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

Abstract

To provide an active ray-sensitive or radiation-sensitive resin composition capable of combining excellent rectangularity of an obtained pattern cross-section shape, and excellent temporal stability in high dimension.SOLUTION: There are provided an active ray-sensitive or radiation-sensitive resin composition containing a compound (P) that is at least one of a compound represented by a specific general formula (1) and a compound represented by a specific general formula (2), wherein a content of the compound (P) is 1 ppm or more and 1000 ppm or less with respect to a total mass of the active ray-sensitive or radiation-sensitive resin composition, and a molecular weight of the compound (P) is 500 or less, a resist film, a pattern forming method, and a method for manufacturing an electronic device.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Since the development of resists for KrF excimer lasers (248 nm), pattern formation methods using chemical amplification have been used to compensate for the loss of sensitivity due to light absorption. For example, in positive-tone chemical amplification methods, a photoacid generator contained in the exposed area is first decomposed by light irradiation to generate acid. Then, during a post-exposure bake (PEB) process or the like, the catalytic action of the generated acid converts alkali-insoluble groups contained in the photosensitive composition into alkali-soluble groups. Development is then performed, for example, using an alkaline solution. This removes the exposed area, resulting in the desired pattern. In the above method, various alkaline developers have been proposed, for example, an aqueous alkaline developer containing 2.38% by mass of TMAH (tetramethylammonium hydroxide) is widely used.

[0003] To achieve miniaturization of semiconductor elements, the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher, and currently, exposure machines using an ArF excimer laser with a wavelength of 193 nm as a light source have been developed. One technique for further improving resolution is to fill the space between the projection lens and the sample with a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") (i.e., the immersion method).

[0004] Many types of conventional resist compositions are known, including, for example, the one described in Patent Document 1. Patent Document 1 describes a photoresist composition containing a polymer having a structural unit containing an acid-dissociable group that dissociates when acted upon by an acid, a radiation-sensitive acid generator, and a solvent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2015-57638 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, there has been a demand for resist compositions that achieve both excellent rectangularity of the cross-sectional shape of the pattern and excellent stability over time at a high level.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which achieves both excellent rectangularity of the cross-sectional shape of the pattern obtained and excellent stability over time at a high level. Another object of the present invention is to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0008] The means for solving the above problems include the following aspects. 〔1〕 Resin (A) whose polarity increases under the action of acid; a compound (B) that generates an acid upon exposure to actinic rays or radiation, and An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) represented by any one of the following compounds: the content of the compound (P) is 1 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, The actinic ray-sensitive or radiation-sensitive resin composition further comprises an acid diffusion controller, and the acid diffusion controller is a basic compound (provided that the composition comprises: (A) an acid generator that generates an acid upon irradiation with actinic rays or radiation; (B) a resin whose solubility in alkali increases due to the action of an acid; and (C) a compound represented by the following formula (1): HS-Y-(R)u···(1) (wherein R represents an acid-decomposable group whose solubility in alkali increases under the action of acid, Y represents a linking group with a valence of u+1, and u represents an integer of 1 to 3), a photosensitive resin composition containing an acid generator A1 described below, a resin B1 described below, an alkali-soluble resin D1 described below, an alkali-soluble resin D2 described below, and tripentylamine, a photosensitive resin composition containing an acid generator A1 described below, a resin B1 described below, an alkali-soluble resin D1 described below, an alkali-soluble resin D2 described below, tripentylamine, and 3-mercaptopropionic acid, and a photosensitive resin composition containing an acid generator A1 described below, a resin B1 described below, an alkali-soluble resin D1 described below, an alkali-soluble resin D2 described below, tripentylamine, and 1-dodecanethiol. [ka] [ka] The numbers in the brackets at the bottom right of each structural unit in the structural formula of resin B1 represent the content (mass %) of the structural unit in the resin. D1: Polyhydroxystyrene resin (p-hydroxystyrene:styrene = 85:15 (mass ratio) copolymer, mass average molecular weight (Mw) 2500) D2: Novolak resin (a novolak resin (mass average molecular weight (Mw) 8000) obtained by mixing m-cresol and p-cresol in a mass ratio of m-cresol / p-cresol = 60 / 40 and subjecting the mixture to addition condensation in the presence of formaldehyde and an acid catalyst) 〔2〕 The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. 〔3〕 The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the content of the compound (P) is 1 ppm or more and 200 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. 〔4〕 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the content of the compound (P) is 1 ppm or more and 100 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. 〔5〕 A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4]. 〔6〕 A pattern forming method comprising the steps of: exposing the resist film according to [5]; and developing the exposed resist film using a developer. 〔7〕 A method for manufacturing an electronic device, comprising the pattern forming method according to [6]. The present invention relates to the above items [1] to [7]. However, other items (e.g., the below described <1> ~ <7> , and [1]~[9]) are also described. <1> Resin (A) whose polarity increases under the action of acid; a compound (B) that generates an acid upon exposure to actinic rays or radiation, and An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) represented by any one of the following compounds: the content of the compound (P) is 1 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, The actinic ray-sensitive or radiation-sensitive resin composition further comprises an acid diffusion controller, wherein the acid diffusion controller is a basic compound. [ka] <2> the content of the compound (P) is 1 ppm or more and 500 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition; <1> 1. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1. <3> the content of the compound (P) is 1 ppm or more and 200 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition; <1> or <2> 1. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1. <4> the content of the compound (P) is 1 ppm or more and 100 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition; <1> ~ <3> 1. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9. <5> <1> ~ <4> 1. A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9. <6> <5> 2. A pattern forming method comprising the steps of: exposing the resist film according to claim 1 to light; and developing the exposed resist film using a developer. <7> <6> A method for manufacturing an electronic device, comprising the pattern forming method according to claim 1 。

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) which is at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), the content of the compound (P) is 1 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (P) has a molecular weight of 500 or less.

[0010] [ka]

[0011] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a substituent. L represents a divalent linking group, and the group represented by L has 1 to 5 carbon atoms. n represents an integer of 1 or more, provided that when n represents 1, L has 1 or 2 carbon atoms. When n represents an integer of 2 or more, multiple Ls may be the same or different. In general formula (2), R3 represents a hydrogen atom or a substituent, provided that when R3 represents a substituent, the atom in R3 that bonds to HC(=O)- is a carbon atom.

[0012] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound (P) is a compound represented by the following general formula (3) or the following general formula (4):

[0013] [ka]

[0014] In general formula (3), R4 and R5 each independently represent a hydrogen atom or a substituent. n represents an integer of 1 or more. In general formula (4), R6 and R7 each independently represent a hydrogen atom or a substituent. n1 represents an integer of 1 or greater. n2 represents an integer of 1 or greater.

[0015] [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the content of the compound (P) is 1 ppm or more and 200 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0016] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the content of the compound (P) is 1 ppm or more and 100 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], further comprising an acid diffusion controller.

[0017] [7] A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6]. [8] A pattern forming method comprising the steps of: exposing the resist film according to [7]; and developing the exposed resist film using a developer. [9] A method for manufacturing an electronic device, comprising the pattern formation method according to [8]. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition which achieves both excellent rectangularity of the cross-sectional shape of the obtained pattern and excellent stability over time at a high level. The present invention further provides a resist film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, when a group (atomic group) is designated without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom.

[0020] Furthermore, in this specification, when it is stated that a compound may have a substituent, the type, position, and number of the substituent are not particularly limited. The number of the substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metallic atomic group excluding a hydrogen atom, which can be selected from the following substituents T.

[0021] (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxalyl group; alkylsulfanyl groups such as a phenylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; and combinations thereof.

[0022] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, electron beams (EB), etc. Unless otherwise specified, "light" as used herein refers to actinic rays or radiation. Unless otherwise specified, the term "exposure" in this specification includes not only exposure to the bright line spectrum of a mercury lamp, far ultraviolet light typified by an excimer laser, extreme ultraviolet light, X-rays, EUV light, and the like, but also exposure to particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

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

[0024] In this specification, the amount of each component in a composition means the total amount of the corresponding substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. As used herein, the term "total solid content" refers to the total mass of the components of the composition excluding the solvent. As described above, the term "solid content" refers to the components excluding the solvent, and may be solid or liquid at 25°C, for example. In this specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Also, in this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0025] (Actinic ray-sensitive or radiation-sensitive resin composition) The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (hereinafter also simply referred to as "composition") comprises: An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) which is at least one of a compound represented by general formula (1) described below and a compound represented by general formula (2) described below, the content of the compound (P) is 1 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, The molecular weight of the compound (P) is 500 or less.

