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

Abstract

The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition capable of forming an actinic ray-sensitive or radiation-sensitive film that suppresses sensitivity reduction and exhibits excellent adhesion to a substrate (particularly adhesion in a dry state), as well as an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a resin whose polarity increases due to the action of an acid, (B) a photoacid generator, (P) an amine oxide, and (D) an acid diffusion controller (excluding an acid diffusion controller corresponding to the amine oxide), wherein the content of the amine oxide (P) is from 0.01 ppm to 1000 ppm relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, and the mass ratio of the acid diffusion controller (D) to the amine oxide (P) is greater than 1 and is from 10,000 to 10,000.

Description

Technical Field

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

[0002] To compensate for the reduced sensitivity caused by light absorption after using a KrF excimer laser (248nm) resist, a patterning method using chemical amplification is used. For example, in the positive chemical amplification method, the photoacid generator contained in the exposed area is first decomposed by light irradiation to generate acid. Then, during a post-exposure bake (PEB) process, the generated acid catalyzes the conversion of alkali-insoluble groups in the photosensitive composition into alkali-soluble groups. Development is then performed using, for example, an alkaline solution. This removes the exposed area, resulting in the desired pattern.

[0003] In the above-mentioned method, various alkaline developers have been proposed. For example, an aqueous alkaline developer containing 2.38% by mass of TMAH (tetramethylammonium hydroxide aqueous solution) is generally used as the alkaline developer.

[0004] To further miniaturize semiconductor devices, the wavelength of exposure light sources has been shortened, and the numerical aperture (NA) of projection lenses has been increased. Currently, exposure systems using ArF excimer lasers with a wavelength of 193 nm as light sources are being developed. One technique for further improving resolution is to fill the space between the projection lens and the sample with a high-refractive-index liquid (hereinafter referred to as "immersion liquid") (i.e., the immersion method).

[0005] Various resist compositions are known. For example, Patent Document 1 describes a resist material characterized by containing one or two or more compounds having an amine oxide structure as a basic component.

[0006] Patent Document 2 describes a photoresist composition containing a polymer having a structural unit including an acid-dissociable group that dissociates by the action of an acid, a radiation-sensitive acid generator, and a solvent.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-102383

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2015-57638 Summary of the Invention

[0011] Technical issues to be solved by the invention

[0012] Development of three-dimensional memory devices that achieve higher memory capacity by stacking cells is underway. As the number of stacked layers increases, thicker resist films must be formed, patterned, and then etched.

[0013] As the resist film thickness increases, the resist film peels off from the substrate more noticeably during the processing step. Furthermore, as the film thickness increases, the light absorption of the resist film affects the exposure wavelength more significantly, resulting in a problem of decreased sensitivity.

[0014] In the process before forming the resist pattern and in the subsequent process, the resist film formed on the substrate (here, also including the resist pattern formed by exposure and development) is usually placed in a dry state (for example, a process placed in a vacuum state). In addition, the present inventors have conducted research this time and found that the adhesion between the resist film and the substrate is sometimes reduced due to the various processes before and after the formation of the resist pattern. This phenomenon is more significantly produced when the resist film is placed in a dry state. In view of the above-mentioned phenomenon about the adhesion between the resist film and the substrate, it is conceivable to change the composition of the resist composition to a composition that can improve the original adhesion, etc., but it is not easy to improve the adhesion between the resist film and the substrate without compromising basic performance such as sensitivity.

[0015] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming an actinic ray-sensitive or radiation-sensitive film having excellent adhesion to a substrate (particularly adhesion in a dry state) while suppressing a decrease in sensitivity.

[0016] Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0017] Means for solving technical problems

[0018] Methods for solving the above-mentioned problems include the following. [1]

[0020] An actinic ray-sensitive or radiation-sensitive resin composition comprising:

[0021] (A) Resins whose polarity is increased by the action of an acid;

[0022] (B) photoacid generator;

[0023] (P) amine oxides; and

[0024] (D) Acid diffusion control agents (except those corresponding to amine oxides),

[0025] The content of the amine oxide (P) is 0.01 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0026] The mass ratio of the acid diffusion controller (D) represented by the following formula to the amine oxide (P) is greater than 1 and 10,000 or less.

[0027] Mass ratio=(content of acid diffusion controller (D)) / (content of amine oxide (P)). [2]

[0029] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the amine oxide (P) is a compound represented by the following general formula (1).

[0030] [Chemical Formula 1]

[0031]

[0032] (In the formula, R1, R2, and R3 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group, and any two of R1, R2, and R3 may be bonded to form a ring structure.) [3]

[0034] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the amine oxide is a compound represented by the following general formula (2).

[0035] [Chemical Formula 2]

[0036]

[0037] In the formula, R4, R5, and R6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group, and L1, L2, and L3 are each independently a divalent linking group. [4]

[0039] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the amine oxide is a compound represented by the following general formula (3).

[0040] [Chemical Formula 3]

[0041]

[0042] In the formula, R7, R8, and R9 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group, and L4, L5, and L6 are each independently a divalent linking group. [5]

[0044] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the amine oxide is a compound represented by the following general formula (4).

[0045] [Chemical Formula 4]

[0046]

[0047] Where R 10 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or a carboxyl group, and n represents an integer from 0 to 5. When n represents an integer greater than 2, multiple R 10 It can be the same or different. [6]

[0049] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the amine oxide is a compound represented by the following general formula (5).

[0050] [Chemical Formula 5]

[0051]

[0052] Where R 1A 、R 2A 、R 3A are each independently an organic group having a heteroatom at the terminal or in the chain and having 6 or less carbon atoms, and R 1A 、R 2A 、R 3A Any two of them may be bonded to form a ring structure. [7]

[0054] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the amine oxide is a compound represented by the following general formula (6).

[0055] [Chemical Formula 6]

[0056]

[0057] (Where R 1B 、R 2B 、R 3B Each independently represents an organic group (except for an unsubstituted alkyl group having 6 or more carbon atoms). 1B 、R 2B 、R 3B Any two of them can be bonded to form a ring structure.) [8]

[0059] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the content of the amine oxide is 0.01 ppm to 100 ppm based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [9]

[0061] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the content of the amine oxide is 0.01 ppm to 10 ppm based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[10]

[0063] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the composition has a solid content concentration of 10% by mass or more.

[11]

[0065] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , wherein the acid diffusion controller (D) is an amine compound, and the amine oxide (P) is an amine oxide formed by oxidizing the nitrogen atom of the amine portion of the acid diffusion controller (D).

[12]

[0067] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , further comprising (H) a surfactant.

[13]

[0069] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[12] .

[14]

[0071] A pattern forming method comprising the steps of: exposing the actinic ray-sensitive or radiation-sensitive film described in

[13] ; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

[15]

[0073] A method for manufacturing an electronic device, comprising the pattern forming method described in

[14] .

[0074] Effects of the Invention

[0075] According to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive resin composition capable of forming an actinic ray-sensitive or radiation-sensitive film having excellent adhesion to a substrate (particularly adhesion in a dry state) while suppressing a decrease in sensitivity.

[0076] According to the present invention, there can also be provided an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION

[0077] Hereinafter, the contents of the present invention will be described in detail.

[0078] The constituent elements described below will be described based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0079] In the notation of groups (atomic groups) in this specification, the notation that does not specify whether it is substituted or unsubstituted includes not only groups without substituents but also groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0080] In this specification, when the phrase "may have a substituent" is used, the type, position, and number of substituents are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of substituents include monovalent non-metallic atomic groups other than hydrogen atoms, such as the following substituents T.

[0081] (Substituent T)

[0082] Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxyvaleryl; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamido groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; nitro groups; and combinations thereof.

[0083] "Actinic rays" or "radiation" as used herein include, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). Unless otherwise specified, "light" as used herein refers to actinic rays or radiation.

[0084] Unless otherwise specified, the term "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), and X-rays, but also exposure using particle beams such as electron beams and ion beams.

[0085] In this specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

[0086] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0087] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of the resin component are defined as polystyrene-equivalent values obtained by GPC measurement using a Gel Permeation Chromatography apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0088] In this specification, when a plurality of substances corresponding to each component are present in a composition, the amount of each component in the composition refers to the total amount of the corresponding plurality of substances present in the composition, unless otherwise specified.

[0089] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0090] In this specification, "total solids" refers to the total mass of the components obtained by removing the solvent from all the components of the composition. As described above, "solids" refers to the components obtained by removing the solvent and may be solid or liquid at 25°C, for example.

[0091] In this specification, "mass %" and "weight %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0092] Furthermore, in this specification, a more preferred embodiment is a combination of two or more preferred embodiments.

[0093] [Actinic ray or radiation-sensitive resin composition]

[0094] The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to simply as "composition") according to the present invention contains:

[0095] An actinic ray-sensitive or radiation-sensitive resin composition comprising:

[0096] (A) Resins whose polarity is increased by the action of an acid;

[0097] (B) photoacid generator;

[0098] (P) amine oxides; and

[0099] (D) Acid diffusion control agents (except those corresponding to amine oxides),

[0100] The content of the amine oxide (P) is 0.01 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0101] The mass ratio of the acid diffusion controller (D) represented by the following formula to the amine oxide (P) is greater than 1 and 10,000 or less.

[0102] Mass ratio=(content of acid diffusion controller (D)) / (content of amine oxide (P)).

[0103] The present invention, by virtue of the above-described structure, can achieve excellent adhesion to the substrate (particularly adhesion in a dry state) while suppressing a decrease in sensitivity.

[0104] The reason for this is not clear, but is speculated as follows.

[0105] First, the present inventors discovered that, by including an amine oxide in an actinic or radiation-sensitive resin composition at a level of 0.01 ppm or more relative to the total mass of the actinic or radiation-sensitive resin composition, as described above, excellent adhesion to a substrate is achieved, particularly in a dry state. While the exact reason for this is unclear, it is presumed that the amine oxide contained in the composition interacts with highly polar groups (e.g., ester groups) in a resin that may be included in the actinic or radiation-sensitive resin composition and highly polar groups (e.g., hydroxyl groups) that may be included in the substrate, thereby improving adhesion between the actinic or radiation-sensitive film and the substrate.

[0106] Furthermore, it is considered that by containing 1000 ppm or less of the amine oxide relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, the light transmittance of the actinic ray-sensitive or radiation-sensitive film during exposure is sufficiently ensured, thereby suppressing a decrease in sensitivity.

[0107] Furthermore, it is believed that the inclusion of an acid diffusion controller (excluding those corresponding to amine oxides) in an actinic ray- or radiation-sensitive resin composition can suppress the excessive diffusion of acid generated in the exposed areas of the actinic ray- or radiation-sensitive film to the unexposed areas. This is believed to suppress sensitivity reduction and enable more reliable formation of a resist pattern of a desired shape.

[0108] Moreover, by setting the mass ratio of the above-mentioned acid diffusion controller (excluding the one corresponding to amine oxide) to the above-mentioned amine oxide (specifically, (acid diffusion controller (excluding the one corresponding to amine oxide) / (content of amine oxide)) to be greater than 1 and less than 10,000, the expression of the photosensitive ray or radiation-sensitive film and the adhesion to the substrate caused by the amine oxide and the suppression of the reduction in sensitivity can be ensured in a balanced manner. It is presumed that the reduction in sensitivity is suppressed and the adhesion between the photosensitive ray or radiation-sensitive film and the substrate is improved.

[0109] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a so-called resist composition, and may be a positive resist composition or a negative resist composition, and may be a resist composition for alkaline development or a resist composition for organic solvent development.

[0110] The composition of the present invention is typically preferably a chemically amplified resist composition.

[0111] Hereinafter, each component contained in the actinic ray-sensitive or radiation-sensitive resin composition (also simply referred to as “composition”) according to the present invention will be described in detail.

[0112] <Amine oxide (P)>

[0113] The composition of the present invention contains an amine oxide (hereinafter also referred to as "amine oxide (P)").

[0114] Amine oxide (P) is not particularly limited and is a + -O - In addition, N + -O - The structure represented has the same meaning as the structure represented by N→O.

[0115] The amine oxide (P) is preferably a compound represented by the following general formula (1).

[0116] [Chemical Formula 7]

[0117]

[0118] In the formula, R1, R2, and R3 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group.

[0119] Furthermore, any two of R1, R2, and R3 may be bonded to form a ring structure.

[0120] The alkyl group is not particularly limited and may be linear or branched. Preferred examples include alkyl groups having 1 to 20 carbon atoms.

[0121] The alkyl group may have a substituent.

[0122] The alkyl group having a substituent is not particularly limited, and examples thereof include hydroxyalkyl groups (preferably having 2 to 10 carbon atoms), alkoxyalkyl groups (preferably having 2 to 10 carbon atoms), cycloalkoxyalkyl groups (preferably having 4 to 10 carbon atoms), acyloxyalkyl groups (preferably having 2 to 10 carbon atoms), alkylthioalkyl groups (preferably having 2 to 10 carbon atoms), cycloalkylthioalkyl groups (preferably having 4 to 10 carbon atoms), and cyanoalkyl groups (preferably having 2 to 10 carbon atoms).

[0123] Specific examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0124] Specific examples of the alkoxyalkyl group include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, isobutoxymethyl, tert-butoxymethyl, tert-amyloxymethyl, and methoxyethyl.

[0125] Specific examples of the cycloalkoxyalkyl group include cyclohexyloxymethyl and cyclopentyloxymethyl.

[0126] Specific examples of the acyloxyalkyl group include formyloxymethyl, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pivaloyloxymethyl, cyclohexanecarbonyloxymethyl, decanoyloxymethyl, and undecanoyloxyethyl.

[0127] Specific examples of the alkylthioalkyl group include methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, butylthiomethyl, isobutylthiomethyl, tert-butylthiomethyl, tert-pentylthiomethyl, and decylthiomethyl.

[0128] Specific examples of the cycloalkylthioalkyl group include cyclohexylthiomethyl group.

[0129] The cycloalkyl group may be monocyclic or polycyclic and is not particularly limited, but preferably has a carbon number of 3 to 20. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0130] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0131] The aryl group is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, naphthacenyl, and fluorenyl.

[0132] The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0133] The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 20 carbon atoms, and specific examples thereof include vinyl, allyl, butenyl, and pentenyl.

[0134] The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0135] The aralkyl group is not particularly limited, but is preferably an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and anthracenmethyl.

[0136] The aralkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0137] Furthermore, any two of R1, R2, and R3 may be bonded to form a ring structure, and the ring structure thus formed may contain a heteroatom such as an oxygen atom.

[0138] Furthermore, the amine oxide (P) is preferably a compound represented by the following general formula (2).

[0139] [Chemical Formula 8]

[0140]

[0141] In the formula, R4, R5, and R6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group. L1, L2, and L3 are each independently a divalent linking group.

[0142] The alkyl groups represented by R4, R5 and R6 are the same as those described above as R1, R2 and R3.

[0143] The cycloalkyl groups as R4, R5 and R6 are the same as the cycloalkyl groups described above as R1, R2 and R3.

[0144] The aryl groups as R4, R5, and R6 are the same as the aryl groups described above as R1, R2, and R3.

[0145] The alkenyl groups of R4, R5 and R6 are the same as the alkenyl groups described above as R1, R2 and R3.

[0146] The aralkyl groups as R4, R5 and R6 are the same as the aralkyl groups described above as R1, R2 and R3.

[0147] The divalent linking group represented by L1, L2, and L3 is not particularly limited, but is preferably an alkylene group (preferably having 1 to 10 carbon atoms).

[0148] L1, L2, and L3 may further have a substituent.

[0149] Furthermore, the amine oxide (P) is preferably a compound represented by the following general formula (3).

[0150] [Chemical Formula 9]

[0151]

[0152] In the formula, R7, R8, and R9 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group. L4, L5, and L6 are each independently a divalent linking group.

[0153] The alkyl groups represented by R7, R8 and R9 are the same as those described above as R1, R2 and R3.

[0154] The cycloalkyl groups for R7, R8 and R9 are the same as those described above for R1, R2 and R3.

[0155] The aryl groups for R7, R8, and R9 are the same as the aryl groups described above for R1, R2, and R3.

[0156] The alkenyl groups for R7, R8, and R9 are the same as the alkenyl groups described above for R1, R2, and R3.

[0157] The aralkyl groups for R7, R8 and R9 are the same as those described above for R1, R2 and R3.

[0158] The divalent linking group represented by L4, L5, and L6 is not particularly limited, but is preferably an alkylene group (preferably having 1 to 10 carbon atoms).

[0159] L4, L5, and L6 may further have a substituent.

[0160] Furthermore, the amine oxide (P) is preferably a compound represented by the following general formula (4).

[0161] [Chemical Formula 10]

[0162]

[0163] Where R 10 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or a carboxyl group. n represents an integer from 0 to 5. When n represents an integer greater than 2, multiple R10 It can be the same or different.

[0164] As R 10 The alkyl group is the same as the alkyl group described above as R1, R2, and R3.

[0165] As R 10 The cycloalkyl group is the same as the cycloalkyl group described above as R1, R2, and R3.

[0166] As R 10 The aryl group is the same as the aryl group described above as R1, R2, and R3.

[0167] As R 10 The alkenyl group is the same as the alkenyl group described above as R1, R2, and R3.

[0168] R 10 Preferred are hydrogen atom, alkyl group or carboxyl group.

[0169] n is preferably 0-4, more preferably 0-2.

