvent containing propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethyl lactate in a mass ratio of 20 / 20 / 60, such that the "moles of added salt / (total mass of the resin (P) and the added salt)" is 0.4 mmol / g. The dissolution rate of the film obtained by applying the above solution with respect to an alkaline developer, which is a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, is measured. The dissolution rate of the film formed by adding salt (a) with respect to the alkaline developer is DR a Let , and the dissolution rate of the membrane formed by adding salt (b) with respect to the alkaline developer is DR b In the case of , DR a and DR b satisfies the following equation (i-1).DR a / DR b ≤0.5… (i-1)[Chemical Formula 2] Claim 2 A light-sensitive or radiation-sensitive resin composition according to claim 1, wherein the total amount of a compound that generates acid upon irradiation with active light or radiation is 0.3 mmol / g or more relative to the total solid content. Claim 3 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the acid diffusion control agent (B) is a compound that generates an acid with a pKa of 0 or higher upon irradiation with active light or radiation. Claim 4 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the acid diffusion control agent (B) is a compound represented by formula (Z-2). Claim 5 The desensitizing photoreactive or radiation-reducing resin composition of claim 1, wherein the acid diffusion control agent (B) comprises an anion represented by the following formula (xa1). [Chemical Formula 3] In equation (xa1), Ar a1 represents a direction ring. R a1 represents a substituent. k1 represents an integer from 0 to 7. If k1 is 2 or greater, multiple R a1 They may be identical or different. If k1 is 2 or greater, multiple R a1 Silver may combine with each other to form rings. Claim 6 A desensitizing photoreactive or radiation-reducing resin composition according to claim 1, wherein the pKa of the acid generated from the compound (A) is -1.5 or higher. Claim 7 The photosensitive or radiation-sensitive resin composition of claim 1, wherein the compound (A) comprises an anion represented by the following formula (ca1). [Chemical Formula 4] In formula (ca1), Ar a2 represents a direction ring. R a2 represents a substituent. k2 represents an integer from 0 to 7. If k2 is 2 or greater, multiple R a2 They may be identical or different. If k2 is 2 or greater, multiple R a2 They may combine with each other to form a ring. Claim 8 A light-sensitive or radiation-sensitive resin composition according to claim 1, wherein the ratio of the compound represented by formula (Z-2) to the total amount of compounds that generate acid upon irradiation with active light or radiation is 50 mol% or more. Claim 9 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (P) comprises repeating units represented by the following formula (Pa1). [Chemical Formula 5] In equation (Pa1), R P1 R represents a hydrogen atom or an alkyl group. P2 represents the energy that is dehydrated by the action of acid. Claim 10 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (P) comprises repeating units represented by the following formula (Pa2). [Chemical Formula 6] In equation (Pa2), R P3 R represents a hydrogen atom or an alkyl group. P4 represents the energy that is dehydrated by the action of acid. Claim 11 delete Claim 12 In claim 1, the DR a and the above DR b A photosensitive or radiation-sensitive resin composition satisfying the following formula (i-2).DR a / DR b ≤0.10… (i-2) Claim 13 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the ClogP of the sulfonium cation in formula (Z-2) is 3 or more and 8 or less. Claim 14 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the ratio of the compound represented by formula (Z-2) to the total amount of compounds that generate acid upon irradiation with active light or radiation is 100 mol%. Claim 15 A photosensitive or radiation-sensitive film formed by a photosensitive or radiation-sensitive resin composition as described in any one of claims 1 to 10 and claims 12 to 14. Claim 16 A pattern forming method comprising: a process of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 10 and claims 12 to 14; a process of exposing the photosensitive or radiation-sensitive film to light; and a process of developing the exposed photosensitive or radiation-sensitive film using a developer. Claim 17 A method for manufacturing an electronic device comprising the pattern forming method described in claim 16. Claim 18 A photosensitive or radiation-sensitive resin composition comprising a resin (P) having repeating units having phenolic hydroxyl groups and repeating units having acid-degradable groups, a compound (A) that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation, and an acid diffusion control agent (B), wherein the resin (P) comprises repeating units represented by the following formula (Pa2), at least one of the compound (A) and the acid diffusion control agent (B) is a compound represented by the following formula (Z-2), and the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A). [Chemical Formula 8] In equation (Pa2), R P3 R represents a hydrogen atom or an alkyl group. P4 represents the group that is detached by the action of acid.[Chemical Formula 9] In equation (Z-2), R Z1 , R Z2 and R Z3 Each represents an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, an acylamino group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or an arylsulfonyl group. n1 represents an integer from 1 to 5. n2 and n3 each represent an integer from 0 to 5. R Z1 If this plural exists, the plural R Z1 They may be identical or different from each other, and may combine to form a ring. R Z2 If there are multiple instances of , multiple R Z2 They may be identical or different from each other, and may combine to form a ring. R Z3 If this plural exists, the plural R Z3 They may be identical or different, and may be combined with each other. Also, the benzene rings in formula (Z-2) may be connected to each other by single bonds or through linkers. X - represents the anion represented by the following formula (xa1). [Chemical Formula 10] In equation (xa1), Ar a1 represents a direction ring. R a1 represents a substituent. k1 represents an integer from 0 to 7. If k1 is 2 or greater, multiple R a1 They may be identical or different. If k1 is 2 or greater, multiple R a1 Silver may combine with each other to form rings.

Images