[0026] The present inventors have found that by adopting the above-described configuration, it is possible to achieve both excellent rectangularity of the cross-sectional shape of the obtained pattern and excellent stability over time at a high level. The reason for this is not clear, but is presumed to be as follows. First, the present inventors have found that the actinic ray-sensitive or radiation-sensitive resin composition contains at least one compound (P) represented by general formula (1) and general formula (2) in a predetermined range of 1 ppm to 1000 ppm relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, as described above, and that the rectangularity of the cross-sectional shape of the pattern is extremely excellent. Although the exact reason for this is unclear, it is presumed that the actinic ray-sensitive or radiation-sensitive resin composition contains the compound (P) in the above-mentioned extremely small amount range, which prevents the acid generated in the exposed areas of the resist film from diffusing excessively into the unexposed areas. Furthermore, by setting the molecular weight of compound (P), which is at least one of the compound represented by general formula (1) and the compound represented by general formula (2), to 500 or less, it is believed that improvement in the flexibility of the resist film is suppressed compared to when the molecular weight of compound (P) exceeds 500. As a result, the acid generated in the exposed areas of the resist film is prevented from diffusing excessively into the unexposed areas, and from this perspective, it is presumed that the rectangularity of the cross-sectional shape of the pattern is also extremely excellent. Furthermore, the present inventors have found through extensive investigations that the stability over time of an actinic ray-sensitive or radiation-sensitive resin composition can be further improved by containing the compound (P) having a molecular weight of 500 or less in the above-mentioned extremely small amount range, but the reason for this is unknown.

[0027] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably a so-called resist composition, and may be a positive resist composition or a negative resist composition. Furthermore, it may be a resist composition for alkali development or a resist composition for organic solvent development. Typically, the composition of the present invention is preferably a chemically amplified resist composition. 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.

[0028] <Compound (P) which is at least one of a compound represented by general formula (1) and a compound represented by general formula (2)> The composition of the present invention contains a compound (P) (hereinafter also referred to as "compound (P)") which is at least one of a compound represented by general formula (1) and a compound represented by general formula (2).

[0029] [ka]

[0030] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a substituent. L represents a divalent linking group, and the group represented by L has 1 to 5 carbon atoms. n represents an integer of 1 or more, provided that when n represents 1, L has 1 or 2 carbon atoms. When n represents an integer of 2 or more, multiple Ls may be the same or different. In general formula (2), R3 represents a hydrogen atom or a substituent, provided that when R3 represents a substituent, the atom in R3 that bonds to HC(=O)- is a carbon atom.

[0031] The substituents represented by R1 and R2 are not particularly limited, and examples thereof include monovalent organic groups, such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, and acyl groups.

[0032] The alkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms, which may be linear or branched. An alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. The alkenyl group may be, for example, an alkenyl group having 2 to 5 carbon atoms, which may be linear or branched, and is preferably an alkenyl group having 2 to 3 carbon atoms. The cycloalkyl group may, for example, be a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms is preferred. The cycloalkyl group may have a heteroatom between the carbon-carbon bonds, such as an oxygen atom, a sulfur atom, or a nitrogen atom. The aryl group includes, for example, an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferred. The heterocyclic group may be monocyclic or polycyclic. Polycyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of aromatic heterocycles include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of non-aromatic heterocycles include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of lactone rings and sultone rings include the lactone structures and sultone structures exemplified for the resins described above. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

[0033] Examples of the acyl group include acyl groups having 1 to 4 carbon atoms, and specific examples include an acetyl group.

[0034] The alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, or acyl group may further have a substituent, for example, the substituent T described above.

[0035] R1 is preferably a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and more preferably a hydrogen atom, an alkyl group, or an aryl group. R2 is preferably a hydrogen atom or an alkyl group.

[0036] L represents a divalent linking group, and the group represented by L has 1 to 5 carbon atoms. The divalent linking group is not particularly limited, but examples thereof include alkylene groups having 1 to 5 carbon atoms, which may be linear or branched, and preferably represents an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. The divalent linking group may further have a substituent, such as the substituent T. The group represented by L has 1 to 5 carbon atoms.

[0037] n represents an integer of 1 or more, provided that when n represents 1, L has 1 or 2 carbon atoms. When n represents 1, the number of carbon atoms in L is 1 or 2. If this condition is not met, it tends to be difficult to improve stability over time and pattern rectangularity. The upper limit of n is not particularly limited, but is 10, for example. n is preferably 1 to 4, and more preferably 1 to 3.

[0038] The substituent R3 is not particularly limited, but may be, for example, a monovalent organic group, specifically an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an acyl group.

[0039] The alkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms, which may be linear or branched. An alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. The alkenyl group may be, for example, an alkenyl group having 2 to 5 carbon atoms, which may be linear or branched, and is preferably an alkenyl group having 2 to 3 carbon atoms. The cycloalkyl group may, for example, be a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms is preferred. The cycloalkyl group may have a heteroatom between the carbon-carbon bonds, such as an oxygen atom, a sulfur atom, or a nitrogen atom.

[0040] The aryl group includes, for example, an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferred. The heterocyclic group may be monocyclic or polycyclic. Polycyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of aromatic heterocycles include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of non-aromatic heterocycles include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of lactone rings and sultone rings include the lactone structures and sultone structures exemplified for the resins described above. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

[0041] Examples of the acyl group include acyl groups having 1 to 4 carbon atoms, and specific examples include an acetyl group.

[0042] The alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, heteroaryl group and acyl group may further have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, such as an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a nitro group, and a formyl group.

[0043] When R3 represents a substituent, the atom bonding to HC(=O)- in R3 is a carbon atom. If this condition is not met, it tends to be difficult to improve stability over time and pattern rectangularity.

[0044] The compound (P) is preferably a compound represented by the following general formula (3) or (4).

[0045] [ka]

[0046] In general formula (3), R4 and R5 each independently represent a hydrogen atom or a substituent. n represents an integer of 1 or more. In general formula (4), R6 and R7 each independently represent a hydrogen atom or a substituent. n1 represents an integer of 1 or greater. n2 represents an integer of 1 or greater.

[0047] Specific examples of the substituent for R4 are the same as the specific examples of the substituent for R1 in the general formula (1), and the preferred ranges are also the same. Specific examples of the substituent for R5 are the same as the specific examples of the substituent for R2 in the general formula (1), and the preferred ranges are also the same. n represents an integer of 1 or more. The upper limit of n is not particularly limited, but is 10, for example. n is preferably 1 to 4, and more preferably 1 to 3.

[0048] Specific examples of the substituent for R6 are the same as the specific examples of the substituent for R1 in the above general formula (1), and the preferred ranges are also the same. Specific examples of the substituent for R7 are the same as the specific examples of the substituent for R2 in the general formula (1), and the preferred ranges are also the same. n1 represents an integer of 1 or greater. The upper limit of n1 is not particularly limited, but is 5, for example. n1 is preferably 1 to 4, and more preferably 1 or 2.

[0049] n2 represents an integer of 1 or greater. The upper limit of n2 is not particularly limited, but is 5, for example. n2 is preferably 1 or 2, and more preferably 1.

[0050] In general formula (4), C3H6 may be linear or branched.

[0051] Specific examples of the compound (P) are given below, but the present invention is not limited to these specific examples. C3H6 may be linear or branched.

[0052] [ka]

[0053] [ka]

[0054] The content of the compound (P) (when a plurality of compounds (P) are present, the total content thereof) is 1 ppm or more and 1000 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. If the content of compound (P) (the total content when there are multiple compounds (P)) is less than 1 ppm, the effects of the present invention cannot be achieved. If the content of compound (P) (the total content when there are multiple compounds (P)) is more than 1000 ppm, it is not possible to achieve both rectangularity of the pattern shape and stability over time. The content of the compound (P) (when a plurality of compounds (P) are present, the total content thereof) is preferably 1 ppm or more and 500 ppm or less, more preferably 1 ppm or more and 200 ppm or less, and even more preferably 1 ppm or more and 100 ppm or less, relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, from the viewpoints of the rectangularity of the obtained pattern shape and stability over time.

[0055] The molecular weight of the compound (P) is not more than 500. When a plurality of compounds (P) are present, the molecular weight of each compound (P) is not more than 500. If the molecular weight of the compound (P) exceeds 500, the plasticity of the compound will be manifested, which will promote the diffusion of the acid generated in the exposed areas of the resist film, resulting in a decrease in the rectangularity of the resulting pattern. The lower limit of the molecular weight of the compound (P) is not particularly limited, but is 30, for example. The molecular weight of the compound (P) is preferably 30 to 400, more preferably 30 to 300, from the viewpoint of suppressing plasticization.