[0170] Furthermore, the amine oxide (P) is preferably a compound represented by the following general formula (5).

[0171] [Chemical Formula 11]

[0172]

[0173] Where R 1A 、R 2A 、R 3A are each independently an organic group having a heteroatom at the terminal or in the chain and having 6 or less carbon atoms. 1A 、R 2A 、R 3A Any two of them may be bonded to form a ring structure.

[0174] The organic group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an alkenyl group.

[0175] The alkyl group is not particularly limited and may be linear or branched. Preferred examples include alkyl groups having 1 to 6 carbon atoms.

[0176] The alkyl group may have a substituent, but the number of carbon atoms as an organic group is 6 or less.

[0177] The cycloalkyl group is a monocyclic ring and is not particularly limited, but preferably has a carbon number of 3 to 6. Specific examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

[0178] The cycloalkyl group may have a substituent, but the number of carbon atoms in the organic group is 6 or less.

[0179] The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 6 carbon atoms, and specific examples thereof include vinyl and allyl groups.

[0180] The alkenyl group may have a substituent, but the number of carbon atoms as an organic group is 6 or less.

[0181] And, R 1A 、R 2A 、R 3A Any two of them may be bonded to form a ring structure, and the ring structure formed may contain a heteroatom such as an oxygen atom.

[0182] Furthermore, the amine oxide (P) is preferably a compound represented by the following general formula (6).

[0183] [Chemical Formula 12]

[0184]

[0185] Where R 1B 、R 2B 、R 3B Each independently represents an organic group (except for an unsubstituted alkyl group having 6 or more carbon atoms). 1B 、R 2B 、R 3B Any two of them may be bonded to form a ring structure.

[0186] The organic group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an aralkyl group.

[0187] The alkyl group is not particularly limited and may be linear or branched. Preferred examples include alkyl groups having 1 to 20 carbon atoms.

[0188] The alkyl group may have a substituent.

[0189] The alkyl group having a substituent is not particularly limited, and examples thereof include hydroxyalkyl groups (preferably having 2 to 10 carbon atoms), alkoxyalkyl groups (preferably having 2 to 10 carbon atoms), cycloalkoxyalkyl groups (preferably having 4 to 10 carbon atoms), acyloxyalkyl groups (preferably having 2 to 10 carbon atoms), alkylthioalkyl groups (preferably having 2 to 10 carbon atoms), cycloalkylthioalkyl groups (preferably having 4 to 10 carbon atoms), and cyanoalkyl groups (preferably having 2 to 10 carbon atoms).

[0190] In addition, the alkyl group is not an unsubstituted alkyl group having 6 or more carbon atoms.

[0191] The cycloalkyl group may be monocyclic or polycyclic and is not particularly limited, but preferably has a carbon number of 3 to 20. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0192] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0193] The aryl group is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, naphthacenyl, and fluorenyl.

[0194] The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0195] The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 20 carbon atoms, and specific examples thereof include vinyl, allyl, butenyl, and pentenyl.

[0196] The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0197] The aralkyl group is not particularly limited, but is preferably an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and anthracenmethyl.

[0198] The aralkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0199] And, R 1B 、R 2B 、R 3B Any two of them may be bonded to form a ring structure, and the ring structure formed may contain a heteroatom such as an oxygen atom.

[0200] The acid diffusion controller (D) described below is an amine compound, and the amine oxide (P) is preferably an amine oxide obtained by oxidizing the nitrogen atom in the amine portion of the acid diffusion controller (D) described below.

[0201] For example, specifically, there can be mentioned an embodiment in which the acid diffusion controller is the compound (D-4) described later, and the amine oxide (P) is the compound (AE-4) described later.

[0202] Specific examples of the amine oxide (P) are given below, but the present invention is not limited to these specific examples.

[0203] [Chemical Formula 13]

[0204]

[0205] [Chemical Formula 14]

[0206]

[0207] [Chemical Formula 15]

[0208]

[0209] The above-mentioned amine oxides (P) may be used alone or in combination of two or more.

[0210] The compound represented by the general formula (1), the compound represented by the general formula (2), the compound represented by the general formula (3), the compound represented by the general formula (4), the compound represented by the general formula (5), and the compound represented by the general formula (6) may be used in combination of two or more.

[0211] The content of the amine oxide (P) (the total amount when a plurality of amine oxides (P) are present) is 0.01 ppm to 1000 ppm based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0212] By setting the content of the amine oxide (P) (the total amount when a plurality of amine oxides (P) are present) to 0.01 ppm or more and 1000 ppm or less, excellent adhesion between the actinic ray-sensitive or radiation-sensitive film and the substrate can be obtained while suppressing sensitivity reduction.

[0213] When the amine oxide (P) content (the total amount when multiple amine oxides (P) are present) is 0.01 ppm or more, the actinic ray sensitivity or the adhesion between the radiation-sensitive film and the substrate is more effectively ensured. Furthermore, when the amine oxide (P) content (the total amount when multiple amine oxides (P) are present) is 1000 ppm or less, sensitivity reduction is more effectively suppressed.

[0214] The content of the amine oxide (P) relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition (the total amount when a plurality of amine oxides (P) are present) is preferably from 0.01 ppm to 100 ppm, more preferably from 0.01 ppm to 10 ppm, and even more preferably from 0.01 ppm to 5 ppm.

[0215] Furthermore, the mass ratio of the acid diffusion controller (D) represented by the following formula to the amine oxide (P) is greater than 1 and 10,000 or less, preferably 5 to 5,000, and more preferably 10 to 1,000.

[0216] Mass ratio=(content of acid diffusion controller (D)) / (content of amine oxide (P)).

[0217] By setting the mass ratio to be greater than 1 and not greater than 10,000, it is possible to obtain excellent adhesion between the actinic ray-sensitive or radiation-sensitive film and the substrate while suppressing a decrease in sensitivity.

[0218] When the mass ratio is 1 or less or greater than 10,000, it is not possible to suppress a decrease in sensitivity, and it is difficult to ensure the actinic ray sensitivity or the adhesion between the radiation-sensitive film and the substrate.

[0219] The method of adding a trace amount of the amine oxide (P) is not particularly limited, and examples thereof include the following methods.

[0220] By using the solvent used in the preparation of the resist composition to prepare a diluted solution of amine oxide (P) in advance, it is possible to accurately measure a trace amount of amine oxide (P). In particular, when the amount of amine oxide (P) added is at a very low level, it is possible to prepare a solution that has been diluted multiple times according to the content of amine oxide (P) to adjust the amount of amine oxide (P) present in the resist composition to the desired amount.

[0221] The content of the amine oxide (P) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be measured by, for example, the following method.

[0222] (Quantitative Method for Amine Oxide (P))

[0223] A resist composition containing amine oxide (P) was prepared and irradiated with ultrasonic waves for 3 minutes using an ultrasonic device (desktop ultrasonic cleaner (#5510), manufactured by Bransonic). The resulting solution was analyzed using a liquid chromatography apparatus (Agilent 1100HPLC G1311A, manufactured by Agilent Technologies, Inc.) using a reverse phase column (Shim-pack CLC-ODS (M), manufactured by SHIMADZU GLC Ltd.) and a UV detector (Agilent 1100HPLC G1315B, manufactured by Agilent Technologies, Inc.). The content of amine oxide (P) was quantified by an absolute calibration curve method using a standard reagent for amine oxide (P).

[0224] The standard reagent is an amine oxide (P) to be quantified, the concentration of which is known.

[0225] The method for producing the amine oxide (P) is not particularly limited, and the amine oxide (P) can be produced by selecting an optimal method according to the structure of the compound. For example, an oxidation reaction using an oxidizing agent containing a nitrogen compound can be exemplified, but the method is not limited thereto.

[0226] <(A) Resin whose polarity is increased by the action of an acid>

[0227] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin whose polarity increases due to the action of an acid (hereinafter also referred to as "resin (A)"). Typically, the resin (A) is preferably a resin whose polarity increases due to the action of an acid, thereby changing its solubility in a developer.

[0228] The resin (resin (A)) whose polarity is increased by the action of an acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound.

[0229] The ethylenically unsaturated compound preferably has 1 to 4 ethylenically unsaturated bonds, more preferably 1. Furthermore, the ethylenically unsaturated compound is preferably a monomer of monomers.

[0230] The molecular weight of the ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, and particularly preferably 100 to 600.

[0231] Furthermore, the resin whose polarity increases due to the action of an acid preferably has an acid-decomposable group, and more preferably contains a structural unit having an acid-decomposable group.

[0232] In this case, in the pattern forming method according to the present invention described below, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0233] [Structural unit having an acid-decomposable group]

[0234] The resin (A) preferably contains a structural unit (also referred to as a "repeating unit") having an acid-decomposable group.

[0235] As resin (A), a known resin can be used as appropriate. For example, the known resins disclosed in paragraphs 0055 to 0191 of U.S. Patent Application Publication No. 2016 / 0274458, paragraphs 0035 to 0085 of U.S. Patent Application Publication No. 2015 / 0004544, and paragraphs 0045 to 0090 of U.S. Patent Application Publication No. 2016 / 0147150 can be preferably used as resin (A).

[0236] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and released by the action of an acid.

[0237] Examples of the polar group include acidic groups (groups that dissociate in a 2.38% by mass tetramethylammonium hydroxide aqueous solution) such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tri(alkylcarbonyl)methylene group, and a tri(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.

[0238] In addition, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), and as a hydroxyl group, an aliphatic alcohol group (for example, a hexafluoroisopropanol group) whose α position is substituted with an electron-withdrawing group such as a fluorine atom is excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferably used.

[0239] Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group.

[0240] Preferred acid-decomposable groups are groups in which a hydrogen atom in these groups is replaced by a group that is detached by the action of an acid (leaving group).

[0241] Examples of the group that is released by the action of an acid (releasing group) include -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 ) and -C(R 01 )(R 02 )(OR 39 )wait.

[0242] Where R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0243] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0244] R 36 ~R 39 、R 01 and R 02 The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and octyl.

[0245] R 36 ~R 39 、R 01 and R 02 The cycloalkyl group may be monocyclic or polycyclic. As a monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferred, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As a polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl, norbornyl, isobornyl, bornyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl, and androstanyl. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

[0246] R 36 ~R 39 、R 01 and R 02 The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0247] R 36 ~R 39 、R 01 and R 02 The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl.

[0248] R 36 ~R 39 、R 01 and R 02 The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl.

[0249] As R 36 With R 37 The ring formed by mutually bonding is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl are preferred.

[0250] The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.

[0251] The resin (A) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.

[0252] [Chemical Formula 16]

[0253]

[0254] In AI, Xa1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group, T represents a single bond or a divalent linking group, Rx 1 ~Rx 3 Each independently represents an alkyl group or a cycloalkyl group, Rx 1 ~Rx 3 Any two of them may be bonded to form a ring structure, or may not form a ring structure.

[0255] Examples of divalent linking groups for T include alkylene, arylene, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene, cycloalkylene, or arylene group, and T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably -CH2-, -(CH2)2-, or -(CH2)3-. T is more preferably a single bond.

[0256] XA 1 A hydrogen atom or an alkyl group is preferred.

[0257] XA 1 The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom other than a fluorine atom.

[0258] XA 1 The alkyl group in Xa preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, and hydroxymethyl. 1 The alkyl group is preferably a methyl group.

[0259] As Rx 1 、Rx 2 and Rx 3 The alkyl group may be linear or branched, and preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1 、Rx 2 and Rx 3 A portion of the carbon-carbon bonds in the alkyl group may be a double bond.

[0260] As Rx 1 、Rx 2 and Rx 3 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0261] As Rx 1 、Rx 2 and Rx 3The ring structure formed by bonding two of the rings is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring and a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring and an adamantane ring. More preferably, it is a cyclopentyl ring, a cyclohexyl ring or an adamantane ring. 1 、Rx 2 and Rx 3 The ring structure formed by two of them being bonded together is also preferably the structure shown below.

[0262] [Chemical Formula 17]

[0263]

[0264] Specific examples of monomers corresponding to the structural unit represented by formula AI are given below, but the present invention is not limited to these specific examples. 1 In the case of methyl, but Xa 1 It may be arbitrarily substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0265] [Chemical Formula 18]

[0266]

[0267] The resin (A) also preferably has the structural units described in paragraphs 0336 to 0369 of US Patent Application Publication No. 2016 / 0070167 as the structural units having an acid-decomposable group.

[0268] Furthermore, the resin (A) may have, as a structural unit having an acid-decomposable group, a structural unit containing a group that decomposes to generate an alcoholic hydroxyl group as described in paragraphs 0363 and 0364 of US Patent Application Publication No. 2016 / 0070167.

[0269] Furthermore, the resin (A) preferably has, as a repeating unit having an acid-decomposable group, a structure in which a phenolic hydroxyl group is protected by a leaving group that decomposes and releases the phenolic hydroxyl group by the action of an acid (acid-decomposable group). In this specification, a phenolic hydroxyl group is a group formed by replacing a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

[0270] Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulae (Y1) to (Y4).

[0271] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0272] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0273] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0274] Formula (Y4): -C(Rn)(H)(Ar)

[0275] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), preferably, at least two of Rx1 to Rx3 are methyl groups.

[0276] Among them, a repeating unit in which Rx1 to Rx3 each independently represent a linear or branched alkyl group is more preferred, and a repeating unit in which Rx1 to Rx3 each independently represent a linear alkyl group is even more preferred.

[0277] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring.

[0278] The alkyl group represented by Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

[0279] The cycloalkyl group represented by Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecyl and adamantyl.

[0280] The cycloalkyl group formed by bonding two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0281] In the cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0282] The group represented by formula (Y1) or formula (Y2) is preferably a mode in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0283] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 With R 38Examples of the monovalent organic group include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. 36 Preferred is a hydrogen atom.

[0284] In formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0285] The repeating unit having a structure in which the phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group) is preferably a repeating unit having a structure in which the hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulae (Y1) to (Y4).

[0286] The repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group) is preferably a repeating unit represented by the following general formula (AII).

[0287] [Chemical Formula 19]

[0288]

[0289] In the general formula (AII),

[0290] R 61 、R 62 and R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 62 It can bond with Ar6 to form a ring. In this case, R 62 represents a single bond or an alkylene group.

[0291] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0292] L6 represents a single bond or an alkylene group.

[0293] Ar6 represents an (n+1) valent aromatic hydrocarbon group, when it is combined with R 62 When they are bonded to form a ring, they represent an aromatic hydrocarbon group with a valence of (n+2).

[0294] When n ≥ 2, Y2 each independently represents a hydrogen atom or a group that is dissociated by the action of an acid. At least one of Y2 represents a group that is dissociated by the action of an acid. The group that is dissociated by the action of an acid as Y2 is preferably a group of formula (Y1) to (Y4).

[0295] n represents an integer of 1 to 4.

[0296] Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). Preferably, the substituent has 8 or less carbon atoms.

[0297] Specific examples of the repeating unit represented by the general formula (AII) are given below, but the present invention is not limited to these specific examples.

[0298] [Chemical Formula 20]

[0299]

[0300] [Chemical Formula 21]

[0301]

[0302] The resin (A) may contain one type of structural unit having an acid-decomposable group alone, or may contain two or more types of such structural units.

[0303] The content of the structural unit having an acid-decomposable group contained in the resin (A) (the total amount when a plurality of structural units having an acid-decomposable group are present) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and even more preferably 15 mol% to 70 mol% relative to all the structural units in the resin (A).

[0304] In the present invention, when the content of a "structural unit" is specified by molar ratio, the "structural unit" is synonymous with the "monomer unit." Furthermore, in the present invention, the "monomer unit" may be modified after polymerization, such as by polymer reactions. This also applies hereinafter.

[0305] [A structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure]

[0306] The resin (A) preferably has at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0307] Any lactone or sultone structure can be used as long as it has a lactone or sultone structure. A 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferred. A structure in which another ring structure is fused to a 5- to 7-membered ring lactone structure to form a bicyclic or spirocyclic structure, or a structure in which another ring structure is fused to a 5- to 7-membered ring sultone structure to form a bicyclic or spirocyclic structure, is more preferred. Furthermore, a structural unit comprising a lactone structure represented by any of the following formulas LC1-1 to LC1-21 or a sultone structure represented by any of the following formulas SL1-1 to SL1-3 is more preferred. Furthermore, the lactone or sultone structure may be directly bonded to the main chain. Preferred structures are LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, and SL1-1.

[0308] [Chemical Formula 22]

[0309]

[0310] The lactone structure portion or the sultone structure portion may have a substituent (Rb 2 ), or may not have the substituent. As a preferred substituent (Rb 2 ), and examples thereof include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms other than fluorine atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. More preferred are alkyl groups having 1 to 4 carbon atoms, cyano groups, and acid-decomposable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, there are multiple substituents (Rb 2 ) may be the same or different. In addition, there are multiple substituents (Rb 2 ) may be bonded to each other to form a ring.

[0311] The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III.

[0312] Furthermore, the resin including a structural unit having an acid-decomposable group preferably includes a structural unit represented by the following formula III.

[0313] [Chemical Formula 23]

[0314]

[0315] In the above formula III,

[0316] A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).

[0317] n is by-R0 The number of repetitions of the structure represented by -Z- represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, -R 0 -Z- does not exist, and A and R 8 Bonded by a single bond.