[0056] The composition of the present invention contains the above-mentioned compound (P), but may also contain a compound represented by the above-mentioned general formula (1), may also contain a compound represented by the above-mentioned general formula (2), or may also contain a compound represented by the above-mentioned general formula (1) and a compound represented by the above-mentioned general formula (2). When the composition of the present invention contains a compound represented by the above general formula (1), the compound represented by the above general formula (1) may be used alone or in combination of two or more types. When the composition of the present invention contains a compound represented by the above general formula (2), the compound represented by the above general formula (2) may be used alone or in combination of two or more types.

[0057] The content of the compound (P) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be measured, for example, by the following method.

[0058] (Compound represented by general formula (1)) A resist solution containing the compound represented by general formula (1) was prepared and analyzed using a GC (gas chromatograph) system (Agilent-6890A, Agilent Technologies) equipped with a wax column (DB-HeavyWAX (#123-7162), Agilent Technologies) and an FID detector (Agilent-6890A, Agilent Technologies). The content of the compound represented by general formula (1) was quantified using the absolute calibration curve method using standard reagents for each compound. The standard reagent is a mixture of a compound represented by general formula (1) of known concentration to be quantified and acetonitrile of known concentration. Commercially available acetonitrile can be used as the acetonitrile.

[0059] (Compound represented by general formula (2)) A resist solution containing the compound represented by formula (2) was prepared and irradiated with ultrasound for 3 minutes using an ultrasonic device (tabletop ultrasonic cleaner (#5510, Bransonic). The resulting solution was analyzed using a liquid chromatograph (Agilent 1100 HPLC G1311A, Agilent Technologies) with a UV detector (Agilent 1100 HPLC G1315B, Agilent Technologies) and a reverse-phase column (Shim-pack CLC-ODS(M), Shimadzu GLC). The content of the compound represented by formula (2) was quantified using an absolute calibration curve method using standard reagents for each compound. The standard reagent is a mixture of the compound represented by general formula (2) to be quantified, the concentration of which is known, and DNPH, the concentration of which is known.

[0060] <Resins whose polarity increases under the action of acid> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention typically preferably contains a resin (hereinafter also referred to as "resin (A)") whose polarity increases and whose solubility in a developer changes due to the action of an acid.

[0061] The resin (resin (A)) whose polarity increases under the action of an acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound. 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 a monomer. 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.

[0062] Furthermore, the resin whose polarity increases under the action of an acid preferably has an acid-decomposable group, and more preferably is a resin having a structural unit having an acid-decomposable group. In this case, in the pattern formation method according to the present invention described below, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is suitably formed.

[0063] [Structural Unit Having an Acid-Decomposable Group] The resin (A) preferably has a structural unit (also referred to as a "repeating unit") having an acid-decomposable group.

[0064] As the resin (A), a known resin can be appropriately used. 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 suitably used as the resin (A).

[0065] The acid-decomposable group preferably has a structure in which a polar group is protected with a group (leaving group) that is decomposed and eliminated by the action of an acid. Examples of the polar group include acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) such as a carboxy 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 tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.

[0066] The alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and excludes aliphatic alcohols in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom (e.g., a hexafluoroisopropanol group).The alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0067] Preferred polar groups include a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group.

[0068] Preferred acid-decomposable groups are those obtained by substituting the hydrogen atom of the above groups with a group that is eliminated by the action of an acid (a leaving group). Examples of the group that is eliminated by the action of an acid (leaving group) include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ) etc. In the formula, 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 and R37 may be bonded to each other to form a ring. 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.

[0069] 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 a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. R 36 ~R 39 , R 01 and R 02 The cycloalkyl group may be monocyclic or polycyclic. Preferred monocyclic groups are cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Preferred polycyclic groups are cycloalkyl groups having 6 to 20 carbon atoms, such as adamantyl, norbornyl, isobornyl, camphanyl, dicyclopentyl, α-pinel, tricyclodecanyl, tetracyclododecyl, and androstanyl. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. 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 a phenyl group, a naphthyl group, and an anthryl group. 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 a benzyl group, a phenethyl group, and a naphthylmethyl group. 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 a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. R 36 and R 37 The ring formed by bonding together is preferably a cycloalkyl group (monocyclic or polycyclic). Preferred cycloalkyl groups are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.

[0070] The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.

[0071] The resin (A) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.

[0072] [ka]

[0073] In formula AI, Xa 1 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 these may or may not be bonded to form a ring structure.

[0074] Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-, in which Rt represents an alkylene group, a cycloalkylene group, or an arylene group; 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.

[0075] Xa 1 is preferably a hydrogen atom or an alkyl group. 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. Xa 1 The alkyl group of Xa preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a hydroxymethyl group. 1 The alkyl group is preferably a methyl group.

[0076] Rx 1 , Rx 2 and Rx 3 The alkyl group may be linear or branched, and preferred examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. 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. Rx 1 , Rx 2 and Rx 3 In the alkyl group, some of the carbon-carbon bonds may be double bonds. Rx 1 , Rx 2 and Rx 3 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

[0077] Rx 1 , Rx 2 and Rx 3The ring structure formed by the bonding of the two is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, or a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring. A cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferred. 1 , Rx 2 and Rx 3 As the ring structure formed by combining the above two, the structure shown below is also preferred.

[0078] [ka]

[0079] Specific examples of monomers corresponding to the structural unit represented by formula AI are listed below, but the present invention is not limited to these specific examples. 1 corresponds to the case where Xa is a methyl group, 1 can be optionally substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0080] [ka]

[0081] It is also preferable that the resin (A) has a structural unit described in paragraphs 0336 to 0369 of US Patent Application Publication No. 2016 / 0070167 as a structural unit having an acid-decomposable group.

[0082] Furthermore, the resin (A) may have, as a structural unit having an acid-decomposable group, a structural unit containing a group that decomposes under the action of an acid to generate an alcoholic hydroxyl group, as described in paragraphs 0363 to 0364 of the specification of U.S. Patent Application Publication No. 2016 / 0070167.

[0083] Furthermore, the resin (A) preferably has a repeating unit having an acid-decomposable group, which is a repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected with a leaving group that decomposes and leaves under the action of acid. In this specification, the phenolic hydroxyl group refers to a group in which a hydrogen atom of an aromatic hydrocarbon group is substituted with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, such as a benzene ring or a naphthalene ring.

[0084] Examples of the leaving group that is decomposed and eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0085] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Among these, it is more preferable that Rx1 to Rx3 are each independently a repeating unit representing a linear or branched alkyl group, and it is even more preferable that Rx1 to Rx3 are each independently a repeating unit representing a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocycle or polycycle. 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, or a t-butyl group. The cycloalkyl group of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. In the groups represented by formulae (Y1) and (Y2), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0086] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 is preferably a hydrogen atom.

[0087] 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.

[0088] As a repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group that is decomposed and eliminated by the action of an acid (acid-decomposable group), a repeating unit having a structure in which the hydrogen atom in the phenolic hydroxyl group is protected with a group represented by any of the formulae (Y1) to (Y4) is preferred.

[0089] As a repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group that is decomposed and eliminated by the action of an acid (acid-decomposable group), a repeating unit represented by the following general formula (AII) is preferred.

[0090] [ka]

[0091] In the general formula (AII), 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 may be bonded to Ar6 to form a ring, in which case R 62 represents a single bond or an alkylene group. X6 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L6 represents a single bond or an alkylene group. Ar6 represents an (n+1)-valent aromatic hydrocarbon group, and R 62 When it is bonded to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. When n≧2, each Y2 independently represents a hydrogen atom or a group which is eliminated by the action of an acid. However, at least one Y2 represents a group which is eliminated by the action of an acid. The group which is eliminated by the action of an acid as Y2 is preferably any one of formulae (Y1) to (Y4). n represents an integer of 1 to 4.

[0092] Each of the above groups may have a substituent, and 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), and those having 8 or less carbon atoms are preferred.

[0093] [ka]

[0094] [ka]

[0095] The resin (A) may contain one type of structural unit having an acid-decomposable group, or may contain two or more types.

[0096] The content of structural units having an acid-decomposable group contained in the resin (A) (the total content if there are multiple structural units having an acid-decomposable group) is preferably 5 mol % to 90 mol %, more preferably 10 mol % to 80 mol %, and even more preferably 15 mol % to 70 mol %, based on all structural units of the resin (A). In the present invention, when the content of a "structural unit" is specified by a molar ratio, the "structural unit" is synonymous with a "monomer unit." In addition, in the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0097] [Structural Unit Having at Least One Structure Selected from the Group Consisting of Lactone Structure, Sultone Structure, and Carbonate Structure] The resin (A) preferably has a structural unit having at least one structure selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0098] Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure is preferred, and a 5- to 7-membered cyclic lactone structure is more preferred, with another ring structure fused to the 5- to 7-membered cyclic lactone structure to form a bicyclo or spiro structure, or a 5- to 7-membered cyclic sultone structure is more preferred, with a structural unit having a lactone structure represented by any of the following formulae LC1-1 to LC1-21, or a sultone structure represented by any of the following formulae SL1-1 to SL1-3. Furthermore, the lactone structure 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.

[0099] [ka]

[0100] The lactone structure portion or the sultone structure portion may be a substituent (Rb 2 ) may or may not have the substituent (Rb 2 Examples of the substituent (Rb) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different. 2 ) may be bonded to each other to form a ring.

[0101] The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III. Furthermore, the resin having a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.

[0102] [ka]

[0103] In the above formula III, A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-). n -R 0 It is the number of repetitions of the structure represented by -Z-, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R 0 -Z- does not exist, A and R 8 are bonded by a single bond. R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. 0 When there are a plurality of groups, each independently represents an alkylene group, a cycloalkylene group, or a combination thereof. 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. R 8 represents a monovalent organic group having a lactone structure or a sultone structure. R 7 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

[0104] R 0 The alkylene group or cycloalkylene group may have a substituent. Z is preferably an ether bond or an ester bond, more preferably an ester bond.

[0105] 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 below are given below, but the present invention is not limited to these specific examples. 7 and R in Formula A-1 described below A 1 corresponds to the case where R is a methyl group, 7 and R A 1 can be optionally substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0106] [ka]

[0107] In addition to the above monomers, the following monomers are also suitably used as raw materials for the resin (A).

[0108] [ka]

[0109] The resin (A) may have a structural unit having a carbonate structure, which is preferably a cyclic carbonate ester structure. The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.

[0110] [ka]

[0111] 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 of 0 or more, R A 2 represents a substituent. A 2When n is 2 or more, each independently represents a substituent, A represents a single bond or a divalent linking group, and Z represents an atomic group which forms a monocyclic structure or a polycyclic structure together with the group represented by —O—C(═O)—O— in the formula.

[0112] Resin (A) also preferably has a structural unit described in paragraphs 0370 to 0414 of U.S. Patent Application Publication No. 2016 / 0070167 as a structural unit having at least one structure selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0113] The resin (A) preferably has a structural unit (a) having at least two lactone structures (hereinafter also referred to as "structural unit (a)"). 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 by a single bond or a linking group. The lactone structure of the structural unit (a) is not particularly limited, but is preferably a 5- to 7-membered ring lactone structure, and is preferably a 5- to 7-membered ring lactone structure to which another ring structure is condensed in the form of a bicyclo structure or a spiro structure. The lactone structure is preferably, for example, a lactone structure represented by any one of the above-mentioned LC1-1 to LC1-21.

[0114] 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.

[0115] [ka]

[0116] 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.

[0117] The alkyl group represented by Ra 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 represented by Ra may be substituted. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; mercapto groups; hydroxy groups; alkoxy groups such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, and a benzyloxy group; and acetoxy groups such as an acetyl group and a propionyl group. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0118] Examples of the lactone structure contained in the Rb partial structure include the lactone structures described above. 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 by a single bond or a linking group, and a structure in which at least two lactone structures form a condensed ring. 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 by a single bond or a linking group will each be described below.

[0119] -Structural unit (a1) having a structure in which at least two lactone structures are fused together- The structure in which at least two lactone structures are fused is preferably a structure in which two or three lactone structures are fused, and more preferably a structure in which two lactone structures are fused. An example of a structural unit having a structure in which at least two lactone structures are fused together (hereinafter, also referred to as "structural unit (a1)") is a structural unit represented by the following formula L-2.

[0120] [ka]

[0121] 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.

[0122] The alkyl groups Re1 to Re8 preferably have 5 or less carbon atoms, and more preferably have 1 carbon atom, for example. Examples of the alkyl group having 5 or less carbon atoms for Re1 to Re8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an s-pentyl group, and a t-pentyl group. Among these, Re1 to Re8 are preferably hydrogen atoms.

[0123] Examples of the divalent linking group for Me1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups. The alkylene group of Me1 preferably has, for example, 1 to 10 carbon atoms, and more preferably has 1 or 2 carbon atoms, and the alkylene group having 1 or 2 carbon atoms is preferably, for example, a methylene group or an ethylene group. The alkylene group of Me1 may be linear or branched, and examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. The cycloalkylene group of Me1 preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms, for example. Examples of the cycloalkylene group of Me1 include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group. As the divalent linking group of Me1, the group combining two or more of the above groups is preferably, for example, a group combining an alkylene group with -COO-, or a group combining -OCO- with an alkylene group.Furthermore, the group combining two or more of the above groups is more preferably a group combining a methylene group with -COO-, or a group combining a -COO- with a methylene group.

[0124] Examples of the divalent linking group of Me2 and Me3 include an alkylene group, -O-, etc. The divalent linking group of Me2 and Me3 is preferably a methylene group, an ethylene group, or -O-, and more preferably -O-.

[0125] A monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP-A-2015-160836.

[0126] Specific examples of the structural unit (a1) are shown below, but the present invention is not limited to these. In each of the following formulas, R9 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and * represents the bonding position to other structural units.

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] -Structural unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group- 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 two to four 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. Examples of the linking group include the same groups as those exemplified as the linking group of M2 in formula L-3 described below. An example of a 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)") is a structural unit represented by the following formula L-3.

[0131] [ka]

[0132] In formula L-3, Ra has the same meaning as Ra in formula L-1 above, 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.

[0133] Examples of the linking group for M1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups. The alkylene group of M1 preferably has, for example, 1 to 10 carbon atoms. The alkylene group of M1 may be linear or branched, and examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. The cycloalkylene group of M1 preferably has 5 to 10 carbon atoms, for example. Examples of the cycloalkylene group of M1 include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group. As the linking group of M1, the group combining two or more of the above groups is preferably, for example, a group combining an alkylene group with -COO-, or a group combining -OCO- with an alkylene group.Furthermore, the group combining two or more of the above groups is more preferably a group combining a methylene group with -COO-, or a group combining a -COO- with a methylene group. Examples of the linking group for M2 include the same groups as those exemplified as the linking group for M1.

[0134] The lactone structure of Lc1 is preferably, for example, a 5- to 7-membered ring lactone structure, and preferably a 5- to 7-membered ring lactone structure to which another ring structure is fused in the form of a bicyclo structure or a spiro structure. The lactone structure is more preferably a lactone structure represented by any of the above LC1-1 to LC1-21. More preferred lactone structures include LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14, and LC1-17. The lactone structure of Lc1 may contain a substituent. Examples of the substituent that may be contained in the lactone structure of Lc1 include the same substituents as the substituent (Rb2) of the lactone structure described above. Examples of the lactone structure of Lc2 include the same lactone structures as those exemplified for the lactone structure of Lc1.

[0135] The structural unit (a2) represented by the above formula L-3 is preferably a structural unit represented by the following formula L-4.

[0136] [ka]

[0137] In formula L-4, Ra has the same meaning as Ra in formula L-1 above, Mf1 and Mf2 each independently represent a single bond or a linking group, Rf1, Rf2, and Rf3 each independently represent a hydrogen atom or an alkyl group, Mf1 and Rf1 may be bonded to each other to form a ring, and Mf2 and Rf2 or Rf3 may each be bonded to each other to form a ring.

[0138] The linking group of Mf1 has the same meaning as the linking group of M1 in the above formula L-3. The linking group of Mf2 has the same meaning as the linking group of M2 in the above formula L-3. The alkyl group of Rf1 may be, for example, an alkyl group having 1 to 4 carbon atoms. The alkyl group of Rf1 having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group. The alkyl group of Rf1 may have a substituent. Examples of the substituent that the alkyl group of Rf1 may have include a hydroxy group, an alkoxy group such as a methoxy group or an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom. The alkyl groups of Rf2 and Rf3 have the same meaning as the alkyl group of Rf1.

[0139] 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 described above among the lactone structures described above. Mf2 and Rf2 or Rf3 may be bonded to each other to form a ring. Examples of the structure in which Mf2 and Rf2 are bonded to each other to form a ring include the lactone structures represented by LC1-7, LC1-8, or LC1-15 among the lactone structures mentioned above. Examples of the structure in which Mf2 and Rf3 are bonded to each other to form a ring include the lactone structures represented by any of the above-mentioned LC1-3 to LC1-6 among the above-mentioned lactone structures. Specific examples of the structural unit (a2) are shown below, but the present invention is not limited to these. * indicates the bonding position to other structural units.

[0140] [ka]

[0141] A structural unit having at least two lactone structures usually has optical isomers, and any of these optical isomers may be used. One optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is primarily used, the optical purity (ee) is preferably 90% or higher, more preferably 95% or higher.