[0318] R 0 represents an alkylene group, a cycloalkylene group or a combination thereof. 0 When there are plural groups, they each independently represent an alkylene group, a cycloalkylene group, or a combination thereof.

[0319] Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When there are multiple Zs, they each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond.

[0320] R 8 It represents a monovalent organic group having a lactone structure or a sultone structure.

[0321] R 7 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

[0322] R 0 The alkylene group or cycloalkylene group may have a substituent.

[0323] Z is preferably an ether bond or an ester bond, more preferably an ester bond.

[0324] Specific examples of monomers corresponding to the structural unit represented by formula III and specific examples of monomers corresponding to the structural unit represented by formula A-1 described later are given below, but the present invention is not limited to these specific examples. 7 and R in the formula A-1 described below A 1 In the case of methyl, but R 7 and R A 1 It may be arbitrarily substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0325] [Chemical Formula 24]

[0326]

[0327] In addition to the above-mentioned monomers, the monomers shown below can also be suitably used as raw materials for the resin (A).

[0328] [Chemical Formula 25]

[0329]

[0330] The resin (A) may also contain a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0331] The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.

[0332] [Chemical Formula 26]

[0333]

[0334] In formula A-1, R A 1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer greater than 0, and R A 2 represents a substituent. When n is 2 or more, R A 2 Each independently represents a substituent, A represents a single bond or a divalent linking group, and Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with the group represented by -OC(=O)-O- in the formula.

[0335] The resin (A) also preferably has the structural units described in paragraphs 0370 to 0414 of US Patent Application Publication No. 2016 / 0070167 as the structural units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0336] The resin (A) preferably contains a structural unit (a) having at least two lactone structures (hereinafter also referred to as "structural unit (a)").

[0337] The at least two lactone structures may be, for example, a structure in which at least two lactone structures are fused together, or a structure in which at least two lactone structures are linked via a single bond or a linking group.

[0338] The lactone structure of the structural unit (a) is not particularly limited, but is preferably a 5- to 7-membered ring lactone structure, and preferably a structure in which another ring structure is fused to the 5- to 7-membered ring lactone structure to form a bicyclic structure or a spirocyclic structure.

[0339] Preferred examples of the lactone structure include lactone structures represented by any one of LC1-1 to LC1-21.

[0340] The structural unit having at least two lactone structures (hereinafter, also referred to as "structural unit (a)") is preferably a structural unit represented by the following formula L-1.

[0341] [Chemical Formula 27]

[0342]

[0343] In formula L-1, Ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having two or more lactone structures.

[0344] The alkyl group of R is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of R may be substituted. Examples of the substituent include halogen atoms such as fluorine, chlorine, and bromine atoms; alkoxy groups such as mercapto, hydroxy, methoxy, ethoxy, isopropoxy, tert-butoxy, and benzyloxy; and acetoxy groups such as acetyl and propionyl. R is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

[0345] Examples of the lactone structure of the Rb partial structure include the above-mentioned lactone structures.

[0346] The partial structure of Rb having two or more lactone structures is preferably, for example, a structure in which at least two lactone structures are linked via a single bond or a linking group, or a structure in which at least two lactone structures are fused.

[0347] The structural unit (a1) having a structure in which at least two lactone structures are fused and the structural unit (a2) having a structure in which at least two lactone structures are linked via a single bond or a linking group are described below.

[0348] -Structural unit (a1) having a structure in which at least two lactone structures are fused-

[0349] The structure in which at least two lactone structures are condensed is preferably a structure in which two or three lactone structures are condensed, and more preferably a structure in which two lactone structures are condensed.

[0350] Examples of the structural unit having a structure in which at least two lactone structures are fused (hereinafter also referred to as "structural unit (a1)") include a structural unit represented by the following formula L-2.

[0351] [Chemical Formula 28]

[0352]

[0353] In formula L-2, Ra has the same meaning as Ra in formula L-1, Re1 to Re8 each independently represent a hydrogen atom or an alkyl group, Me1 represents a single bond or a divalent linking group, and Me2 and Me3 each independently represent a divalent linking group.

[0354] The alkyl group of Re1 to Re8 preferably has 5 or less carbon atoms, and more preferably has 1 carbon atom.

[0355] Examples of the alkyl group having 5 or less carbon atoms in Re1 to Re8 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, and tert-pentyl.

[0356] Among them, Re1 to Re8 are preferably hydrogen atoms.

[0357] Examples of the divalent linking group of Me1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.

[0358] The alkylene group of Me1 preferably has, for example, 1 to 10 carbon atoms, and more preferably has 1 or 2 carbon atoms. Examples of the alkylene group having 1 or 2 carbon atoms include a methylene group and an ethylene group.

[0359] The alkylene group of Me1 may be linear or branched, and examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0360] The cycloalkylene group of Me1 preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms.

[0361] Examples of the cycloalkylene group of Me1 include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and cyclodecylene.

[0362] As the divalent linking group of Me1, a group composed of the above two or more groups is preferably a group composed of an alkylene group and -COO-, and a group composed of a -OCO- and an alkylene group. Furthermore, a group composed of the above two or more groups is more preferably a group composed of a methylene group and a -COO- group, and a group composed of a -COO- group and a methylene group.

[0363] Examples of the divalent linking group of Me2 and Me3 include alkylene, -O-, etc. The divalent linking group of Me2 and Me3 is preferably methylene, ethylene, or -O-, and more preferably -O-.

[0364] The monomer corresponding to the structural unit (a1) can be synthesized by the method described in, for example, JP-A-2015-160836.

[0365] Specific examples of the structural unit (a1) are shown below, but the present invention is not limited thereto. In the following formulae, R9 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and * represents a bonding position to another structural unit.

[0366] [Chemical Formula 29]

[0367]

[0368] [Chemical formula 30]

[0369]

[0370] [Chemical Formula 31]

[0371]

[0372] -Structural unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group-

[0373] The structure in which at least two lactone structures are linked by a single bond or a linking group is preferably a structure in which 2 to 4 lactone structures are linked by a single bond or a linking group, and more preferably a structure in which two lactone structures are linked by a single bond or a linking group.

[0374] Examples of the linking group include the same groups as those exemplified as the linking group of M2 in the formula L-3 described later.

[0375] Examples of the structural unit having a structure in which two or more lactone structures are linked by a single bond or a linking group (hereinafter also referred to as "structural unit (a2)") include a structural unit represented by the following formula L-3.

[0376] [Chemical Formula 32]

[0377]

[0378] In formula L-3, Ra has the same meaning as Ra in the above formula L-1, M1 and M2 each independently represent a single bond or a linking group, and Lc1 and Lc2 each independently represent a group having a lactone structure.

[0379] Examples of the linking group of M1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.

[0380] The alkylene group of M1 preferably has 1 to 10 carbon atoms, for example.

[0381] The alkylene group of M1 may be linear or branched, and examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0382] The cycloalkylene group of M1 preferably has 5 to 10 carbon atoms, for example.

[0383] Examples of the cycloalkylene group of M1 include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and cyclodecylene.

[0384] As the linking group of M1, a group composed of a combination of two or more of the above groups is preferably a group composed of a combination of an alkylene group and -COO-, and a group composed of a combination of -OCO- and an alkylene group. Furthermore, a group composed of a combination of two or more of the above groups is more preferably a group composed of a combination of a methylene group and a -COO- group, and a group composed of a combination of a -COO- group and a methylene group.

[0385] Examples of the linking group of M2 include the same groups as those exemplified for the linking group of M1.

[0386] The lactone structure possessed by Lc1 is preferably, for example, a 5- to 7-membered ring lactone structure, preferably a structure in which another ring structure is fused to the 5- to 7-membered ring lactone structure to form a bicyclic structure or a spirocyclic structure. The lactone structure is more preferably a lactone structure represented by any of LC1-1 to LC1-21. Further preferred lactone structures include LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14, and LC1-17.

[0387] The lactone structure of Lc1 may contain a substituent. The substituent that the lactone structure of Lc1 may contain includes, for example, the substituents (Rb 2 ) the same substituents.

[0388] Examples of the lactone structure contained in Lc2 include the same structures as those exemplified for the lactone structure contained in Lc1.

[0389] The structural unit (a2) is preferably a structural unit represented by the following formula L-4 as the structural unit represented by the above-mentioned formula L-3.

[0390] [Chemical Formula 33]

[0391]

[0392] In formula L-4, Ra has the same meaning as Ra in the above formula L-1, Mf1 and Mf2 each independently represent a single bond or a connecting group, Rf1, Rf2 and Rf3 each independently represent a hydrogen atom or an alkyl group, Mf1 and Rf1 can be bonded to each other to form a ring, and Mf2 and Rf2 or Rf3 can be bonded to each other to form a ring.

[0393] The linking group of Mf1 has the same meaning as the linking group of M1 in the above formula L-3.

[0394] The meaning of the linking group of Mf2 is the same as the linking group of M2 in the above formula L-3.

[0395] Examples of the alkyl group represented by Rf1 include alkyl groups having 1 to 4 carbon atoms. The alkyl group represented by Rf1 having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, more preferably a methyl group. The alkyl group represented by Rf1 may have a substituent. Examples of substituents that the alkyl group represented by Rf1 may have include a hydroxyl group, an alkoxy group such as a methoxy group and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom.

[0396] The alkyl groups of Rf2 and Rf3 have the same meaning as the alkyl group of Rf1.

[0397] Mf1 and Rf1 may be bonded to each other to form a ring. Examples of the structure in which Mf1 and Rf1 are bonded to each other to form a ring include the lactone structures represented by LC1-13, LC1-14, or LC1-17 among the lactone structures.

[0398] Mf2 and Rf2 or Rf3 may be bonded to each other to form a ring.

[0399] Examples of the structure in which Mf2 and Rf2 are bonded to each other to form a ring include the lactone structure represented by LC1-7, LC1-8 or LC1-15 among the above lactone structures.

[0400] Examples of the structure in which Mf2 and Rf3 are bonded to each other to form a ring include the lactone structure represented by any one of LC1-3 to LC1-6 among the above lactone structures.

[0401] Specific examples of the structural unit (a2) are shown below, but the present invention is not limited thereto. * indicates a bonding position to another structural unit.

[0402] [Chemical Formula 34]

[0403]

[0404] Structural units having at least two lactone structures generally exist as optical isomers, but any optical isomer may be used. Furthermore, a single optical isomer may be used alone, or a mixture of multiple optical isomers may be used. When a single optical isomer is used primarily, its optical purity (ee) is preferably 90% or greater, more preferably 95% or greater.

[0405] The content of the structural units having at least two lactone structures is preferably 10 to 60 mol %, more preferably 20 to 50 mol %, and even more preferably 30 to 50 mol % relative to all structural units in the resin (A).

[0406] In order to improve the effect of the present invention, two or more structural units having at least two lactone structures may be used in combination. When containing two or more repeating units having at least two lactone structures, the total content of the structural units having at least two lactone structures is preferably within the above range.

[0407] The resin (A) may contain one type of structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more types of such structural units in combination.

[0408] The content of the structural units having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure contained in the resin (A) (when a plurality of structural units having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure are present, the total content) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 65 mol%, and even more preferably 20 mol% to 60 mol%.

[0409] [Structural unit with polar group]

[0410] The resin (A) preferably contains a structural unit having a polar group.

[0411] Examples of the polar group include a hydroxyl group, a cyano group, and a carboxyl group.

[0412] The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. Furthermore, the structural unit having a polar group preferably does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornyl group.

[0413] Specific examples of monomers corresponding to the structural unit having a polar group are given below, but the present invention is not limited to these specific examples. In addition, although the following specific examples are described as methacrylate compounds, they may also be acrylate compounds.

[0414] [Chemical Formula 35]

[0415]

[0416] Specific examples of the structural unit having a polar group include the structural units disclosed in paragraphs 0415 to 0433 of US Patent Application Publication No. 2016 / 0070167.

[0417] The resin (A) may contain one type of structural unit having a polar group alone, or may contain two or more types of such structural units in combination.

[0418] The content of the structural unit having a polar group is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, and even more preferably 10 to 25 mol %, based on all repeating units in the resin (A).

[0419] [Structural unit having neither an acid-decomposable group nor a polar group]

[0420] Resin (A) may further include a structural unit having neither an acid-degradable group nor a polar group. The structural unit having neither an acid-degradable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of structural units having neither an acid-degradable group nor a polar group include the structural units described in paragraphs 236-237 of U.S. Patent Application Publication No. 2016 / 0026083. Preferred examples of monomers corresponding to structural units having neither an acid-degradable group nor a polar group are shown below.

[0421] [Chemical Formula 36]

[0422]

[0423] Specific examples of the structural unit having neither an acid-decomposable group nor a polar group include the structural unit disclosed in paragraph 0433 of US Patent Application Publication No. 2016 / 0070167.

[0424] The resin (A) may contain one type of structural unit having neither an acid-decomposable group nor a polar group alone, or may contain two or more types of such structural units in combination.

[0425] The content of the structural unit having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, and even more preferably 5 to 25 mol % based on all structural units in the resin (A).

[0426] [Repeating unit (a1)]

[0427] The resin (A) may further have the following repeating unit (a1).

[0428] The repeating unit (a1) is a repeating unit derived from a monomer (also referred to as "monomer a1") having a glass transition temperature of 50°C or lower when forming a homopolymer.

[0429] Furthermore, the repeating unit (a1) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a1) does not have an acid-decomposable group.

[0430] (Method for measuring glass transition temperature of homopolymer)

[0431] The glass transition temperature of the homopolymer was determined by using catalog or literature values when available. Otherwise, it was measured using differential scanning calorimetry (DSC). The homopolymer weight-average molecular weight (Mw) used for Tg measurement was set to 18,000, and the dispersion (Mw / Mn) was set to 1.7. A thermal analysis DSC differential scanning calorimeter model Q1000 manufactured by TA Instruments was used as the DSC apparatus, and measurements were performed at a heating rate of 10°C / min.

[0432] The homopolymer used for Tg measurement may be synthesized using corresponding monomers by a known method, and for example, may be synthesized by a conventional dropping polymerization method, etc. An example is shown below.

[0433] 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were heated to 80°C under a nitrogen flow. While stirring the solution, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2'-azobisisobutyrate was added dropwise over a period of 6 hours. After the addition was completed, the mixture was stirred at 80°C for another 2 hours. After the reaction solution was naturally cooled, it was reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). The obtained homopolymer was used for DSC measurement. The DSC apparatus and the heating rate were set as described above.

[0434] The glass transition temperature (Tg) of monomer a1 is not particularly limited as long as it is 50°C or less when formed into a homopolymer. From the perspective of improving the resolution of the dot pattern and suppressing the roughness of the resist pattern sidewalls that may occur during etching, the Tg when formed into a homopolymer is preferably 30°C or less. The lower limit of the Tg when monomer a1 is formed into a homopolymer is not particularly limited, but is preferably -80°C or greater, more preferably -70°C or greater, further preferably -60°C or greater, and particularly preferably -50°C or greater. By setting the lower limit of the Tg when monomer a1 is formed into a homopolymer within the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, which is preferred.

[0435] From the viewpoint of easier volatilization of the residual solvent, the repeating unit (a1) is preferably a repeating unit which may contain a heteroatom in the chain and has a non-acid-decomposable alkyl group having 2 or more carbon atoms. In this specification, "non-acid-decomposable" means having the property of not undergoing a dissociation / decomposition reaction with an acid generated by a photoacid generator.

[0436] More specifically, the “non-acid-decomposable alkyl group” includes an alkyl group that is not detached from the resin (A) by the action of an acid generated by a photoacid generator or an alkyl group that is not decomposed by the action of an acid generated by a photoacid generator.

[0437] The non-acid-decomposable alkyl group may be either linear or branched.

[0438] Hereinafter, the repeating unit which may contain a heteroatom in the chain and has a non-acid-decomposable alkyl group having 2 or more carbon atoms will be described.

[0439] The non-acid-decomposable alkyl group having 2 or more carbon atoms and optionally containing a heteroatom in the chain is not particularly limited, and examples thereof include alkyl groups having 2 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms and containing a heteroatom in the chain.

[0440] Examples of alkyl groups having 2 to 20 carbon atoms and containing a heteroatom in the chain include alkyl groups in which one or two or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these. R6 above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0441] Specifically, examples of the non-acid-decomposable alkyl group having 2 or more carbon atoms and which may contain a heteroatom in the chain include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, 2-ethylhexyl, and monovalent alkyl groups in which one or two or more -CH2- groups are substituted by -O- or -O-CO-.

[0442] The number of carbon atoms in the non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain, is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and even more preferably 2 or more and 8 or less. The lower limit of the number of carbon atoms in the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more.

[0443] Furthermore, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (eg, substituent T).

[0444] The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

[0445] [Chemical Formula 37]

[0446]

[0447] In the general formula (1-2), R1 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and R2 represents a non-acid-decomposable alkyl group having 2 or more carbon atoms and optionally containing a heteroatom in the chain.

[0448] The halogen atom represented by R<1 > is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0449] The alkyl group represented by R1 is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, specifically methyl, ethyl, and tert-butyl groups. Among them, alkyl groups having 1 to 3 carbon atoms are preferred, and methyl is more preferred.

[0450] The cycloalkyl group represented by R<1> is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups.

[0451] Among them, R1 is preferably a hydrogen atom or a methyl group.

[0452] The definition and preferred embodiment of the non-acid-decomposable alkyl group having 2 or more carbon atoms and optionally containing a heteroatom in the chain represented by R2 are as described above.

[0453] Furthermore, from the viewpoint of easier volatilization of the residual solvent, the repeating unit (a1) may be a repeating unit comprising a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group.

[0454] Hereinafter, a repeating unit including a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group will be described.

[0455] The non-acid-decomposable alkyl group may be either linear or branched.

[0456] The number of carbon atoms of the non-acid-decomposable alkyl group is preferably 2 or more. From the viewpoint of making the Tg of the homopolymer 50° C. or less, the upper limit of the number of carbon atoms of the non-acid-decomposable alkyl group is preferably, for example, 20 or less.

[0457] The non-acid-decomposable alkyl group which may contain a heteroatom in the chain is not particularly limited, and examples thereof include alkyl groups having 2 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms containing a heteroatom in the chain. Furthermore, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group.

[0458] Examples of alkyl groups having 2 to 20 carbon atoms and containing a heteroatom in the chain include alkyl groups in which one or two or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these. R6 above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0459] The number of carbon atoms of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain is preferably 2 to 16, more preferably 2 to 10, and even more preferably 2 to 8 from the viewpoint of achieving better crack resistance (less prone to cracking).

[0460] Furthermore, the non-acid-decomposable alkyl group may have a substituent (eg, substituent T).

[0461] Specific examples of the repeating unit containing a non-acid-decomposable alkyl group having a carboxyl group and a heteroatom in the chain include repeating units having the following structures.

[0462] [Chemical Formula 38]

[0463]

[0464] The number of carbon atoms of the non-acid-decomposable cycloalkyl group is preferably 5 or more. From the viewpoint of setting the Tg of the homopolymer to 50°C or less, the upper limit of the number of carbon atoms of the non-acid-decomposable cycloalkyl group is, for example, preferably 20 or less, more preferably 16 or less, and even more preferably 10 or less.

[0465] The non-acid-decomposable cycloalkyl group which may contain a heteroatom on the ring is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 20 carbon atoms (more specifically, cyclohexyl groups) and cycloalkyl groups having 5 to 20 carbon atoms containing a heteroatom on the ring. Furthermore, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group.

[0466] Examples of cycloalkyl groups having 5 to 20 carbon atoms and containing a heteroatom in the ring include alkyl groups in which one or two or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. R6 above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0467] Furthermore, the non-acid-decomposable cycloalkyl group may have a substituent (eg, substituent T).

[0468] As a repeating unit containing a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group, a repeating unit represented by the following general formula (1-3) is preferred from the viewpoint of further improving the effects of the present invention.

[0469] [Chemical Formula 39]

[0470]

[0471] In the general formula (1-3), R3 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R4 represents a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group.

[0472] In the general formula (1-3), R3 has the same meaning as R1 described above, and preferred embodiments are also the same.

[0473] The definition and preferred embodiment of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or the non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group represented by R4 are as described above.

[0474] Among them, R4 is preferably a non-acid decomposable cycloalkyl group which may contain a heteroatom on the ring and has a carboxyl group or a hydroxyl group. As an example of this embodiment, a repeating unit of the following structure can be mentioned.

[0475] [Chemical Formula 40]

[0476]

[0477] Examples of monomer a1 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), n-butyl methacrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (-70°C), isononyl acrylate (-82°C), lauryl methacrylate (-65°C), 2-hydroxyethyl acrylate (-15°C), 2-hydroxypropyl methacrylate (26°C), 1-[2-(methacryloyloxy)ethyl] succinate (9°C), 2-ethylhexyl methacrylate (-10°C), sec-butyl acrylate (-26°C), methoxypolyethylene glycol monomethacrylate (n=2) (-20°C), and hexadecyl acrylate (35°C). The values in parentheses indicate the Tg (°C) when the homopolymer is prepared.

[0478] Methoxypolyethylene glycol monomethacrylate (n=2) is a compound having the following structure.

[0479] [Chemical Formula 41]

[0480]

[0481] Monomer a1 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, hexadecyl acrylate, 2-hydroxyethyl acrylate, and a compound represented by the following MA-5.

[0482] [Chemical Formula 42]

[0483]

[0484] The resin (A) may contain only one type of repeating unit (a1), or may contain two or more types of the repeating unit (a1).

[0485] In the resin (A), the content of the repeating unit (a1) relative to all the repeating units in the resin (A) (when a plurality of repeating units (a1) are present, the total amount thereof) is preferably 5 mol% or more, more preferably 10 mol% or more, and is preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less. Furthermore, the content of the repeating unit (a1) relative to all the repeating units in the resin (A) (when a plurality of repeating units (a1) are present, the total amount thereof) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 5 to 30 mol%.

[0486] [Repeating unit (a4) having a phenolic hydroxyl group]

[0487] The resin (A) may contain a repeating unit (a4) having a phenolic hydroxyl group.

[0488] The resin (A) contains the repeating unit (a4), so that the dissolution rate during alkaline development is further improved and the etching resistance is excellent.

[0489] The repeating unit having a phenolic hydroxyl group is not particularly limited, and examples thereof include a hydroxystyrene repeating unit and a hydroxystyrene (meth)acrylate repeating unit. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I).

[0490] [Chemical Formula 43]

[0491]

[0492] Where,

[0493] R 41 、R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0494] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0495] L4 represents a single bond or a divalent linking group.

[0496] Ar4 represents an (n+1) valent aromatic hydrocarbon group, when it is combined with R 42 When they are bonded to form a ring, they represent an aromatic hydrocarbon group with a valence of (n+2).

[0497] n represents an integer of 1 to 5.

[0498] In order to make the repeating unit represented by the general formula (I) highly polar, it is also preferred that n is an integer of 2 or more or X4 is -COO- or -CONR 64 -.

[0499] As R in the general formula (I) 41 、R 42 and R 43 The alkyl group represented by is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0500] As R in the general formula (I) 41 、R 42 and R 43 The cycloalkyl group represented by may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl, which may have a substituent.

[0501] As R in the general formula (I) 41 、R 42 , and R 43 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0502] As R in the general formula (I) 41 、R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group represented by is preferably the same as the above R 41 、R 42 and R 43 The alkyl group in is the same as the alkyl group.

[0503] Preferred substituents in the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a urea group, a carbamate group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. Preferably, the substituent has 8 or less carbon atoms.

[0504] Ar4 represents an (n+1)-valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group in which n is 1 may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms, such as phenylene, tolylene, naphthylene, and anthracene, or an aromatic hydrocarbon group containing a heterocycle, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0505] Specific examples of the (n+1)-valent aromatic hydrocarbon group when n is an integer of 2 or greater include preferably groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group.

[0506] The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

[0507] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include R 41 、R 42 and R 43 alkyl groups mentioned above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.

[0508] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group which may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms.

[0509] X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0510] The divalent linking group of L4 is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, and octylene, which may have a substituent.

[0511] Ar4 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group. The repeating unit represented by general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar4 is preferably a benzene ring group.

[0512] Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto.

[0513] [Chemical Formula 44]

[0514]

[0515] The resin (A) may have one type of repeating unit (a4) alone, or may have two or more types of the repeating units (a4) in combination.

[0516] In resin (A), the content of repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, relative to all repeating units in resin (A). Furthermore, the content of repeating unit (a4) is preferably 85 mol% or less, more preferably 80 mol% or less, relative to all repeating units in resin (A).

[0517] In addition to the above-mentioned structural units, the resin (A) may have various structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer solutions, substrate adhesion, resist profile, and further adjusting resolution, heat resistance, sensitivity, etc., which are generally required properties of resists. Such structural units include, but are not limited to, structural units corresponding to other monomers.

[0518] Examples of other monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters.

[0519] Furthermore, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the various structural units described above may be copolymerized.

[0520] In the resin (A), the molar ratio of each structural unit is appropriately set in order to adjust various properties.

[0521] When the actinic ray- or radiation-sensitive resin composition of the present invention is for argon fluoride (ArF) laser exposure, the resin (A) preferably contains substantially no aromatic groups from the perspective of ArF light transmittance. More specifically, the proportion of structural units containing aromatic groups in the resin (A) is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, i.e., it is even more preferred that no structural units containing aromatic groups are contained. Furthermore, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0522] Resin (A) preferably has all structural units composed of (meth)acrylate structural units. In this case, any of the following structural units can be used: a structural unit in which all structural units are methacrylate structural units, a structural unit in which all structural units are acrylate structural units, or a structural unit in which all structural units are composed of methacrylate structural units and acrylate structural units. However, the proportion of acrylate structural units relative to all structural units in resin (A) is preferably 50 mol% or less.

[0523] When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for krypton fluoride (KrF) exposure, electron beam (EB) exposure, or extreme ultraviolet (EUV) exposure, the resin (A) preferably contains a structural unit having an aromatic hydrocarbon group. More preferably, the resin (A) contains a structural unit having a phenolic hydroxyl group.

[0524] As a structural unit which has a phenolic hydroxyl group, the said repeating unit (a4) is mentioned, for example.

[0525] When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a structure in which the hydrogen atom of the phenolic hydroxyl group is protected by a group (leaving group) that decomposes and leaves by the action of an acid.

[0526] The content of the structural unit having an aromatic hydrocarbon group in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and further preferably 50 mol% to 100 mol%, relative to all repeating units in the resin (A).

[0527] The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000.

[0528] The degree of dispersion (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, further preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0.

[0529] Specific examples of the resin (A) include resins A-1 to A-17 used in Examples, but the present invention is not limited thereto.

[0530] The resin (A) may be used alone or in combination of two or more.

[0531] The content of the resin (A) relative to the total solids content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 97% by mass or less.

[0532] [Alkali-soluble resin having phenolic hydroxyl groups]

[0533] When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a crosslinking agent (G) described below, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as "resin (C)"). The resin (C) preferably contains a structural unit having a phenolic hydroxyl group.

[0534] At this time, typically, it is preferred to form a negative pattern.

[0535] The crosslinking agent (G) may be in a form supported on the resin (C).

[0536] In addition, among the resins (C), the resins whose polarity is increased by the action of an acid are treated as resins whose polarity is increased by the action of an acid. In this case, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a resin whose polarity is increased by the action of an acid as the resin (C), and may also contain at least a resin (C) other than the resin whose polarity is increased by the action of an acid and a resin whose polarity is increased by the action of an acid.

[0537] The resin (C) may contain the above-mentioned acid-decomposable group.

[0538] The structural unit having a phenolic hydroxyl group in the resin (C) is not particularly limited, but is preferably the repeating unit (a4).

[0539] The resin (C) may be used alone or in combination of two or more.

[0540] The content of the resin (C) in the total solids content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0541] As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of US Patent Application Publication No. 2016 / 0282720 can be preferably used.

[0542] 〔Hydrophobic resin〕

[0543] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further contains a hydrophobic resin (also referred to as a hydrophobic resin (E)).

[0544] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains at least a hydrophobic resin (E) other than a resin whose polarity is increased by the action of an acid, and a resin whose polarity is increased by the action of an acid.

[0545] The actinic ray- or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (E), which can control the static and dynamic contact angles of the actinic ray- or radiation-sensitive film surface. This improves developing characteristics, suppresses degassing, enhances immersion liquid conformability during immersion exposure, and reduces immersion defects.

[0546] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and does not need to contribute to uniform mixing of polar and non-polar substances.

[0547] Furthermore, in the present invention, the resin having fluorine atoms is treated as a hydrophobic resin and a fluorine-containing resin described below. Furthermore, the resin containing a structural unit having an acid-decomposable group preferably does not have fluorine atoms.

[0548] From the viewpoint of being concentrated on the film surface, the hydrophobic resin (E) is preferably a resin containing at least one structural unit selected from the group consisting of a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain of the resin.

[0549] When the hydrophobic resin (E) contains fluorine atoms or silicon atoms, the fluorine atoms or silicon atoms in the hydrophobic resin (E) may be contained in the main chain or in the side chain of the resin.

[0550] The hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).

[0551] (x) acid group

[0552] (y) A group that decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group).

[0553] (z) Groups that decompose by the action of an acid

[0554] Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group.

[0555] The acid group is preferably a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group, or a bis(alkylcarbonyl)methylene group.

[0556] Examples of the group (y) that decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer include a lactone group, a carboxylate group (-COO-), an anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylate thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO2O-) and a sulfonate group (-SO2O-), preferably a lactone group or a carboxylate group (-COO-).

[0557] Structural units containing these groups are structural units in which these groups are directly bonded to the main chain of the resin. Examples include structural units formed from acrylates and methacrylates. These structural units can be bonded to the main chain of the resin via a linking group. Alternatively, these structural units can be used during the polymerization of polymerization initiators or chain transfer agents containing these groups and introduced into the terminal ends of the resin.

[0558] Examples of the structural unit having a lactone group include the same structural units as those having a lactone structure described above in the section of the resin (A).

[0559] The content of the structural unit having the group (y) that is decomposed by the action of an alkaline developer and has increased solubility in the alkaline developer is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and even more preferably 5 to 95 mol %, based on all the structural units in the hydrophobic resin (E).

[0560] The structural unit having a group (z) decomposable by the action of an acid in the hydrophobic resin (E) may include the same structural units as those having an acid-decomposable group mentioned in the resin (A). The structural unit having a group (z) decomposable by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the structural unit having a group (z) decomposable by the action of an acid relative to all the structural units in the resin (E) is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and even more preferably 20 mol% to 60 mol%.

[0561] The hydrophobic resin (E) may further have a structural unit different from the above-mentioned structural units.

[0562] The proportion of structural units containing fluorine atoms is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, relative to all structural units contained in the hydrophobic resin (E). Furthermore, the proportion of structural units containing silicon atoms is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, relative to all structural units contained in the hydrophobic resin (E).

[0563] On the other hand, particularly when the hydrophobic resin (E) contains a CH3 partial structure in the side chain, it is also preferred that the hydrophobic resin (E) contains substantially no fluorine atoms and silicon atoms. Furthermore, the hydrophobic resin (E) is preferably composed essentially only of structural units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

[0564] The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

[0565] The total content of residual monomers and oligomers in the hydrophobic resin (E) is preferably 0.01% to 5% by mass, more preferably 0.01% to 3% by mass. Furthermore, the dispersion degree (Mw / Mn) is preferably in the range of 1 to 5, more preferably 1 to 3.

[0566] As the hydrophobic resin (E), it is possible to appropriately select and use a known resin as a single resin or a mixture thereof. For example, it is possible to preferably use the known resins disclosed in paragraphs 0451 to 0704 in U.S. Patent Application Publication No. 2015 / 0168830 and paragraphs 0340 to 0356 in U.S. Patent Application Publication No. 2016 / 0274458 as the hydrophobic resin (E). In addition, the structural units disclosed in paragraphs 0177 to 0258 in U.S. Patent Application Publication No. 2016 / 0237190 are also preferably used as the structural units constituting the hydrophobic resin (E).

[0567] -Fluorine-containing resin-

[0568] The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as a fluorine-containing resin).

[0569] When the hydrophobic resin (E) contains a fluorine atom, the partial structure containing a fluorine atom is preferably a resin containing an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom.

[0570] The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.

[0571] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom.

[0572] Examples of the aryl group having a fluorine atom include groups in which at least one hydrogen atom in an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom.

[0573] As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom, groups represented by formulae F2 to F4 are preferred.

[0574] [Chemical Formula 45]

[0575]

[0576] In formulas F2 to F4,

[0577] R 57 ~R 68 Each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). 57 ~R 61 At least one of R 62 ~R 64 At least one of R 65 ~R 68 At least one of them independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.

[0578] Preferred R 57 ~R 61 and R 65 ~R 67 are all fluorine atoms. 62 、R 63 and R 68 It is preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted by a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 62 With R 63 Can be connected to each other to form a ring.

[0579] Among them, from the viewpoint of achieving more excellent effects of the present invention, the fluorine-containing resin preferably has alkali decomposability.

[0580] Alkali-degradable fluororesins mean that, when 100 mg of the fluororesin is added to a mixture of 2 mL of a pH 10 buffer solution and 8 mL of THF and allowed to stand at 40°C for 10 minutes, at least 30 mol% of the total degradable groups in the fluororesin are hydrolyzed. The decomposition rate can be calculated from the ratio of the starting material to the decomposition product by NMR analysis.

[0581] The fluorine-containing resin preferably has a structural unit represented by Formula X from the viewpoints of focus depth tolerance, pattern linearity, improvement of development characteristics, suppression of degassing, improvement of immersion liquid followability in immersion exposure, and reduction of immersion defects.

[0582] Furthermore, from the viewpoints of depth of focus tolerance, pattern linearity, improvement of development characteristics, suppression of degassing, improvement of immersion liquid followability during immersion exposure, and reduction of immersion defects, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a fluorine-containing resin having a structural unit represented by formula X.

[0583] [Chemical Formula 46]

[0584]

[0585] In formula X, Z represents a halogen atom, R 11 The group represented by OCH2- or R 12 OC(=O)CH2- represented group, R 11 and R 12 Each independently represents a substituent, X represents an oxygen atom or a sulfur atom, L represents a (n+1) valent linking group, R 10 represents a group having a group which decomposes by the action of an alkaline aqueous solution and increases the solubility of the fluorine-containing resin in the alkaline aqueous solution, n represents a positive integer, and when n is 2 or more, a plurality of R 10 They can be the same as each other or different.