[0142] The content of the structural unit having at least two lactone structures is preferably 10 mol % to 60 mol %, more preferably 20 mol % to 50 mol %, and even more preferably 30 mol % to 50 mol %, based on all structural units in the resin (A). To enhance the effects of the present invention, two or more types of structural units having at least two lactone structures can be used in combination. When two or more types of repeating units having at least two lactone structures are contained, it is preferable that the total content of the structural units having at least two lactone structures falls within the above-mentioned range.

[0143] The resin (A) may contain one type of structural unit having at least one type selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more types of structural units in combination.

[0144] The content of structural units having at least one selected from the group consisting of lactone structures, sultone structures, and carbonate structures contained in resin (A) (when there are a plurality of structural units having at least one selected from the group consisting of lactone structures, sultone structures, and carbonate structures, the total content thereof) is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 65 mol %, and even more preferably 20 mol % to 60 mol %, relative to all structural units of resin (A).

[0145] [Structural Unit Having a Polar Group] The resin (A) preferably has a structural unit having a polar group. Examples of the polar group include a hydroxyl group, a cyano group, and a carboxyl group. 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.

[0146] Specific examples of monomers corresponding to structural units having a polar group are listed below, but the present invention is not limited to these specific examples. Furthermore, although the following specific examples are described as methacrylic acid ester compounds, they may also be acrylic acid ester compounds.

[0147] [ka]

[0148] Other specific examples of structural units having a polar group include the structural units disclosed in paragraphs 0415 to 0433 of the specification of US Patent Application Publication No. 2016 / 0070167. The resin (A) may contain one type of structural unit having a polar group on its own, or may contain two or more types in combination. The content of the structural unit having a polar group is preferably 5 mol % to 40 mol %, more preferably 5 mol % to 30 mol %, and even more preferably 10 mol % to 25 mol %, based on all structural units in the resin (A).

[0149] [Structural Unit Having Neither an Acid-Decomposable Group nor a Polar Group] The resin (A) may further have a structural unit having neither an acid-decomposable group nor a polar group. The structural unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the structural unit having neither an acid-decomposable group nor a polar group include the structural units described in paragraphs 0236 to 0237 of U.S. Patent Application Publication No. 2016 / 0026083. Preferred examples of monomers corresponding to the structural unit having neither an acid-decomposable group nor a polar group are shown below.

[0150] [ka]

[0151] Other specific examples of structural units that have neither an acid-decomposable group nor a polar group include the structural units disclosed in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167. The resin (A) may contain one type of structural unit that has neither an acid-decomposable group nor a polar group, or may contain two or more types in combination. The content of structural units having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol %, more preferably from 5 to 30 mol %, and even more preferably from 5 to 25 mol %, based on all structural units in the resin (A).

[0152] [Repeating unit (a1)] The resin (A) may further have the following repeating unit (a1): The repeating unit (a1) is a repeating unit derived from a monomer (also referred to as "monomer a1") that has a glass transition temperature of 50°C or lower when made into a homopolymer. The repeating unit (a1) is a non-acid-decomposable repeating unit, and therefore does not have an acid-decomposable group.

[0153] (Method for measuring the glass transition temperature of homopolymers) The glass transition temperature of the homopolymer is measured by differential scanning calorimetry (DSC) if available from a catalog or literature source. If not available, the homopolymer is measured by differential scanning calorimetry (DSC). The weight-average molecular weight (Mw) of the homopolymer used for Tg measurement is 18,000, and the polydispersity (Mw / Mn) is 1.7. The DSC device used is a thermal analysis DSC differential scanning calorimeter model Q1000 manufactured by TA Instruments Japan, Inc., and the measurement is performed at a heating rate of 10°C / min. The homopolymer to be subjected to Tg measurement may be synthesized using the corresponding monomer by a known method, for example, a general dropping polymerization method, etc. An example is shown below. 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80°C under a nitrogen stream. While stirring this 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 6 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for an additional 2 hours. The reaction solution was allowed to cool, then reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the resulting solid was dried to obtain a homopolymer (Mw: 18,000, Mw / Mn: 1.7). The resulting homopolymer was subjected to DSC measurement. The DSC equipment and heating rate were as described above.

[0154] Monomer a1 is not particularly limited as long as its glass transition temperature (Tg) when made into a homopolymer is 50°C or less, and from the viewpoints of improving the resolution of the dot pattern and suppressing roughness on the side walls of the resist pattern that may occur during etching, it is preferable that the Tg when made into a homopolymer is 30°C or less. The lower limit of the Tg when made into a homopolymer of monomer a1 is not particularly limited, but is preferably -80°C or higher, more preferably -70°C or higher, even more preferably -60°C or higher, and particularly preferably -50°C or higher. By setting the lower limit of the Tg when made into a homopolymer of monomer a1 within the above range, the fluidity of the pattern when heated is suppressed, and the perpendicularity of the dot pattern is further improved, which is preferable.

[0155] The repeating unit (a1) is preferably a repeating unit having a non-acid-decomposable alkyl group having two or more carbon atoms, which may contain a heteroatom in the chain, in order to facilitate the volatilization of residual solvents. In this specification, "non-acid-decomposable" means that the repeating unit has the property of not undergoing elimination / decomposition reactions due to the acid generated by the photoacid generator. In other words, the "non-acid-decomposable alkyl group" more specifically includes an alkyl group that does not leave the resin (A) due to the action of an acid generated by a photoacid generator, or an alkyl group that does not decompose due to the action of an acid generated by a photoacid generator. The non-acid-decomposable alkyl group may be either linear or branched. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having two or more carbon atoms, which may contain a heteroatom in the chain, will be described.

[0156] The non-acid-decomposable alkyl group having 2 or more carbon atoms and which may contain a heteroatom in the chain is not particularly limited, but 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. Examples of alkyl groups having 2 to 20 carbon atoms and containing a heteroatom in the chain include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group formed by combining two or more of these groups, where R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of non-acid-decomposable alkyl groups 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, and 2-ethylhexyl groups, as well as monovalent alkyl groups in which one or more -CH2- groups are substituted with -O- or -O-CO-.

[0157] 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. The non-acid-decomposable alkyl group having two or more carbon atoms may have a substituent (for example, the substituent T).

[0158] The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

[0159] [ka]

[0160] 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 two or more carbon atoms and optionally containing a heteroatom in the chain.

[0161] The halogen atom represented by R1 is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R1 is not particularly limited, but examples thereof include alkyl groups having 1 to 10 carbon atoms, specifically methyl groups, ethyl groups, tert-butyl groups, etc. Among these, alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred. The cycloalkyl group represented by R1 is not particularly limited, but examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups and the like. Among these, R1 is preferably a hydrogen atom or a methyl group.

[0162] The definition and preferred embodiments of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain represented by R2 are as described above.

[0163] Furthermore, the repeating unit (a1) may be a repeating unit having a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring, in order to make the residual solvent more easily volatilized. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring, will be described.

[0164] The non-acid-decomposable alkyl group may be either a straight-chain or branched-chain alkyl group. The non-acid-decomposable alkyl group preferably has 2 or more carbon atoms, and from the viewpoint of ensuring that the Tg of the homopolymer is 50° C. or less, the upper limit of the number of carbon atoms in the non-acid-decomposable alkyl group is preferably, for example, 20 or less.

[0165] The non-acid-decomposable alkyl group, which may contain a heteroatom in the chain, is not particularly limited, and examples thereof include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms and containing a heteroatom in the chain, in which at least one hydrogen atom is substituted with a carboxy group or a hydroxyl group. Examples of alkyl groups having 2 to 20 carbon atoms and containing a heteroatom in the chain include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group formed by combining two or more of these groups, where R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0166] The number of carbon atoms in 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, in terms of better crack resistance (less likely to cause cracks). The non-acid-decomposable alkyl group may have a substituent (for example, the substituent T). Specific examples of repeating units having a non-acid-decomposable alkyl group having a carboxy group and containing a hetero atom in the chain include repeating units of the following structure.

[0167] [ka]

[0168] The number of carbon atoms in the non-acid-decomposable cycloalkyl group is preferably 5 or more, and from the viewpoint of making the Tg of the homopolymer 50°C or less, the upper limit of the number of carbon atoms in 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.

[0169] The non-acid-decomposable cycloalkyl group, which may contain a heteroatom as a ring member, is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group) and a cycloalkyl group having 5 to 20 carbon atoms and containing a heteroatom as a ring member, in which at least one hydrogen atom is substituted with a carboxy group or a hydroxyl group. Examples of cycloalkyl groups having 5 to 20 carbon atoms and containing a heteroatom in the ring include cycloalkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group formed by combining two or more of these. R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The non-acid-decomposable cycloalkyl group may have a substituent (for example, the substituent T).