[0586] Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0587] As R 11 and R 12 Examples of the substituents of include alkyl groups (preferably having 1 to 4 carbon atoms), cycloalkyl groups (preferably having 6 to 10 carbon atoms), and aryl groups (preferably having 6 to 10 carbon atoms). 11 and R 12 The substituent may further have a substituent, and examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), and a carboxyl group.

[0588] The linking group of L is preferably a divalent or trivalent linking group (in other words, n is preferably 1 or 2), more preferably a divalent linking group (in other words, n is preferably 1). The linking group of L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof.

[0589] For example, when n is 1 and the linking group of L is a divalent linking group, examples of the divalent aliphatic group include alkylene, alkenylene, alkynylene, and polyalkyleneoxy groups. Among them, alkylene and alkenylene are preferred, and alkylene is more preferred.

[0590] The divalent aliphatic group may have a chain structure or a cyclic structure, but a chain structure is preferred over a cyclic structure, and a straight-chain structure is preferred over a branched chain structure. The divalent aliphatic group may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.

[0591] Examples of the divalent aromatic group include arylene groups, of which phenylene groups and naphthylene groups are preferred.

[0592] The divalent aromatic group may have a substituent, and examples of the substituent in the above-mentioned divalent aliphatic group include an alkyl group.

[0593] Furthermore, L may be a divalent group formed by removing two hydrogen atoms at arbitrary positions from the structure represented by the above-mentioned formulae LC1-1 to LC1-21 or SL1-1 to SL-3.

[0594] When n is 2 or greater, specific examples of the (n+1)-valent linking group include groups obtained by removing arbitrary (n-1) hydrogen atoms from the specific examples of the above-mentioned divalent linking group.

[0595] Specific examples of L include the following linking groups.

[0596] [Chemical Formula 47]

[0597] -CH2--CH2CH2--CH2CH2CH2--CH2CH2CH2CH2-

[0598] -CH2CH2CH2CH2CH2--CH2CH2CH2CH2CH2CH2-

[0599]

[0600] Furthermore, as described above, these linking groups may further have a substituent.

[0601] As R 10 , preferably a group represented by the following formula W.

[0602] -YR 20 Formula W

[0603] In the above formula W, Y represents a group that is decomposed by the action of an alkaline aqueous solution and has increased solubility in the alkaline aqueous solution. 20 Represents an electron-withdrawing group.

[0604] As Y, there can be mentioned a carboxylate group (-COO- or OCO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylate thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO2O-) and a sulfonate group (-SO2O-), preferably a carboxylate group.

[0605] The electron-withdrawing group is preferably a partial structure represented by the following formula EW: * in formula EW represents a bond directly connected to the group Y in formula W.

[0606] [Chemical Formula 48]

[0607]

[0608] In the formula EW,

[0609] n ew For-C(R ew1 )(R ew2 )- represents the number of repetitions of the linking group, which is an integer of 0 or 1. ew When it is 0, it means a single bond, which means there is a direct bond with Y ew1 .

[0610] Y ew1 Examples include a halogen atom, a cyano group, a nitro group, and -C(R f1 )(R f2 )-R f3 alkyl, halogenated aryl, oxy, carbonyl, sulfonyl, sulfinyl and combinations thereof. ew1 When it is a halogen atom, cyano group or nitro group, n ew is 1.)

[0611] R ew1 and R ew2 Each independently represents an arbitrary group, for example, a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), or an aryl group (preferably having 6 to 10 carbon atoms).

[0612] R ew1 、R ew2 and Y ew1 At least two of them may be connected to each other to form a ring.

[0613] Furthermore, "halogenated (cyclo)alkyl" refers to an alkyl group or cycloalkyl group that is at least partially halogenated, and "halogenated aryl" refers to an aryl group that is at least partially halogenated.

[0614] As Y ew1 , preferably a halogen atom, -C(R f1 )(R f2 )-R f3 Represents a halo(cyclo)alkyl or haloaryl group.

[0615] R f1 represents a halogen atom, a perhalogenated alkyl group, a perhalogenated cycloalkyl group or a perhalogenated aryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group.

[0616] R f2 and R f3 Each independently represents a hydrogen atom, a halogen atom or an organic group, R f2 With R f3 Examples of the organic group include alkyl, cycloalkyl and alkoxy groups, which may be substituted by a halogen atom (preferably a fluorine atom). f2 and R f3 Preferably, it is (halo)alkyl or (halo)cycloalkyl. More preferably, R f2 Represents R f1 The same group or the same group as R f3 Connect to form a ring.

[0617] As R f2 With R f3 Examples of the ring formed by connecting the groups include a (halo)cycloalkyl ring.

[0618] As R f1 ~R f3 The (halogen)alkyl group in the group may be either linear or branched. The linear (halogen)alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.

[0619] As R f1 ~R f3 In, or R f2 With R f3 The (halogen)cycloalkyl group in the ring formed by connecting the groups may be monocyclic or polycyclic. When the ring is polycyclic, the (halogen)cycloalkyl group may be bridged. In other words, in this case, the (halogen)cycloalkyl group may have a bridged structure.

[0620] Examples of these (halogen)cycloalkyl groups include groups represented by the following formulae and halogenated groups thereof: In addition, a part of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[0621] [Chemical Formula 49]

[0622]

[0623] As R f2 and R f3 In, or R f2 With R f3 The (halogen)cycloalkyl group in the ring formed by connecting is preferably -C (n) F (2n -2) a fluorocycloalkyl group represented by H. The number of carbon atoms n is not particularly limited, but is preferably 5 to 13, more preferably 6.

[0624] As Y ew1 In, or R f1 The (per)halogenated aryl group in the (n) F (n-1) Here, the number of carbon atoms n is not particularly limited, but is preferably 5 to 13, more preferably 6.

[0625] As R ew1 、R ew2 and Y ew1 At least two of them may be linked to each other to form a ring, which is preferably a cycloalkyl group or a heterocyclic group.

[0626] Each group and each ring constituting the partial structure represented by the above formula EW may further have a substituent.

[0627] In the above formula W, R 20 An alkyl group substituted with one or more substituted groups selected from the group consisting of a halogen atom, a cyano group, and a nitro group is preferred, an alkyl group substituted with a halogen atom (haloalkyl) is more preferred, and a fluoroalkyl group is further preferred. The alkyl group substituted with one or more substituted groups selected from the group consisting of a halogen atom, a cyano group, and a nitro group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

[0628] More specifically, R 20 Preferably, -C(R' 1 )(R' f1 )(R' f2 ) or -C(R' 1 )(R' 2 )(R' f1 ) represents an atomic group. R' 1 and R' 2R' represents independently a hydrogen atom or an alkyl group which is not substituted by an electron-withdrawing group (preferably unsubstituted). f1 and R' f2 Each independently represents a halogen atom, a cyano group, a nitro group or a perfluoroalkyl group.

[0629] As R' 1 and R' 2 The alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0630] As R' f1 and R' f2 The perfluoroalkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0631] As R 20 Preferred specific examples include -CF3, -C2F5, -C3F7, -C4F9, -CF(CF3)2, -CF(CF3)C2F5, -CF2CF(CF3)2, -C(CF3)3, -C5F 11 、-C6F 13 、-C7F 15 、-C8F 17 , -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, -CH(CF3)C2F5, -CH2CF(CF3)2, and -CH2CN. Among them, -CF3, -C2F5, -C3F7, -C4F9, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN are preferred, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN are more preferred, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN are further preferred, and -CH2C2F5, -CH(CF3)2, or -CH2CN are particularly preferred, and -CH2C2F5 or -CH(CF3)2 are particularly preferred.

[0632] As the structural unit represented by the formula X, a structural unit represented by the following formula X-1 or formula X-2 is preferred, and a structural unit represented by the formula X-1 is more preferred.

[0633] [Chemical Formula 50]

[0634]

[0635] In formula X-1, R 20 represents an electron-withdrawing group, L 2 represents a divalent linking group, X 2 represents an oxygen atom or a sulfur atom, Z 2 represents a halogen atom.

[0636] In formula X-2, R 20 represents an electron-withdrawing group, L 3 represents a divalent linking group, X 3 represents an oxygen atom or a sulfur atom, Z 3 represents a halogen atom.

[0637] As L 2 and L 3 Specific examples and preferred examples of the divalent linking group are the same as those described for L as the divalent linking group in the above formula X.

[0638] As R 2 and R 3 The electron withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above. A halo(cyclo)alkyl group is more preferable.

[0639] In the above formula X-1, L 2 With R 2 will not bond to each other to form a ring. In the above formula X-2, L 3 With R 3 They do not bond to each other to form a ring.

[0640] As X 2 and X 3 , preferably an oxygen atom.

[0641] As Z 2 and Z 3 , preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

[0642] Furthermore, as the structural unit represented by the formula X, a structural unit represented by the formula X-3 is also preferred.

[0643] [Chemical Formula 51]

[0644]

[0645] In formula X-3, R 20 Represents an electron-withdrawing group, R 21 represents a hydrogen atom, an alkyl group or an aryl group, L 4 represents a divalent linking group, X 4 represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

[0646] As L 4 Specific examples and preferred examples of the divalent linking group are the same as those described for L in formula X as the divalent linking group.

[0647] As R 4 The electron withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above. A halo(cyclo)alkyl group is more preferable.

[0648] In the above formula X-3, L 4 With R 4 They do not bond to each other to form a ring.

[0649] As X 4 , preferably an oxygen atom.

[0650] Furthermore, as the structural unit represented by formula X, a structural unit represented by formula Y-1 or a structural unit represented by formula Y-2 is also preferred.

[0651] [Chemical Formula 52]

[0652]

[0653] In formula Y-1 and formula Y-2, Z represents a halogen atom, R 11 The group represented by OCH2- or R 12 OC(=O)CH2- represented group, R 11 and R 12 Each independently represents a substituent, R 20 Represents an electron-withdrawing group.

[0654] As R 20 The electron withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above. A halo(cyclo)alkyl group is more preferable.

[0655] As the halogen atom of Z, R 11 The group represented by OCH2- and the group represented by R 12 Specific examples and preferred examples of the group represented by OC(=O)CH2- are the same as those described in the above formula 1.

[0656] The content of the structural unit represented by formula X is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, and further preferably 30 to 100 mol %, based on all structural units in the fluorine-containing resin.

[0657] Preferred examples of the structural units constituting the hydrophobic resin (E) are shown below.

[0658] Preferred examples of the hydrophobic resin (E) include resins obtained by arbitrarily combining these structural units and resins F-1 and F-2 used in Examples, but the present invention is not limited thereto.

[0659] [Chemical Formula 53]

[0660]

[0661] [Chemical Formula 54]

[0662]

[0663] The hydrophobic resin (E) may be used alone or in combination of two or more.

[0664] From the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure, it is preferred to use a mixture of two or more hydrophobic resins (E) having different surface energies.

[0665] The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.

[0666] (B) Photoacid generator

[0667] The composition according to the present invention contains a photoacid generator (hereinafter also referred to as "photoacid generator (B)").

[0668] The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.

[0669] The photoacid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation. Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

[0670] As the photoacid generator, known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, known compounds disclosed in paragraphs 0125 to 0319 of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0086 to 0094 of U.S. Patent Application Publication No. 2015 / 0004544, and paragraphs 0323 to 0402 of U.S. Patent Application Publication No. 2016 / 0237190 can be preferably used as the photoacid generator (B).

[0671] [Compounds represented by formula ZI, ZII and ZIII]

[0672] Preferred embodiments of the photoacid generator (B) include compounds represented by the following formulae ZI, ZII, and ZIII.

[0673] [Chemical Formula 55]

[0674]

[0675] In the above formula ZI,

[0676] R 201 、R 202 and R 203 Each independently represents an organic group.

[0677] As R 201 、R 202 and R 203 The number of carbon atoms in the organic group is preferably 1-30, more preferably 1-20.

[0678] And, R 201 ~R 203 Two of them may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group in the ring. 201 ~R 203 Examples of the group formed by bonding two of the groups include alkylene (e.g., butylene, pentylene) and -CH2-CH2-O-CH2-CH2-.

[0679] Z - Indicates anion.

[0680] [Cation in the compound represented by formula ZI]

[0681] Preferred embodiments of the cation in formula ZI include corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described later.

[0682] In addition, the photoacid generator (B) may also be a compound having a plurality of structures represented by the formula ZI. For example, R 201 ~R 203 At least one of the R 201 ~R 203 A compound having a structure in which at least one of the compounds is bonded by a single bond or a linking group.

[0683] -Compound ZI-1-

[0684] First, compound (ZI-1) will be described.

[0685] Compound (ZI-1) is the above formula ZI R 201 ~R 203 An arylsulfonium compound in which at least one of the groups is an aryl group, that is, a compound in which the arylsulfonium group is used as a cation.

[0686] In the arylsulfonium compound, R 201 ~R 203 All are aryl, or R 201 ~R203 Part of the alkyl group is an aryl group, and the rest are an alkyl group or a cycloalkyl group.

[0687] Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0688] The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

[0689] The alkyl group or cycloalkyl group that the arylsulfonium compound may have as needed is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0690] R 201 ~R 203 The aryl group, alkyl group and cycloalkyl group in the group may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group as a substituent.

[0691] -Compound ZI-2-

[0692] Next, compound (ZI-2) will be described.

[0693] Compound (ZI-2) is a compound of formula ZI wherein R 201 ~R 203 Each independently represents a compound of an organic group that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0694] As R 201 ~R 203 The organic group having no aromatic ring preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.

[0695] R 201 ~R 203 Each independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and further preferably a linear or branched 2-oxoalkyl group.

[0696] As R 201 ~R 203 The alkyl and cycloalkyl groups in the alkyl group are preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched-chain alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl).

[0697] R 201 ~R 203 It may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0698] -Compound ZI-3-

[0699] Next, compound (ZI-3) will be described.

[0700] The compound (ZI-3) is represented by the following formula ZI-3 and has a phenacylsulfonium salt structure.

[0701] [Chemical Formula 56]

[0702]

[0703] In formula ZI-3, R 1c ~R 5c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group, and R 6c and R 7c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group, and R x and R y Each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

[0704] R 1c ~R 5c Any two or more of R 5c With R 6c 、R 6c With R 7c 、R 5c With R x and R x With R y They may be bonded to form a ring structure, and the ring structure may independently contain an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond.

[0705] Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0706] As R 1c ~R 5c Any two or more of R 6c With R 7c and R x With R y Examples of the group formed by bonding include butylene and pentylene.

[0707] As R 5c With R 6c and R 5c With R x The group formed by the bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0708] Zc - Indicates anion.

[0709] -Compound ZI-4-

[0710] Next, compound (ZI-4) will be described.

[0711] The compound (ZI-4) is represented by the following formula ZI-4.

[0712] [Chemical Formula 57]

[0713]

[0714] In formula ZI-4, l represents an integer of 0 to 2, r represents an integer of 0 to 8, and R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group, and these groups may have a substituent, R 14 Each independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group, and these groups may have a substituent. 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, which may have a substituent. 15 They may be bonded to each other to form a ring.

[0715] When 2 R 15 When they are bonded to each other to form a ring, heteroatoms such as oxygen atoms and nitrogen atoms may be contained in the ring skeleton. 15 The alkylene groups are preferably bonded to each other to form a ring structure.

[0716] Z - Indicates anion.

[0717] In formula ZI-4, R 13 、R 14 and R 15 The alkyl group is linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group, a tert-butyl group or the like.

[0718] [Cation in the compound represented by formula ZII or formula ZIII]

[0719] Next, formulae ZII and ZIII are described.

[0720] In Formula ZII and Formula ZIII, R 204 ~R 207 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0721] As R 204 ~R 207 R is an aryl group, preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0722] As R 204 ~R 207 The alkyl and cycloalkyl groups preferably include straight-chain alkyl groups having 1 to 10 carbon atoms, branched-chain alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0723] R 204 ~R 207 The aryl group, alkyl group and cycloalkyl group of R may each independently have a substituent. 204 ~R 207 The aryl, alkyl and cycloalkyl groups may have substituents, for example, alkyl groups (for example, having 1 to 15 carbon atoms), cycloalkyl groups (for example, having 3 to 15 carbon atoms), aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups and phenylthio groups.

[0724] Z - Indicates anion.

[0725] [Anions in compounds represented by formula ZI to formula ZIII]

[0726] As Z in formula ZI - 、Z in formula ZII - 、Zc in formula ZI-3 - And Z in formula ZI-4 - , preferably an anion represented by the following formula An-1.

[0727] [Chemical Formula 58]

[0728]

[0729] In formula An-1, pf represents an integer of 0 to 10, qf represents an integer of 0 to 10, rf represents an integer of 1 to 3, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, when rf is an integer of 2 or more, multiple -C(Xf)2- may be the same or different, R 4 and R 5 Each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When pf is an integer greater than 2, multiple -CR 4f R 5f - can be the same or different, L f represents a divalent linking group, and when qf is an integer greater than 2, multiple L f They may be the same or different, and W represents an organic group containing a cyclic structure.

[0730] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0731] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More preferably, Xf is a fluorine atom or CF3. It is particularly preferred that both Xf are fluorine atoms.

[0732] R 4f and R 5f Each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. 4f and R 5f They can be the same or different.

[0733] As R 4f and R 5f The alkyl group may have a substituent, and preferably has 1 to 4 carbon atoms. 4f and R 5f Preferred is a hydrogen atom.

[0734] Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in Formula An-1.

[0735] L f represents a divalent linking group, and when there are multiple L f They can be the same or different.

[0736] Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups obtained by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene- are more preferred.

[0737] W represents an organic group containing a cyclic structure, among which a cyclic organic group is preferred.

[0738] Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

[0739] The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl. Preferred are alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl.

[0740] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0741] The heterocyclic group may be monocyclic or polycyclic. Polycyclic heterocyclic groups can further inhibit acid diffusion. Furthermore, the heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocyclic rings include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples of lactone and sultone rings include the lactone and sultone structures exemplified in the resins described above. Particularly preferred heterocyclic rings in the heterocyclic group are furan rings, thiophene rings, pyridine rings, and decahydroisoquinoline rings.

[0742] The cyclic organic group may have a substituent. Examples of such substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atoms that constitute the cyclic organic group (the carbon atoms that contribute to ring formation) may be carbonyl carbon atoms.

[0743] As the anion represented by the formula An-1, SO3 can be preferably mentioned. - -CF2-CH2-OCO-(L f )q'-W、SO3 - -CF2-CHF-CH2-OCO-(L f )q'-W、SO3 - -CF2-COO-(L f )q'-W、SO3 - -CF2-CF2-CH2-CH2-(L f ) qf -W, SO3 - -CF2-CH(CF3)-OCO-(L f )q'-W. Here, L f , qf and W are the same as those in formula An-1. q' represents an integer of 0 to 10.

[0744] In one embodiment, Z in formula ZI - 、Z in formula ZII - 、Zc in formula ZI-3 - And Z in formula ZI-4 - , and an anion represented by the following formula 4 is also preferred.

[0745] [Chemical Formula 59]

[0746]

[0747] In formula 4, X B1 and X B2 Each independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. B1 and X B2 Preferred is a hydrogen atom.

[0748] X B3 and X B4 Each independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is a fluorine atom or a monovalent organic group having a fluorine atom, and more preferably X B3 and X B4 Both of them are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 Both of these are alkyl groups substituted with fluorine.

[0749] L f , qf and W are the same as those in Formula 3.

[0750] As Z in formula ZI - 、Z in formula ZII - 、Zc in formula ZI-3 - And Z in formula ZI-4 - , preferably an anion represented by the following formula 5.

[0751] [Chemical Formula 60]

[0752]

[0753] In formula 5, Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and Xb each independently represents a hydrogen atom or an organic group without a fluorine atom. 4f 、R 5f , L f The definitions and preferred methods of W are the same as those in Formula 3.

[0754] Z in formula ZI - 、Z in formula ZII - 、Zc in formula ZI-3 - And Z in formula ZI-4 - It may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0755] As Z in formula ZI - , Z in formula ZII - 、Zc in formula ZI-3 -And Z in formula ZI-4 - , and an aromatic sulfonic acid anion represented by the following formula SA1 is also preferred.

[0756] [Chemical Formula 61]

[0757]

[0758] In formula SA1, Ar represents an aromatic group and may further have a sulfonic acid anion and -(DR B ) other than a substituent. Examples of the substituent that may be present include a fluorine atom, a hydroxyl group, and the like.

[0759] n represents an integer greater than or equal to 0. n is preferably 1 to 4, more preferably 2 to 3, and particularly preferably 3.

[0760] D represents a single bond or a divalent linking group. Examples of the divalent linking group include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate groups, ester groups, and groups composed of two or more of these.

[0761] R B Represents a hydrocarbon group.

[0762] Preferably D is a single bond, R B It is an aliphatic hydrocarbon structure. B More preferred is isopropyl or cyclohexyl.

[0763] Preferred examples of the sulfonium cation in Formula ZI and the sulfonium cation or iodonium cation in Formula ZII are shown below.

[0764] [Chemical Formula 62]

[0765]

[0766] The anion Z in formula ZI and formula ZII is shown below: - 、Zc in formula ZI-3 - And Z in formula ZI-4 - The preferred example.

[0767] [Chemical Formula 63]

[0768]

[0769] Any combination of the above-mentioned cations and anions can be used as the photoacid generator.

[0770] The photoacid generator is an ionic compound containing a cation and an anion, and the anion preferably contains an ion represented by any one of the above-mentioned formula An-1, the following formula An-2, and the following formula An-3.

[0771] [Chemical Formula 64]

[0772]

[0773] In formula An-2 and formula An-3, Rfa each independently represents a monovalent organic group having a fluorine atom, and a plurality of Rfa may be bonded to each other to form a ring.

[0774] Rfa is preferably an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0775] Furthermore, it is preferred that a plurality of Rfa groups are bonded to each other to form a ring.

[0776] Furthermore, as the photoacid generator, compounds C-1 to C-15 used in the examples can also be preferably mentioned, but the present invention is not limited thereto.

[0777] The photoacid generator may be in the form of a low molecular weight compound or in the form of being embedded in a part of a polymer. Furthermore, the low molecular weight compound form and the form of being embedded in a part of a polymer may be used in combination.

[0778] The photoacid generator is preferably in the form of a low molecular weight compound.

[0779] When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0780] When the photoacid generator is in a form of being embedded in a part of the polymer, it may be embedded in a part of the resin (A) or in a resin different from the resin (A).

[0781] The photoacid generator may be used alone or in combination of two or more.

[0782] The content of the photoacid generator in the composition (the total amount when two or more types are present) is preferably 0.1% by mass to 35% by mass, more preferably 0.5% by mass to 25% by mass, further preferably 2% by mass to 20% by mass, and particularly preferably 2.5% by mass to 20% by mass, based on the total solid content of the composition.

[0783] When the photoacid generator contains a compound represented by the above-mentioned formula ZI-3 or formula ZI-4, the content of the photoacid generator contained in the composition (when multiple types are present, the total amount) is preferably 5% by mass to 35% by mass, and more preferably 7% by mass to 30% by mass, based on the total solid content of the composition.

[0784] <(D) Acid diffusion controller (excluding those corresponding to amine oxides)>

[0785] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains an acid diffusion controller (excluding those corresponding to amine oxides) (also referred to as "acid diffusion controller (D)").

[0786] The acid diffusion controller (D) is a compound different from the above-mentioned amine oxide (P).

[0787] As a preferred embodiment, the acid diffusion controller (D) is preferably an amine compound.

[0788] The acid diffusion controller (D) traps the acid generated from the acid generator during exposure and functions as a quencher, suppressing the reaction of the acid-decomposable resin in the unexposed area due to the excess acid. Examples of the acid diffusion controller (D) include a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, an onium salt (DC) that is relatively weak acid relative to the acid generator, a low molecular weight compound (DD) containing a nitrogen atom and a group that dissociates upon the action of an acid, and an onium salt compound (DE) containing a nitrogen atom in the cation portion.

[0789] Among them, from the viewpoint of linearity of a pattern obtained over time, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing compound as the acid diffusion controller (D), and more preferably contains a nitrogen-containing basic compound.

[0790] In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a known acid diffusion controller can be appropriately used. For example, the known compounds disclosed in paragraphs 0627 to 0664 of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0095 to 0187 of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs 0403 to 0423 of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs 0259 to 0328 of U.S. Patent Application Publication No. 2016 / 0274458 can be preferably used as the acid diffusion controller (D).

[0791] [Basic compounds (DA)]

[0792] Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulas A to E.

[0793] [Chemical Formula 65]

[0794]

[0795] In formulas A and E,

[0796] R 200 、R 201 and R 202 R may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 20 carbon atoms). 201 With R 202 They may be bonded to each other to form a ring.

[0797] R 203 、R 204 、R 205 and R 206 They may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0798] The alkyl group in Formula A and Formula E may have a substituent or may be unsubstituted.

[0799] As the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.

[0800] The alkyl groups in Formula A and Formula E are more preferably unsubstituted.

[0801] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, and more preferably a compound having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond.

[0802] [Basic compounds whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (DB)]

[0803] A basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") is a compound having a proton-accepting functional group and which decomposes by irradiation with actinic rays or radiation, thereby reducing or eliminating the proton-accepting property or changing from proton-accepting property to acidic property.

[0804] A proton-accepting functional group is a functional group having a group or electron capable of electrostatically interacting with a proton, and includes, for example, a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π conjugation. An example of a nitrogen atom having an unshared electron pair that does not contribute to π conjugation is a nitrogen atom having a partial structure represented by the following formula.

[0805] [Chemical Formula 66]

[0806]

[0807] Preferred partial structures of the proton-accepting functional group include, for example, crown ether, azacrown ether, primary amine, secondary amine, tertiary amine, pyridine, imidazole, and pyrazine structures.

[0808] Compound (DB) decomposes upon irradiation with actinic rays or radiation, thereby generating a compound whose proton-accepting property decreases or disappears, or whose proton-accepting property changes to an acidic state. Here, the decrease or disappearance of proton-accepting property, or the change from proton-accepting property to an acidic state, refers to a change in proton-accepting property caused by the addition of a proton to a proton-accepting functional group. Specifically, this refers to a decrease in the equilibrium constant in the chemical equilibrium when a proton adduct is generated from a compound (DB) having a proton-accepting functional group and a proton.

[0809] The proton acceptor property can be confirmed by pH measurement.

[0810] The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and even more preferably -13<pKa<-3.

[0811] The acid dissociation constant pKa represents the acid dissociation constant pKa in aqueous solution, for example, as defined in Chemistry Handbook (II) (revised 4th edition, 1993, compiled by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. The acid dissociation constant pKa in aqueous solution can be specifically measured by using an infinite dilution aqueous solution to determine the acid dissociation constant at 25°C. Alternatively, it can be obtained by using the following software package 1 and calculating the value of a database based on Hammett's substituent constant and a known literature value. The values of all pKa recorded in this specification represent the values obtained by calculation using the software package.

[0812] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0813] [Onium salt (DC) that is a relatively weak acid relative to the photoacid generator]

[0814] In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, an onium salt (DC) that becomes a relatively weak acid with respect to the photoacid generator can be used as the acid diffusion controller (D).

[0815] When a photoacid generator is used in combination with an onium salt that generates an acid relatively weak compared to the acid generated by the photoacid generator, if the acid generated by the photoacid generator collides with the onium salt containing unreacted weak acid anions upon irradiation with actinic rays or radiation, the weak acid is released through salt exchange, generating an onium salt containing a strong acid anion. This process exchanges the strong acid for the weaker acid with lower catalytic activity, thus ostensibly deactivating the acid and controlling its diffusion.

[0816] From the viewpoint of depth of focus tolerance and pattern linearity, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further contains at least one compound selected from the group consisting of compounds represented by Formula d1-1 to Formula d1-3.

[0817] [Chemical Formula 67]

[0818]

[0819] In formulas d1-1 to d1-3, R 51 represents a hydrocarbon group which may have a substituent, Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, wherein no fluorine atom is bonded to the carbon atom adjacent to the S atom, and R 52 represents an organic group, Y 3 represents a linear, branched or cyclic alkylene or arylene group, Rf represents a hydrocarbon group containing a fluorine atom, M + Each independently represents an ammonium cation, a sulfonium cation or an iodonium cation.

[0820] As M + Preferred examples of the sulfonium cation or iodonium cation represented by include the sulfonium cation exemplified by Formula ZI and the iodonium cation exemplified by Formula ZII.

[0821] The onium salt (DC) that is a relatively weak acid relative to the photoacid generator may be a compound having a cationic site and an anionic site in the same molecule, wherein the cationic site and anionic site are linked by a covalent bond (hereinafter also referred to as "compound (DCA)").

[0822] The compound (DCA) is preferably a compound represented by any one of the following formulas C-1 to C-3.

[0823] [Chemical Formula 68]

[0824]

[0825] In formulas C-1 to C-3, R 1 、R 2 and R 3Each independently represents a substituent having 1 or more carbon atoms.

[0826] L 1 It represents a divalent linking group or a single bond that connects the cationic portion and the anionic portion.

[0827] -X - Indicates a group selected from -COO - 、-SO3 - 、-SO2 - and -N - -R 4 The anion site in R 4 It represents a monovalent substituent having at least one of a carbonyl group (—C(═O)—), a sulfonyl group (—S(═O) 2 —), and a sulfinyl group (—S(═O)—) at the bonding site to the adjacent nitrogen atom.

[0828] R 1 、R 2 、R 3 、R 4 and L 1 can be bonded to each other to form a ring structure. 1 ~R 3 The two together represent a divalent substituent, and may be bonded to the nitrogen atom via a double bond.

[0829] As R 1 ~R 3 The substituent having 1 or more carbon atoms in may be an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, or an arylaminocarbonyl group. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

[0830] L as a divalent linking group 1 Examples of the group include linear or branched alkylene groups, cycloalkylene groups, arylene groups, carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these groups. 1 An alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these is preferred.

[0831] [Low molecular weight compound having a nitrogen atom and a group that can be separated by the action of an acid (DD)]

[0832] The low molecular weight compound (DD) having a nitrogen atom and a group detachable by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having a group detachable by the action of an acid on the nitrogen atom.

[0833] The group that is released by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group.

[0834] The molecular weight of the compound (DD) is preferably 100 to 1,000, more preferably 100 to 700, and even more preferably 100 to 500.

[0835] Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group may be represented by the following formula d-1.

[0836] [Chemical Formula 69]

[0837]

[0838] In formula d-1,

[0839] R b Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). b Can be connected to each other to form a ring.

[0840] R b The alkyl, cycloalkyl, aryl and aralkyl groups represented by R may be independently substituted by a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group or a halogen atom. b The same applies to the alkoxyalkyl groups represented.

[0841] As R b , preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group, more preferably a linear or branched alkyl group or a cycloalkyl group.

[0842] As two R b Examples of the rings formed by mutually connecting hydrocarbons include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

[0843] Examples of specific structures of the group represented by formula d-1 include the structure disclosed in paragraph 0466 of US Patent Application Publication No. 2012 / 0135348, but the present invention is not limited thereto.

[0844] The compound (DD) preferably has a structure represented by Formula 6 below.

[0845] [Chemical Formula 70]

[0846]

[0847] In formula 6,

[0848] 1 represents an integer from 0 to 2, m represents an integer from 1 to 3, and 1+m=3 is satisfied.

[0849] R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. a Can be the same or different, 2 R a They may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.

[0850] R b The meaning is the same as R in the above formula d-1 b The same, preferred examples are also the same.

[0851] In formula 6, as R a The alkyl, cycloalkyl, aryl and aralkyl groups may be substituted independently by the same groups as those mentioned above as the following groups, which may be substituted as R b The alkyl, cycloalkyl, aryl and aralkyl groups are substituted.

[0852] As the above R a Specific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted by the above groups) include the same as those for R b The same groups as those exemplified above.

[0853] Specific structures of particularly preferred compounds (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph 0475 of US Patent Application Publication No. 2012 / 0135348.

[0854] The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic site is preferably an amino group, more preferably an aliphatic amino group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferred that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group and halogen atom, etc.) is not directly connected to the nitrogen atom.

[0855] Preferred specific structures of compound (DE) include the compounds disclosed in paragraph 0203 of US Patent Application Publication No. 2015 / 0309408, but are not limited thereto.

[0856] Preferred examples of other acid diffusion controllers (D) are shown below.

[0857] [Chemical Formula 71]

[0858]

[0859] [Chemical Formula 72]

[0860]

[0861] [Chemical Formula 73]

[0862]

[0863] [Chemical Formula 74]

[0864]

[0865] [Chemical Formula 75]

[0866]

[0867] In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, the acid diffusion controller (D) may be used alone or in combination of two or more.

[0868] The content of the acid diffusion controller (D) in the composition (the total when two or more are present) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the composition.

[0869] Solvents

[0870] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a solvent (also referred to as "solvent (F)"), and more preferably contains an organic solvent.

[0871] In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, known resist solvents can be used as appropriate. For example, known solvents disclosed in paragraphs 0665 to 0670 of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0210 to 0235 of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs 0424 to 0426 of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs 0357 to 0366 of U.S. Patent Application Publication No. 2016 / 0274458 can be preferably used.

[0872] Examples of the solvent that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvic acids.

[0873] As the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in its structure and a solvent not containing a hydroxyl group can be used.

[0874] The hydroxyl-containing solvent and the hydroxyl-free solvent can be appropriately selected from the compounds exemplified above. Hydroxyl-containing solvents are preferably alkylene glycol monoalkyl ethers or alkyl lactates, and more preferably propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate. Furthermore, hydroxyl-free solvents are preferably alkylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, optionally ring-containing monoketone compounds, cyclic lactones, or alkyl acetates. Among these, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone are even more preferred. Propylene carbonate is also preferred as a hydroxyl-free solvent. Among these, from the viewpoint of uniformity of the formed layer, it is particularly preferred that the solvent contains γ-butyrolactone.

[0875] The mixing ratio (mass ratio) of the hydroxyl-containing solvent to the hydroxyl-free solvent is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of the hydroxyl-free solvent is preferred.

[0876] The solvent preferably contains propylene glycol monomethyl ether acetate. It may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more solvents containing propylene glycol monomethyl ether acetate.

[0877] The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, but is preferably 0.5 to 50% by mass, more preferably 1.0 to 45% by mass, and even more preferably 1.0 to 40% by mass.