[0170] As a repeating unit having a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring member, a repeating unit represented by the following general formula (1-3) is particularly preferred in terms of achieving the effects of the present invention:

[0171] [ka]

[0172] 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 having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring.

[0173] In the general formula (1-3), R3 has the same meaning as R1 described above, and the preferred embodiments are also the same.

[0174] The definition and preferred embodiments of the non-acid-decomposable alkyl group having a carboxy group or a hydroxy group and optionally containing a heteroatom in the chain, represented by R4, or the non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group and optionally containing a heteroatom in the ring member, are as described above. Among these, R4 is preferably a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group, which may contain a heteroatom as a ring member. Examples of this embodiment include repeating units having the following structure.

[0175] [ka]

[0176] 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), and 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), hexadecyl acrylate (35°C), etc. The values ​​in parentheses indicate the Tg (°C) of the homopolymer.

[0177] Methoxypolyethylene glycol monomethacrylate (n=2) is a compound having the following structure:

[0178] [ka]

[0179] 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, or a compound represented by the following MA-5.

[0180] [ka]

[0181] The resin (A) may contain only one type of repeating unit (a1), or may contain two or more types. In the resin (A), the content of the repeating unit (a1) (the total content if there are multiple repeating units (a1)) is preferably 5 mol % or more, more preferably 10 mol % or more, and preferably 50 mol % or less, more preferably 40 mol % or less, and even more preferably 30 mol % or less, based on all repeating units in the resin (A). In particular, the content of the repeating unit (a1) (the total content if there are multiple repeating units (a1)) in the resin (A) is preferably 5 to 50 mol %, more preferably 5 to 40 mol %, and even more preferably 5 to 30 mol % based on all repeating units in the resin (A).

[0182] [Repeating unit (a4) having a phenolic hydroxyl group] The resin (A) may have a repeating unit (a4) having a phenolic hydroxyl group. By containing the repeating unit (a4), the resin (A) has an excellent dissolution rate during alkaline development and excellent etching resistance.

[0183] The repeating unit having a phenolic hydroxyl group is not particularly limited, but may be a hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit. As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (I) is preferred.

[0184] [ka]

[0185] During the ceremony, 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, provided that R 42 may be bonded to Ar4 to form a ring, in which case R 42 represents a single bond or an alkylene group. X4 is a single bond, -COO-, or -CONR 64 - represents R64 represents a hydrogen atom or an alkyl group. L4 represents a single bond or a divalent linking group. Ar4 represents an (n+1)-valent aromatic hydrocarbon group, and R 42 When it is bonded to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1 to 5. For the purpose of increasing the polarity of the repeating unit represented by general formula (I), n is an integer of 2 or more, or X4 is -COO- or -CONR 64 It is also preferable that

[0186] R in general formula (I) 41 , R 42 , and R 43 The alkyl group represented by the formula (I) is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, or dodecyl group, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and even more preferably an alkyl group having 3 or less carbon atoms.

[0187] R in general formula (I) 41 , R 42 , and R 43 The cycloalkyl group represented by the formula (I) may be monocyclic or polycyclic. Preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent. R in general formula (I) 41 , R 42 , and R 43 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. R in general formula (I) 41 , R 42 , and R 43 The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) is the same as that of the above R 41 , R 42 , and R 43The same alkyl groups as those in the above are preferred.

[0188] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane 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, and the number of carbon atoms in the substituent is preferably 8 or less.

[0189] Ar4 represents an (n+1)-valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or an aromatic hydrocarbon group containing a heterocycle, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0190] When n is an integer of 2 or greater, specific examples of the (n+1)-valent aromatic hydrocarbon group are preferably groups obtained by removing any (n-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group. The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

[0191] Examples of the substituent that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include, for example, R 41 , R 42 , and R 43 alkyl groups such as those mentioned above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl; and the like. -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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, which may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms. X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0192] The divalent linking group represented by L4 is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group, which may have a substituent. 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. Of these, 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.

[0193] Specific examples of repeating units having a phenolic hydroxyl group are shown below, but the present invention is not limited to these. In the formula, a represents 1 or 2.

[0194] [ka]

[0195] The resin (A) may contain one type of repeating unit (a4) alone, or two or more types in combination. In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit (a4) is preferably 85 mol% or less, more preferably 80 mol% or less, based on the total repeating units in the resin (A).

[0196] In addition to the above structural units, resin (A) may contain various structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, and also general required properties of a resist, such as resolution, heat resistance, sensitivity, etc. Examples of such structural units include, but are not limited to, structural units corresponding to other monomers.

[0197] Examples of other monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the various structural units described above may be copolymerized. In the resin (A), the molar ratio of each constituent unit is appropriately set in order to adjust various properties.

[0198] When the actinic ray- or radiation-sensitive resin composition according to the present invention is intended for exposure to an argon fluoride (ArF) laser, from the viewpoint of ArF light transmittance, it is preferable that the resin (A) be substantially free of aromatic groups. More specifically, of all the structural units of the resin (A), structural units having aromatic groups preferably account for 5 mol% or less of the total, more preferably 3 mol% or less, and ideally 0 mol%, i.e., it is even more preferable that the resin (A) has no structural units having aromatic groups. Furthermore, it is preferable that the resin (A) have a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0199] It is preferable that all of the structural units of the resin (A) are (meth)acrylate structural units. In this case, any of those in which all the structural units are methacrylate structural units, all the structural units are acrylate structural units, or all the structural units are a combination of methacrylate structural units and acrylate structural units can be used, but it is preferable that the acrylate structural units account for 50 mol % or less of the total structural units of the resin (A).

[0200] When the actinic ray- or radiation-sensitive resin composition according to the present invention is for use in 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, and more preferably contains a structural unit having a phenolic hydroxyl group. Examples of structural units having a phenolic hydroxyl group include the repeating unit (a4) described above. When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is for use in 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 with a group (leaving group) that decomposes and leaves when acted upon by the action of an acid. The content of the structural units having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol % to 100 mol %, more preferably 40 mol % to 100 mol %, and even more preferably 50 mol % to 100 mol %, based on all structural units in the resin (A).

[0201] The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, still more preferably from 3,000 to 15,000, and particularly preferably from 3,000 to 11,000. The dispersity (Mw / Mn) is preferably from 1.0 to 3.0, more preferably from 1.0 to 2.6, still more preferably from 1.0 to 2.0, and particularly preferably from 1.1 to 2.0.

[0202] Specific examples of the resin (A) include resins A-1 to A-13 used in the examples, but are not limited to these.

[0203] The resin (A) may be used alone or in combination of two or more kinds. The content of the resin (A) 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, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. There is no upper limit, but it is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 97% by mass or less.

[0204] [Alkali-soluble resin having a phenolic hydroxyl group] 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)"). Resin (C) preferably has a structural unit having a phenolic hydroxyl group. In this case, typically, a negative pattern is preferably formed. The crosslinking agent (G) may be supported on the resin (C). Among resins (C), those that correspond to resins whose polarity increases by the action of an acid are treated as resins whose polarity increases by the action of an acid. In such cases, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a resin whose polarity increases by the action of an acid as resin (C), or may contain at least a resin (C) other than a resin whose polarity increases by the action of an acid and a resin whose polarity increases by the action of an acid. The resin (C) may contain the above-mentioned acid-decomposable group. The structural unit having a phenolic hydroxyl group contained in the resin (C) is not particularly limited, but is preferably the repeating unit (a4) described above.

[0205] The resin (C) may be used alone or in combination of two or more kinds. The content of the resin (C) in the total solid content of the actinic ray- or radiation-sensitive resin composition according to 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. There is no upper limit, but it is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of US Patent Application Publication No. 016 / 0282720 can be suitably used.

[0206] [Hydrophobic resin] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a hydrophobic resin (also referred to as "hydrophobic resin (E)"). 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 increases by the action of an acid, and a resin whose polarity increases by the action of an acid. The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains the hydrophobic resin (E), which makes it possible to control the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film, thereby improving development characteristics, suppressing outgassing, improving immersion liquid followability in immersion exposure, and reducing immersion defects. The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. In the present invention, a resin having a fluorine atom is treated as a hydrophobic resin or a fluorine-containing resin described later. Furthermore, the resin having a structural unit having an acid-decomposable group preferably does not contain a fluorine atom.

[0207] From the viewpoint of uneven distribution on the surface layer of the film, the hydrophobic resin (E) is preferably a resin containing a structural unit having at least one selected from the group consisting of a "fluorine atom," a "silicon atom," and a "CH partial structure contained in the side chain portion of the resin." When the hydrophobic resin (E) contains a fluorine atom or a silicon atom, the fluorine atom or silicon atom in the hydrophobic resin (E) may be contained in the main chain or in the side chain of the resin.