[0878] When a film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed to KrF excimer laser light, the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more.

[0879] The solid content concentration refers to the mass percentage of the resist components other than the solvent and the amine oxide (P) relative to the total mass of the composition.

[0880] Cross-linking agent

[0881] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter also referred to as "crosslinking agent (G)").

[0882] As the crosslinking agent (G), a known compound can be used as appropriate. For example, the known compounds disclosed in paragraphs 0379 to 0431 of U.S. Patent Application Publication No. 2016 / 0147154 and paragraphs 0064 to 0141 of U.S. Patent Application Publication No. 2016 / 0282720 can be preferably used as the crosslinking agent (G).

[0883] The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking the resin. Examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, a xylan ring, and an oxetane ring.

[0884] The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, a xylan ring, or an oxetane ring.

[0885] The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinkable groups.

[0886] The crosslinking agent (G) is more preferably a phenol derivative, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure) having a methylol group or an alkoxymethyl group.

[0887] The cross-linking agent may be used alone or in combination of two or more.

[0888] The content of the crosslinking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, relative to the total solid content of the composition.

[0889] <(H) Surfactant>

[0890] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain a surfactant (also referred to as "surfactant (H)").

[0891] In a preferred embodiment, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention further contains a surfactant (H). When containing a surfactant, it is preferably at least one of a fluorine-based surfactant and a silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or a surfactant having both a fluorine atom and a silicon atom).

[0892] By incorporating a surfactant into the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a resist pattern having good sensitivity and resolution, good adhesion, and few development defects can be obtained when using an exposure light source having a wavelength of 250 nm or less, particularly a wavelength of 220 nm or less.

[0893] Examples of the fluorine-based or silicone-based surfactant include the surfactants described in paragraph 0276 of US Patent Application Publication No. 2008 / 0248425.

[0894] Furthermore, surfactants other than fluorine-based or silicone-based surfactants described in paragraph 0280 of US Patent Application Publication No. 2008 / 0248425 may also be used.

[0895] These surfactants may be used alone or in combination of two or more.

[0896] When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass %, based on the total solid content of the composition.

[0897] On the other hand, by increasing the surfactant content to 0.0001% by mass or more relative to the total solids content of the composition, the uneven distribution of the hydrophobic resin surface increases, thereby making the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic and improving water-conformability during immersion exposure.

[0898] <Other additives>

[0899] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain other known additives.

[0900] Examples of other additives include acid growth agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution accelerators.

[0901] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably prepared by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the resultant, and then applying the resultant to a predetermined support (substrate).

[0902] The pore size (pore diameter) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less.

[0903] Furthermore, when the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less.

[0904] The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. During filtration, as disclosed in Japanese Patent Application Laid-Open No. 2002-62667, filtration can be performed in a cycle, or multiple filters can be connected in series or in parallel. Furthermore, the composition can be filtered multiple times. Furthermore, the composition can be degassed before and after filtration.

[0905] The thickness of the resist film formed from the actinic ray- or radiation-sensitive resin composition of the present invention is not particularly limited, but is preferably 90 nm or less, more preferably 85 nm or less, from the perspective of improving resolution. Such a film thickness can be achieved by setting the solids concentration in the composition within an appropriate range to provide an appropriate viscosity and improve coating and film-forming properties.

[0906] <Application>

[0907] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon exposure to light. More specifically, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used in the manufacturing process of semiconductors such as ICs (Integrated Circuits), the manufacture of circuit substrates such as liquid crystal displays or thermal heads, the production of mold structures for imprinting, other photosensitive etching processes, or the manufacture of lithographic printing plates or acid-curable compositions. Resist patterns formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, and MEMS (Micro Electro Mechanical Systems).

[0908] (Photosensitive or radiation-sensitive film)

[0909] The actinic ray-sensitive or radiation-sensitive film (preferably a resist film) of the present invention is a film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. The actinic ray-sensitive or radiation-sensitive film of the present invention is a cured product of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.

[0910] The cured product in the present invention may be a cured product obtained by removing at least a portion of the solvent from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.

[0911] Specifically, the actinic ray-sensitive or radiation-sensitive film according to the present invention can be obtained by, for example, applying the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention on a support such as a substrate and then drying the coating.

[0912] The drying refers to removing at least a portion of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.

[0913] The drying method is not particularly limited, and a known method can be used, and examples thereof include drying by heating (for example, 70° C. to 130° C., 30 seconds to 300 seconds).

[0914] The heating method is not particularly limited, and a known heating method can be used. Examples of the heating method include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.

[0915] The components contained in the actinic ray-sensitive or radiation-sensitive film according to the present invention are the same as those obtained by removing the solvent from the components contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, and preferred aspects are also the same.

[0916] The content of each component contained in the actinic ray-sensitive or radiation-sensitive film involved in the present invention is equivalent to replacing the description of "total solid content" in the description of the content of each component other than the solvent of the actinic ray-sensitive or radiation-sensitive resin composition involved in the present invention with "total mass of the actinic ray-sensitive or radiation-sensitive film".

[0917] The thickness of the actinic ray-sensitive or radiation-sensitive film according to the present invention is not particularly limited, but is preferably 50 nm to 150 nm, and more preferably 80 nm to 130 nm.

[0918] Furthermore, as memory devices become three-dimensional, when forming a thick photosensitive or radiation-sensitive film, the thickness is preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and even more preferably 2 μm or more and 20 μm or less.

[0919] [Pattern Formation Method]

[0920] The pattern forming method of the present invention includes the following steps:

[0921] a step of exposing the actinic ray-sensitive or radiation-sensitive film (preferably a resist film) according to the present invention to actinic rays or radiation (exposure step); and

[0922] A step of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step using a developer

[0923] (Development process).

[0924] Furthermore, the pattern forming method according to the present invention may include the following steps: forming an actinic ray-sensitive or radiation-sensitive film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (film forming step);

[0925] a step of exposing the actinic ray-sensitive or radiation-sensitive film to actinic rays or radiation (exposure step); and

[0926] A step of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step using a developer (development step).

[0927] <Film Formation Process>

[0928] The pattern forming method of the present invention may include a film forming step. Examples of methods for forming an actinic ray-sensitive or radiation-sensitive film in the film forming step include methods for forming an actinic ray-sensitive or radiation-sensitive film by drying as described above in the section on the actinic ray-sensitive or radiation-sensitive film.

[0929] [Carrier]

[0930] The carrier is not particularly limited, and in addition to the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit substrates such as liquid crystals or thermal heads, substrates commonly used in photolithography processes such as other photosensitive etching processes can also be used. Specific examples of the carrier include inorganic substrates such as silicon, SiO2, and SiN.

[0931] Exposure process

[0932] The exposure step is a step of exposing an actinic ray-sensitive or radiation-sensitive film to light.

[0933] The exposure method may be immersion exposure.

[0934] The pattern forming method according to the present invention may include multiple exposure steps.

[0935] The type of light (actinic rays or radiation) used in exposure can be selected in consideration of the properties of the photoacid generator and the desired pattern shape, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams, with far ultraviolet light being preferred.

[0936] For example, the wavelength of actinic rays is preferably 250 nm or less, more preferably 220 nm or less, and even more preferably 1 to 200 nm.

[0937] Specifically, the light used is KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), or electron beams, and preferably ArF excimer laser, EUV, or electron beams.

[0938] Among them, the exposure in the exposure step is preferably performed by liquid immersion exposure using an argon fluoride laser.

[0939] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0940] <Development Process>

[0941] The developer used in the development step may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), but is preferably an aqueous alkaline solution.

[0942] 〔Alkaline developer〕

[0943] As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is preferably used, but in addition, aqueous alkaline solutions of inorganic bases, primary amines, secondary amines, tertiary amines, alkanolamines, cyclic amines, and the like can also be used.

[0944] The alkaline developer may also contain an appropriate amount of at least one of an alcohol and a surfactant. The alkaline developer preferably has an alkali concentration of 0.1% to 20% by mass and a pH of 10 to 15.

[0945] The development time using the alkaline developer is preferably 10 seconds to 300 seconds.

[0946] The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

[0947] 〔Organic developer〕

[0948] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0949] -Ketone solvents-

[0950] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0951] -Ester solvents-

[0952] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0953] -Other solvents-

[0954] As the alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent, solvents disclosed in paragraphs 0715 to 0718 of U.S. Patent Application Publication No. 2016 / 0070167 can be used.

[0955] The above solvents may be mixed with multiple types or with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.

[0956] The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the developer.

[0957] 〔Surfactant〕

[0958] The organic developer may contain an appropriate amount of a known surfactant as needed.

[0959] The content of the surfactant is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and even more preferably 0.01% by mass to 0.5% by mass, relative to the total mass of the developer.

[0960] 〔Acid diffusion controller〕

[0961] The organic developer may contain the above-mentioned acid diffusion controller.

[0962] [Development Method]

[0963] As a developing method, for example, a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of causing the developer to bulge on the surface of the substrate and remain stationary for a certain period of time due to surface tension (puddle method), a method of spraying the developer onto the surface of the substrate (spray method), or a method of continuously spraying the developer while scanning a developer spray nozzle at a certain speed on a substrate rotating at a certain speed (dynamic dispense method).

[0964] A development step using an aqueous alkaline solution (alkaline development step) and a development step using a developer containing an organic solvent (organic solvent development step) may be combined. This allows pattern formation while leaving only the region with intermediate exposure intensities undissolved, thereby enabling formation of a finer pattern.

[0965] <Preheating process, post-exposure heating process>

[0966] The pattern forming method according to the present invention preferably includes a pre-heating (PB: PreBake) step before the exposure step.

[0967] The pattern forming method according to the present invention may include multiple preheating steps.

[0968] The pattern forming method according to the present invention preferably includes a post-exposure bake (PEB) step after the exposure step and before the development step.

[0969] The pattern forming method according to the present invention may include multiple post-exposure heating steps.

[0970] The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C, in both the preheating step and the post-exposure heating step.

[0971] The heating time in both the preheating step and the post-exposure heating step is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and even more preferably 30 seconds to 90 seconds.

[0972] Heating may be performed by a mechanism provided in the exposure device and the developing device, or by using a hot plate or the like.

[0973] <Resist Underlayer Film Formation Step>

[0974] The pattern forming method according to the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) before the film forming step.

[0975] The resist underlayer film forming step is a step of forming a resist underlayer film (e.g., SOG (Spin On Glass), SOC (Spin On Carbon), an antireflective film, etc.) between the resist film and the carrier. As the resist underlayer film, a known organic or inorganic material can be used as appropriate.

[0976] <Protective film formation process>

[0977] The pattern forming method according to the present invention may further include a step of forming a protective film (protective film forming step) before the development step.

[0978] The protective film forming process is the process of forming a protective film (top coat) on the upper layer of the resist film. As a protective film, known materials can be suitably used. For example, it is possible to preferably use a protective film forming composition disclosed in U.S. Patent Application Publication No. 2007 / 0178407 specification, U.S. Patent Application Publication No. 2008 / 0085466 specification, U.S. Patent Application Publication No. 2007 / 0275326 specification, U.S. Patent Application Publication No. 2016 / 0299432 specification, U.S. Patent Application Publication No. 2013 / 0244438 specification, International Publication No. 2016 / 157988. As a protective film forming composition, it is preferably containing the above-mentioned acid diffusion control agent.

[0979] A protective film may be formed on the upper layer of the resist film containing the hydrophobic resin.

[0980] <Rinsing process>

[0981] The pattern forming method according to the present invention preferably includes a step of washing with a rinsing liquid (rinsing step) after the development step.

[0982] [In the case of a development process using an alkaline developer]

[0983] The rinse solution used in the rinse step following the development step using an alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of a surfactant. In this case, after the development or rinse step, a treatment using a supercritical fluid may be performed to remove the developer or rinse solution adhering to the pattern. Furthermore, after the rinse or supercritical fluid treatment, a heat treatment may be performed to remove any residual moisture from the pattern.

[0984] [In the case of a development process using an organic developer]

[0985] The rinsing liquid used in the rinsing step following the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a conventional solution containing an organic solvent can be used. The rinsing liquid preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0986] Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent include the same solvents as described for the developer containing an organic solvent.

[0987] As the rinsing liquid used in the rinsing step in this case, a rinsing liquid containing a monohydric alcohol is more preferred.

[0988] Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specifically, examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl carbinol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol.

[0989] The components may be mixed in multiple forms or may be mixed with organic solvents other than those listed above.

[0990] The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

[0991] The rinsing solution may contain an appropriate amount of a surfactant.

[0992] In the rinsing process, a rinsing liquid containing an organic solvent is used to clean the substrate that has been developed using an organic developer. The method of the cleaning process is not particularly limited. For example, a method of continuously spraying a rinsing liquid on a substrate rotating at a certain speed (spin coating method), a method of immersing the substrate in a tank filled with a rinsing liquid for a certain period of time (immersion method), or a method of spraying a rinsing liquid onto the surface of the substrate (spray coating method) can be applied. Among them, it is preferred to use a spin coating method for cleaning, and after cleaning, the substrate is rotated at a speed of 2,000 rpm to 4,000 rpm (rotations / minute) and the rinsing liquid is removed from the substrate. In addition, it is also preferred to include a heating process (Post Bake) after the rinsing process. The developer and rinsing liquid remaining between and inside the patterns are removed by this heating process. In the heating process after the rinsing process, the heating temperature is preferably 40 to 160°C, and more preferably 70 to 95°C. The heating time is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 90 seconds.

[0993] <Improvement of surface roughness>

[0994] The method for improving the surface roughness of the pattern can also be applied to the pattern formed by the pattern forming method involved in the present invention. As a method for improving the surface roughness of the pattern, for example, the method disclosed in U.S. Patent Application Publication No. 2015 / 0104957, in which a resist pattern is treated by a plasma containing a hydrogen gas, can be cited. In addition, known methods such as those described in Japanese Patent Application Publication No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" can also be applied.

[0995] Furthermore, the resist pattern formed by the above method can be used as a core material (core portion) of the spacer process disclosed in, for example, Japanese Patent Application Laid-Open No. 3-270227 and US Patent Application Publication No. 2013 / 0209941.

[0996] [Method for manufacturing electronic device]

[0997] The method for manufacturing an electronic device according to the present invention includes the pattern forming method according to the present invention. The electronic device manufactured by the method for manufacturing an electronic device according to the present invention is preferably mounted on an electrical or electronic device (e.g., home appliances, OA (Office Automation)-related equipment, media-related equipment, optical equipment, and communication equipment).

[0998] Example

[0999] Below, embodiment is given and embodiment of the present invention is further specifically described.As long as it does not depart from the purpose of embodiment of the present invention, then can change suitably the material, usage amount, ratio, processing content and processing step etc. shown in following embodiment.Therefore, the scope of embodiment of the present invention is not limited to the specific example shown below.In addition, unless otherwise stated, otherwise "part" and "%" are mass references.

[1000] Resin (A)

[1001] The structures of the resins (A-1 to A-17) used are shown below.

[1002] As described above, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). 13 The composition ratio (mol %) of the resin was measured by C-NMR (Nuclear Magnetic Resonance).

[1003] [Chemical Formula 76]

[1004]

[1005] [Chemical Formula 77]

[1006]

[1007] [Chemical Formula 78]

[1008]

[1009] In addition, the unit of the content ratio of each repeating unit of the above resin is mol%.

[1010] Regarding the value of the glass transition temperature (Tg) when the monomer a1 corresponding to the repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature (Tg) of 50°C or less when forming a homopolymer in this specification and examples is formed into a homopolymer, reference can be made to the description of PCT / JP2018 / 018239.

[1011] <Photoacid generator>

[1012] The structures of the photoacid generators (C-1 to C-15) used are shown below. n Bu represents n-butyl, and tBu represents tert-butyl.

[1013] [Chemical Formula 79]

[1014]

[1015] [Chemical formula 80]

[1016]

[1017] [Chemical Formula 81]

[1018]

[1019] <Acid diffusion controller (D)>

[1020] The structure of the acid diffusion controller (D) used is shown below.

[1021] [Chemical Formula 82]

[1022]

[1023] Tri-n-pentylamine (D-9)

[1024] [Chemical Formula 83]

[1025]

[1026] The structures of the cross-linking agents used are shown below.

[1027] [Chemical Formula 84]

[1028]

[1029] The structure of the hydrophobic resin used is shown below. In addition, as described above, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (Mw / Mn) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene conversion). 13 The composition ratio (mol %) of the resin was measured by C-NMR (Nuclear Magnetic Resonance).

[1030] [Chemical Formula 85]

[1031]

[1032] The structures of the amine oxides (P) are shown in Table 1 below.

[1033] [Table 1-1]

[1034] Table 1

[1035]

[1036] [Table 1-2]

[1037] Table 1 (continued)

[1038]

[1039] The surfactants used are shown below.

[1040] [Chemical Formula 86]

[1041]

[1042] E-2: Megafac R-41 (manufactured by DIC Corporation)

[1043] E-3: KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1044] E-4: Megafac F176 (manufactured by DIC Corporation)

[1045] E-5: Megafac R08 (manufactured by DIC Corporation)

[1046] The solvents used are shown below.