[0208] The hydrophobic resin (E) preferably has at least one group selected from the group consisting of the following (x) to (z): (x) Acid group (y) A group that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group). (z) Groups that decompose under the action of acid

[0209] 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 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 tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group. The acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl)methylene group.

[0210] Examples of the group (y) that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO-), and a sulfonate group (-S0-), and a lactone group or a carboxylic acid ester group (-COO-) is preferred. The structural unit containing these groups is a structural unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include structural units based on acrylic acid esters and methacrylic acid esters. In this structural unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, this structural unit may be introduced into the end of the resin using a polymerization initiator or chain transfer agent having these groups during polymerization. Examples of structural units having a lactone group include the same structural units having a lactone structure as those explained above in the section on resin (A).

[0211] The content of the structural unit having a group (y) that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer is preferably from 1 to 100 mol %, more preferably from 3 to 98 mol %, and even more preferably from 5 to 95 mol %, based on all structural units in the hydrophobic resin (E).

[0212] In the hydrophobic resin (E), the structural unit having a group (z) that decomposes under the action of acid may be the same as the structural unit having an acid-decomposable group listed for the resin (A). The structural unit having a group (z) that decomposes under the action of acid may have at least one of a fluorine atom and a silicon atom. The content of the structural unit having a group (z) that decomposes under the action of acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and even more preferably 20 mol% to 60 mol%, based on the total structural units in the resin (E).

[0213] The hydrophobic resin (E) may further have a structural unit other than the above-mentioned structural units.

[0214] The fluorine atom-containing structural units preferably account for 10 mol % to 100 mol %, more preferably 30 mol % to 100 mol %, of all structural units contained in the hydrophobic resin (E), and the silicon atom-containing structural units preferably account for 10 mol % to 100 mol %, more preferably 20 mol % to 100 mol %, of all structural units contained in the hydrophobic resin (E).

[0215] On the other hand, particularly when the hydrophobic resin (E) contains a CH3 partial structure in the side chain portion, it is also preferable that the hydrophobic resin (E) is substantially free of fluorine atoms and silicon atoms.Furthermore, it is preferable that the hydrophobic resin (E) is substantially composed only of structural units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

[0216] The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000.

[0217] The total content of residual monomer and oligomer components contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and the dispersity (Mw / Mn) is preferably in the range of 1 to 5, more preferably 1 to 3.

[0218] As the hydrophobic resin (E), known resins can be appropriately selected and used alone or in mixtures thereof. For example, known resins disclosed in paragraphs

[0451] to

[0704] of U.S. Patent Application Publication No. 2015 / 0168830 and paragraphs

[0340] to

[0356] of U.S. Patent Application Publication No. 2016 / 0274458 can be suitably used as the hydrophobic resin (E). In addition, the structural units disclosed in paragraphs

[0177] to

[0258] of U.S. Patent Application Publication No. 2016 / 0237190 are also suitable as structural units constituting the hydrophobic resin (E).

[0219] -Fluorine-containing resin- The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as a "fluorine-containing resin"). When the hydrophobic resin (E) contains a fluorine atom, it is preferably a resin having, as a partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

[0220] The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of aryl groups having a fluorine atom include aryl groups such as phenyl and naphthyl groups in which at least one hydrogen atom has been substituted with a fluorine atom.

[0221] 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.

[0222] [ka]

[0223] In formulas F2 to F4, R 57 ~R 68 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched), provided that R 57 ~R 61 At least one of R 62 ~R 64 and at least one of R 65 ~R 68 At least one of the groups independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom. R 57 ~R 61 and R65 ~R 67 Preferably, all of R are fluorine atoms. 62 , R 63 and R 68 is preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom has been substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 62 and R 63 may be linked to each other to form a ring.

[0224] In particular, the fluorine-containing resin is preferably alkali-decomposable, as this will provide better effects according to the present invention. The term "alkali-decomposable" for a fluororesin means that 30 mol% or more of the total amount of decomposable groups in the fluororesin is hydrolyzed after 10 minutes 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. The decomposition rate can be calculated from the ratio of the raw material to the decomposed product by NMR analysis.

[0225] From the viewpoints of improving the tolerance of the depth of focus, pattern linearity, development characteristics, suppressing outgassing, improving the immersion liquid followability in immersion exposure, and reducing immersion defects, the fluorine-containing resin preferably has a constitutional unit represented by formula X. From the viewpoints of improving the latitude of the depth of focus, pattern linearity, development characteristics, suppressing outgassing, improving the immersion liquid followability in immersion exposure, and reducing immersion defects, it is preferable that the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention further contains a fluorine-containing resin having a structural unit represented by formula X.

[0226] [ka]

[0227] In formula X, Z is a halogen atom, R 11 A group represented by OCH2- or R 12 represents a group represented by OC(=O)CH2-, and R 11 and R 12each independently represents a substituent, X represents an oxygen atom or a sulfur atom, L represents an (n+1)-valent linking group, R 10 represents a group having a group that is decomposed by the action of an alkaline aqueous solution to increase 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 may be the same as or different from each other.

[0228] Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. R 11 and R 12 Examples of the substituent as R include an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms), and an aryl group (preferably having 6 to 10 carbon atoms). 11 and R 12 The substituent as may further have a substituent, and such further substituent includes 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 carboxy group. The linking group represented by L is preferably a divalent or trivalent linking group (in other words, n is preferably 1 or 2), and more preferably a divalent linking group (in other words, n is preferably 1). The linking group represented by L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof. For example, when n is 1 and the linking group represented by L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, and a polyalkyleneoxy group. Among these, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred. The divalent aliphatic group may have a chain structure or a cyclic structure, but a chain structure is preferable to a cyclic structure, and a straight-chain structure is preferable to 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. Examples of the divalent aromatic group include an arylene group, of which a phenylene group and a naphthylene group are preferred. The divalent aromatic group may have a substituent, and examples of the substituents in the divalent aliphatic group include an alkyl group. Furthermore, L may be a divalent group obtained by removing two hydrogen atoms at any position from the structure represented by the above formulae LC1-1 to LC1-21 or SL1-1 to SL-3. When n is 2 or more, specific examples of the (n+1)-valent linking group include groups obtained by removing any (n-1) hydrogen atoms from the specific examples of the divalent linking groups described above. Specific examples of L include the following linking groups.

[0229] [ka]

[0230] As described above, these linking groups may further have a substituent.

[0231] R 10 is preferably a group represented by the following formula W. -YR 20 formula W

[0232] In the above formula W, Y represents a group that is decomposed by the action of an alkaline aqueous solution, thereby increasing the solubility in the alkaline aqueous solution. 20represents an electron-withdrawing group.

[0233] Examples of Y include a carboxylic acid ester group (-COO- or OCO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO-), and a sulfonate group (-SOO-), and a carboxylic acid ester group is preferred.

[0234] The electron-withdrawing group is preferably a partial structure represented by the following formula EW: * in formula EW represents a bond directly bonded to group Y in formula W.

[0235] [ka]

[0236] In the formula EW, n ew -C(R ew1 )(R ew2 n is the number of repetitions of the linking group represented by -, and represents an integer of 0 or 1. ew If is 0, it represents a single bond, and Y ew1 indicates that the bond is Y ew1 represents a halogen atom, a cyano group, a nitro group, or -C(R f1 )(R f2 )-R f3 Examples of the halo(cyclo)alkyl group include a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, and combinations thereof. (However, Y ew1 is a halogen atom, a cyano group, or a nitro group, n ew is 1.) R ew1 and R ew2 each independently represents any 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). R ew1 , Rew2 and Y ew1 At least two of these may be linked to each other to form a ring. The term "halo(cyclo)alkyl group" refers to an alkyl group or cycloalkyl group that is at least partially halogenated, and the term "haloaryl group" refers to an aryl group that is at least partially halogenated.

[0237] Y ew1 Examples of the aryl group include halogen atoms, -C(R f1 )(R f2 )-R f3 A halo(cyclo)alkyl group represented by the following formula or a haloaryl group is preferred.

[0238] R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group. R f2 and R f3 each independently represents a hydrogen atom, a halogen atom, or an organic group; R f2 and R f3 and may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom). R f2 and R f3 is preferably a (halo)alkyl group or a (halo)cycloalkyl group. f2 is R f1 or R f3 It is more preferable that they are linked to form a ring. R f2 and R f3 Examples of the ring formed by linking these include a (halo)cycloalkyl ring.