[1047] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1048] S-2: Propylene glycol monomethyl ether (PGME)

[1049] S-3: Ethyl lactate

[1050] S-4: Ethyl 3-ethoxypropionate

[1051] S-5: 2-Heptanone

[1052] S-6: Methyl 3-methoxypropionate

[1053] S-7: 3-Methoxybutyl acetate

[1054] S-8: Butyl acetate

[1055] (Examples 1 to 60 and Comparative Examples 1 to 6)

[1056] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (KrF Exposure)

[1057] (Examples 1 to 7, 15 to 18, 23 to 29, 36 to 60, Comparative Examples 1 to 6)

[1058] The components shown in Table 2 were mixed to obtain a solution having the solid content concentration (mass %) described in Table 2. The obtained solution was then filtered through a polyethylene filter having a pore size of 3 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).

[1059] In the examples and comparative examples, the solid content in the resist composition refers to all components except the solvent and the amine oxide (P). The obtained resist composition was used in the examples and comparative examples.

[1060] In the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[1061] <Determination of Amine Oxide (P) Content in Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition>

[1062] The amine oxide (P) in the actinic ray-sensitive or radiation-sensitive resin composition shown in Table 2 was added in the content described in Table 2.

[1063] In addition, the content of amine oxide (P) was measured as follows.

[1064] (Quantitative Method for Amine Oxide (P))

[1065] A resist composition containing amine oxide (P) was prepared and irradiated with ultrasonic waves for 3 minutes using an ultrasonic device (desktop ultrasonic cleaner (#5510), manufactured by Bransonic). The resulting solution was analyzed using a liquid chromatography apparatus (Agilent 1100HPLC G1311A, manufactured by Agilent Technologies, Inc.) using a reverse phase column (Shim-pack CLC-ODS (M), manufactured by SHIMADZU GLC Ltd.) and a UV detector (Agilent 1100HPLC G1315B, manufactured by Agilent Technologies, Inc.).

[1066] The content of amine oxide (P) was quantified by the absolute calibration curve method using standard reagents of amine oxide (P).

[1067] The standard reagent is an amine oxide (P) to be quantified, the concentration of which is known.

[1068] <Pattern formation method (1): KrF exposure, alkaline aqueous solution development>

[1069] Using a spin coater "ACT-8" manufactured by Tokyo Electron Limited, an 8-inch Si substrate (manufactured by Advanced Materials Technology, Inc. (hereinafter also referred to as the "substrate") treated with hexamethyldisilazane was dripped with the resist composition described in Table 2 prepared above, without an antireflection layer, while the substrate was stationary. After the dripping, the substrate was rotated, maintaining its rotation speed at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds. After that, the rotation speed was increased to the film thickness setting speed (1200 rpm) and maintained for 60 seconds. After that, the substrate was heated and dried on a hot plate at 130°C for 60 seconds, forming a positive resist film with a film thickness of 12 μm.

[1070] This resist film was pattern-exposed using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C, wavelength 248 nm) under exposure conditions of NA = 0.60 and σ = 0.75 through a mask having a line and space pattern with a space width of 4.5 μm and a pitch width of 25 μm, such that the pattern formed after reduced projection exposure and development had a space width of 4.5 μm and a pitch width of 25 μm. After exposure, the film was baked at 120°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds, dried, and then baked at 110°C for 60 seconds, forming an isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm.

[1071] The pattern exposure was performed using a mask having a line and space pattern with a space width of 4.5 μm and a pitch width of 25 μm after reduced projection exposure. The exposure amount was set to the optimum exposure amount (sensitivity) (mJ / cm2) for forming an isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm. 2 In the above determination of sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1072] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1073] Performance Evaluation

[1074] [Substrate Adhesion]

[1075] The evaluation pattern wafer was vacuum-treated (evacuated) for 60 seconds in a chamber of a CD-SEM (Critical Dimension-Scanning Electron Microscope) (S-9380II, manufactured by Hitachi, Ltd.) with the pressure in the chamber set to 0.002 Pa.

[1076] After the vacuum treatment, the evaluation pattern wafer was observed with an optical microscope to evaluate adhesion. Specifically, the number of film peelings of the pattern formed on the substrate surface ( / 8-inch wafer) was counted and evaluated based on the following criteria.

[1077] "A": 0 film peeling

[1078] "B": 1 or more and less than 5 film peelings

[1079] "C": 5 or more and less than 50 film peelings

[1080] "D": 50 or more film peelings

[1081] [Sensitivity]

[1082] For each resist composition, identical resist compositions were prepared except that they did not contain amine oxide (P), and isolated space patterns were formed in the same manner as described above. The sensitivity of the resulting isolated space patterns was determined as described above. Using the sensitivity of the isolated space patterns formed using the resist compositions containing no amine oxide (P) as a benchmark, the sensitivity of the isolated space patterns formed using the resist compositions containing amine oxide (P) was evaluated according to the following criteria.

[1083] Among them, the resist composition of Comparative Example 1 did not contain amine oxide (P), and its sensitivity was evaluated as A.

[1084] (Judgment Criteria)

[1085] A: The observed sensitivity reduction is less than 1mJ / cm 2

[1086] B: Observed sensitivity reduction of 1 mJ / cm 2 Above and less than 2mJ / cm 2

[1087] C: Observed sensitivity reduction of 2 mJ / cm 2 Above and less than 3mJ / cm 2

[1088] D: Observed sensitivity reduction is 3 mJ / cm 2 above

[1089] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (ArF Exposure)

[1090] (Examples 8-10, 19-20, 30-31)

[1091] The various components listed in Table 2 were mixed to give the solid content concentrations (mass %) listed in Table 2 to obtain solutions. The resulting solution was filtered first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm. The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the Examples.

[1092] In the present embodiment, the solid content in the resist composition refers to all components except the solvent and the amine oxide (P).

[1093] In the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[1094] The content of amine oxide (P) was measured in the same manner as above.

[1095] <Pattern Formation Method (2): ArF Immersion Exposure, Alkaline Aqueous Solution Development (Positive)>

[1096] An organic antireflective film-forming composition SOC9110D and a Si-containing antireflective film-forming composition HM9825 were applied to a silicon wafer to form an antireflective film. A resist composition was applied to the resulting antireflective film and baked (PB: Prebake) at 100°C for 60 seconds to form a 100 nm thick resist film.

[1097] An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annular, outer sigma 0.9, inner sigma 0.6) was used for the resulting wafer, and exposure was performed through a 6% halftone mask of a 1:1 line and space pattern with a line width of 100nm. Ultrapure water was used as the immersion liquid. Then, it was baked at 90°C (PEB: PostExposure Bake, post-exposure baking) for 60 seconds. Next, tetramethylammonium hydroxide aqueous solution (2.38% by mass) was used as a developer to immerse the surface of the wafer in a rotary manner for 30 seconds and rinsed with pure water to form a 1:1 line and space (LS) pattern with a line width of 100nm.

[1098] In addition, the optimal exposure dose (sensitivity) (mJ / cm2) for forming a 1:1 line and space (LS) pattern with a line width of 100 nm was set. 2 In the above determination of sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1099] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1100] <Pattern Formation Method (3): ArF Immersion Exposure, Organic Solvent Development (Negative)>

[1101] An organic antireflective film-forming composition SOC9110D and a Si-containing antireflective film-forming composition HM9825 were applied to a silicon wafer to form an antireflective film. A resist composition was applied to the resulting antireflective film and baked (PB: Prebake) at 100°C for 60 seconds to form a 100 nm thick resist film.

[1102] The resulting wafer was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annular, outer sigma 0.9, inner sigma 0.6) through a 6% halftone mask with a 1:1 line and space pattern with a line width of 100 nm. Ultrapure water was used as the immersion liquid. Then, it was baked at 90°C (PEB: PostExposure Bake) for 60 seconds. Next, it was developed by immersing in butyl acetate for 30 seconds as a developer and rinsed with methyl isobutyl carbinol (MIBC), thereby forming a 1:1 line and space (LS) pattern with a line width of 100 nm.

[1103] In addition, the optimal exposure dose (sensitivity) (mJ / cm2) for forming a 1:1 line and space (LS) pattern with a line width of 100 nm was set. 2 In the above determination of sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1104] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1105] Performance Evaluation

[1106] Adhesion to the substrate was evaluated using the same evaluation method and evaluation criteria as those for KrF exposure.

[1107] [Sensitivity]

[1108] For each resist composition, identical resist compositions were prepared except that they did not contain amine oxide (P), and line-and-space patterns were formed in the same manner as described above. The sensitivity of the resulting isolated space patterns was determined as described above. Using the sensitivity of the line-and-space patterns formed using the resist compositions containing amine oxide (P) as a benchmark, the sensitivity reduction of the line-and-space patterns formed using the resist compositions containing amine oxide (P) was evaluated according to the following criteria.

[1109] (Judgment Criteria)

[1110] A: The observed sensitivity reduction is less than 1mJ / cm 2

[1111] B: Observed sensitivity reduction of 1 mJ / cm 2 Above and less than 2mJ / cm 2

[1112] C: Observed sensitivity reduction of 2 mJ / cm 2 Above and less than 3mJ / cm 2

[1113] D: Observed sensitivity reduction is 3 mJ / cm 2 above

[1114] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (EUV Exposure)

[1115] (Examples 11-12, 21, 32-33)

[1116] The various components listed in Table 2 were mixed to give the solid content concentrations (mass %) listed in Table 2 to obtain solutions. The resulting solution was filtered first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm. The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the Examples.

[1117] In the present embodiment, the solid content in the resist composition refers to all components except the solvent and the amine oxide (P).

[1118] In the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[1119] The content of amine oxide (P) was measured in the same manner as above.

[1120] <Pattern Formation Method (4): EUV Exposure, Alkaline Development (Positive)>

[1121] AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 30 nm thick underlayer film. A resist composition was applied thereon and baked (PB) at 120°C for 60 seconds to form a 30 nm thick resist film.

[1122] The resist film was patterned using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). A reticle with a line size of 40 nm and a line:space ratio of 1:1 was used.

[1123] The exposed resist film was baked (PEB) at 120°C for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (TMAH, 2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. The silicon wafer was rotated at 4000 rpm for 30 seconds and further baked at 90°C for 60 seconds, resulting in a line-and-space pattern with an 80nm pitch and a 40nm line width (40nm space width).

[1124] In addition, the optimal exposure dose (sensitivity) (mJ / cm2) for forming a line and space (LS) pattern with a line width of 40 nm was set. 2In the above determination of sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1125] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1126] <Pattern Formation Method (5): EUV Exposure, Organic Solvent Development (Negative)>

[1127] AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 30 nm thick underlayer film. The resist composition shown in Table 2 was applied thereto and baked (PB) at 120°C for 60 seconds to form a 30 nm thick resist film.

[1128] The resist film was patterned using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). A reticle with a line size of 40 nm and a line:space ratio of 1:1 was used.

[1129] The exposed resist film was baked (PEB) at 120°C for 60 seconds and then developed with butyl acetate for 30 seconds. The silicon wafer was rotated at 4000 rpm for 30 seconds and then baked at 90°C for 60 seconds, resulting in a line-and-space pattern with an 80nm pitch and a 40nm line width (40nm space width).

[1130] The optimum exposure dose for forming a line and space (LS) pattern with a line width of 40 nm is set as the sensitivity (mJ / cm 2 In the above determination of sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1131] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1132] Performance Evaluation

[1133] Adhesion to the substrate was evaluated using the same evaluation method and evaluation criteria as those for KrF exposure.

[1134] [Sensitivity]

[1135] For each resist composition, identical resist compositions were prepared except that they did not contain amine oxide (P), and line-and-space patterns were formed in the same manner as described above. The sensitivity of the resulting isolated space patterns was determined as described above. Using the sensitivity of the line-and-space patterns formed using the resist compositions containing amine oxide (P) as a benchmark, the sensitivity reduction of the line-and-space patterns formed using the resist compositions containing amine oxide (P) was evaluated according to the following criteria.

[1136] (Judgment Criteria)

[1137] A: The observed sensitivity reduction is less than 1mJ / cm 2

[1138] B: Observed sensitivity reduction of 1 mJ / cm 2 Above and less than 2mJ / cm 2

[1139] C: Observed sensitivity reduction of 2 mJ / cm 2 Above and less than 3mJ / cm 2

[1140] D: Observed sensitivity reduction is 3 mJ / cm 2 above

[1141] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (EB Exposure)

[1142] (Examples 13, 14, 22, 34, 35)

[1143] The various components shown in Table 2 were mixed to obtain a solution so as to have the solid content concentration (mass %) described in Table 2. The obtained liquid was filtered through a polytetrafluoroethylene filter having a pore size of 0.03 μm to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).

[1144] In the present embodiment, the solid content in the resist composition refers to all components except the solvent and the amine oxide (P).

[1145] In the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[1146] The content of the amine oxide (P) specific additive was measured in the same manner as above.

[1147] <Pattern Formation Method (6): EB Exposure, Alkaline Development (Positive)>

[1148] The resist composition shown in Table 2 was applied on a 6-inch wafer using a spin coater Mark 8 manufactured by Tokyo Electron Limited and baked (PB) on a hot plate at 110° C. for 90 seconds to obtain a resist film having a film thickness of 80 nm.

[1149] The resist film was patterned using an electron beam lithography apparatus (manufactured by ELIONIX INC.; ELS-7500, accelerating voltage 50 KeV). A mask with a line size of 100 nm and a line:space ratio of 1:1 was used as a mask. After irradiation, the film was baked (PEB) on a hot plate at 110°C for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution as a developer for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a line and space pattern with a pitch of 200 nm and a line width of 100 nm (space width of 100 nm).

[1150] The optimum exposure for forming a line and space (LS) pattern with a line width of 100 nm is defined as sensitivity (μC / cm 2 In the above determination of sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1151] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1152] Performance Evaluation

[1153] Adhesion to the substrate was evaluated using the same evaluation method and evaluation criteria as those for KrF exposure.

[1154] [Sensitivity]

[1155] For each resist composition, identical resist compositions were prepared except that they did not contain amine oxide (P), and line-and-space patterns were formed in the same manner as described above. The sensitivity of the resulting isolated space patterns was determined as described above. Using the sensitivity of the line-and-space patterns formed using the resist compositions containing amine oxide (P) as a benchmark, the sensitivity reduction of the line-and-space patterns formed using the resist compositions containing amine oxide (P) was evaluated according to the following criteria.

[1156] (Judgment Criteria)

[1157] A: The observed sensitivity reduction is less than 1μC / cm 2

[1158] B: Observed sensitivity reduction of 1 μC / cm 2 Above and less than 2μC / cm 2

[1159] C: Observed sensitivity reduction is 2μC / cm 2 Above and less than 3μC / cm 2

[1160] D: Observed sensitivity reduction of 3 μC / cm 2 above

[1161] The obtained evaluation results are shown in Table 3.

[1162]

[1163]

[1164]

[1165] [Table 3-1]

[1166] Table 3

[1167]

[1168] [Table 3-2]

[1169] Table 3 (continued)

[1170]

[1171] [Table 3-3]

[1172] Table 3 (continued)

[1173]

[1174] The results in Table 3 show that the composition of the present invention can achieve excellent adhesion between the resist film and the substrate while suppressing a decrease in sensitivity.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising: (A) Resins whose polarity is increased by the action of an acid; (B) photoacid generator; (P) amine oxides; and (D) an acid diffusion controller, wherein Except for those equivalent to amine oxides, The content of the amine oxide (P) is 0.01 ppm or more and 20 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, The mass ratio of the acid diffusion controller (D) to the amine oxide (P) represented by the following formula is greater than 1 and 10,000 or less: Mass ratio=(content of acid diffusion controller (D)) / (content of amine oxide (P)).

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The amine oxide (P) is a compound represented by the following general formula (1): In the formula, R1, R2, and R3 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group, and any two of R1, R2, and R3 may be optionally bonded to form a ring structure.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The amine oxide (P) is a compound represented by the following general formula (2): In the formula, R4, R5, and R6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group, and L1, L2, and L3 are each independently a divalent linking group.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The amine oxide (P) is a compound represented by the following general formula (3): In the formula, R7, R8, and R9 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an aralkyl group, and L4, L5, and L6 are each independently a divalent linking group.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The amine oxide (P) is a compound represented by the following general formula (4): Where R 10 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or a carboxyl group, and n represents an integer from 0 to 5. When n represents an integer greater than 2, multiple R 10 Same or different.

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The amine oxide (P) is a compound represented by the following general formula (5): Where R 1A 、R 2A 、R 3A are each independently an organic group having a heteroatom at the terminal or in the chain and having 6 or less carbon atoms, and R 1A 、R 2A 、R 3A Any two of them are optionally bonded to form a ring structure.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The amine oxide (P) is a compound represented by the following general formula (6): Where R 1B 、R 2B 、R 3B Each independently represents an organic group, excluding unsubstituted alkyl groups having 6 or more carbon atoms, and R 1B 、R 2B 、R 3B Any two of them are optionally bonded to form a ring structure.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein The content of the amine oxide (P) is 0.01 ppm or more and 10 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein The composition has a solid content concentration of 10% by mass or more.

10. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein The acid diffusion controller (D) is an amine compound, and the amine oxide (P) is an amine oxide formed by oxidizing the nitrogen atom of the amine portion of the acid diffusion controller (D). 11 . The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , further comprising (H) a surfactant. 12 . An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 .

13. A pattern forming method comprising the following steps: A step of exposing the actinic ray-sensitive or radiation-sensitive film according to claim 12; and A step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

14. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 13.

Images