[0239] R f1 ~R f3The (halo)alkyl group in the formula (I) may be either linear or branched, and linear (halo)alkyl groups preferably have 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.

[0240] R f1 ~R f3 In or R f2 and R f3 The (halo)cycloalkyl group in the ring formed by linking and may be monocyclic or polycyclic. In the case of a polycyclic ring, the (halo)cycloalkyl group may be bridged. That is, in this case, the (halo)cycloalkyl group may have a bridged structure. Examples of these (halo)cycloalkyl groups include those represented by the following formulae and halogenated versions of these groups: In addition, some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[0241] [ka]

[0242] R f2 and R f3 In or R f2 and R f3 The (halo)cycloalkyl group in the ring formed by linking with is, for example, -C (n) F (2n-2) A fluorocycloalkyl group represented by H is preferred. Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0243] Y ew1 In or R f1 The (per)haloaryl group in the formula (I) is -C (n) F (n-1) Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0244] R ew1 , R ew2 and Yew1 The ring that may be formed by combining at least two of these is preferably a cycloalkyl group or a heterocyclic group.

[0245] Each group and each ring constituting the partial structure represented by the above formula EW may further have a substituent.

[0246] In the above formula W, R 20 is preferably an alkyl group substituted with one or more groups selected from the group consisting of a halogen atom, a cyano group, and a nitro group, more preferably an alkyl group substituted with a halogen atom (haloalkyl group), and even more preferably a fluoroalkyl group. The alkyl group substituted with one or more 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. More specifically, R 20 is -C(R' 1 )(R' f1 )(R' f2 ) or -C(R' 1 )(R' 2 )(R' f1 Preferably, R' is an atomic group represented by the formula: 1 and R' 2 R' each independently represents a hydrogen atom or an alkyl group that is not substituted with 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. R' 1 and R' 2 The alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. R' f1 and R' f2 The perfluoroalkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. R 20Preferred specific examples include -CF3, -C2F5, -C3F7, -C4F9, -CF(CF3)2, -CF(CF3)C2F5, -CF2CF(CF3)2, -C(CF3)3, -C5F 11 , -CF 13 , -C7F 15 , -C8F 17 , -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, -CH(CF3)C2F5, -CH2CF(CF3)2, and -CH2CN. Among these, -CF3, -C2F5, -C3F7, -C4F9, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN is preferred, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN is more preferred, -CH2C2F5, -CH(CF3)2, or -CH2CN is even more preferred, and -CH2C2F5 or -CH(CF3)2 is particularly preferred.

[0247] As the constitutional unit represented by formula X, a constitutional unit represented by formula X-1 or X-2 below is preferred, and a constitutional unit represented by formula X-1 is more preferred.

[0248] [ka]

[0249] In formula X-1, R 20 represents an electron-withdrawing group, and L 2 represents a divalent linking group, and X 2 represents an oxygen atom or a sulfur atom, Z 2 represents a halogen atom. In formula X-2, R 20 represents an electron-withdrawing group, and L 3 represents a divalent linking group, and X 3 represents an oxygen atom or a sulfur atom, Z 3 represents a halogen atom.

[0250] L 2 and L 3Specific examples and preferred examples of the divalent linking group as L are the same as those explained for L as the divalent linking group in formula X above. R 2 and R 3 The electron-withdrawing group as is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above, but a halo(cyclo)alkyl group is more preferred.

[0251] In the above formula X-1, L 2 and R 2 and do not bond to each other to form a ring, and in the above formula X-2, L 3 and R 3 and do not bond to each other to form a ring.

[0252] X 2 and X 3 is preferably an oxygen atom. Z 2 and Z 3 is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

[0253] Furthermore, as the constitutional unit represented by formula X, a constitutional unit represented by formula X-3 is also preferred.

[0254] [ka]

[0255] In formula X-3, R 20 represents an electron-withdrawing group, and R 21 represents a hydrogen atom, an alkyl group, or an aryl group; L 4 represents a divalent linking group, and X 4 represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

[0256] L 4 Specific examples and preferred examples of the divalent linking group as L are the same as those explained for L as the divalent linking group of formula X. R 4The electron-withdrawing group as is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above, but is more preferably a halo(cyclo)alkyl group.

[0257] In the above formula X-3, L 4 and R 4 and do not bond to each other to form a ring. X 4 is preferably an oxygen atom.

[0258] Furthermore, as the constitutional unit represented by formula X, a constitutional unit represented by formula Y-1 or a constitutional unit represented by formula Y-2 is also preferred.

[0259] [ka]

[0260] In formula Y-1 and formula Y-2, Z is a halogen atom, R 11 A group represented by OCH2- or R 12 represents a group represented by OC(=O)CH2-, and R 11 and R 12 each independently represents a substituent, R 20 represents an electron-withdrawing group.

[0261] R 20 The electron-withdrawing group as is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above, but is more preferably a halo(cyclo)alkyl group.

[0262] Z as a halogen atom, R 11 A group represented by OCH2- and R 12 Specific and preferred examples of the group represented by OC(=O)CH2- are the same as those explained in formula 1 above.

[0263] The content of the structural unit represented by formula X is preferably 10 mol % to 100 mol %, more preferably 20 mol % to 100 mol %, and even more preferably 30 mol % to 100 mol %, based on all structural units of the fluorine-containing resin.

[0264] Preferred examples of the structural units constituting the hydrophobic resin (E) are shown below. Preferred examples of the hydrophobic resin (E) include, but are not limited to, resins containing any combination of these structural units, or resins F-1 to F-3 used in the examples.

[0265] [ka]

[0266] [ka]

[0267] The hydrophobic resin (E) may be used alone or in combination of two or more kinds. It is preferable to use a mixture of two or more hydrophobic resins (E) having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure. 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, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.

[0268] <Photoacid generator> The composition according to the present invention preferably contains a photoacid generator (hereinafter also referred to as "photoacid generator (B)"). A photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation. The photoacid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation, such as a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound.

[0269] The photoacid generator may be selected from known compounds that generate an acid upon irradiation with actinic rays or radiation, either singly or in mixtures thereof. For example, known compounds disclosed in U.S. Patent Application Publication No. 2016 / 0070167, paragraphs

[0125] to

[0319] , U.S. Patent Application Publication No. 2015 / 0004544, paragraphs

[0086] to

[0094] , and U.S. Patent Application Publication No. 2016 / 0237190, paragraphs

[0323] to

[0402] may be suitably used as the photoacid generator (B).

[0270] [Compounds represented by formulas ZI, ZII and ZIII] Suitable embodiments of the photoacid generator (B) include, for example, compounds represented by the following formulae ZI, ZII and ZIII.

[0271] [ka]

[0272] In the above formula ZI, R 201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203 The organic group as the aryl group preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms. Also, R 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. 201 ~R203 Examples of groups formed by combining two of these include alkylene groups (for example, butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-. Z - represents an anion.

[0273] [Cation in the compound represented by formula ZI] Suitable embodiments of the cation in formula ZI include the corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below. The photoacid generator (C) may be a compound having a plurality of structures represented by formula ZI. For example, R 201 ~R 203 and R of another compound of formula ZI 201 ~R 203 and at least one of the above may be bonded via a single bond or a linking group.

[0274] -Compound ZI-1- First, the compound (ZI-1) will be explained. Compound (ZI-1) is a compound represented by the formula ZI above, 201 ~R 203 At least one of the groups is an aryl group, that is, an arylsulfonium compound, that is, a compound having an arylsulfonium as the cation. Aryl sulfonium compounds are R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0275] 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 having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium compound optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

[0276] R 201 ~R 203 The aryl group, alkyl group, and cycloalkyl 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.

[0277] -Compound ZI-2- Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound represented by the formula ZI, 201 ~R 203 are each independently an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom. R 201 ~R 203 The organic group having no aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms. R 201 ~R 203are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group.

[0278] R 201 ~R 203 The alkyl group and cycloalkyl group preferably include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group). R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0279] -Compound ZI-3- Next, the compound (ZI-3) will be described. Compound (ZI-3) is represented by the following formula ZI-3 and is a compound having a phenacylsulfonium salt structure.

[0280] [ka]

[0281] 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; 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; R x and Ry 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.

[0282] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring structure, and each ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic fused 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.

[0283] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and R y Examples of the group formed by bonding include a butylene group and a pentylene group. R 5c and R 6c , and R 5c and R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group. Zc - represents an anion.

[0284] -Compound ZI-4- Next, the compound (ZI-4) will be described. The compound (ZI-4) is represented by the following formula ZI-4.

[0285] [ka]

[0286] 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 group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group, and these groups may have a substituent; R 14 each independently represents a group having 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 cycloalkyl group, and these groups may have a substituent; R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group, and these groups may have a substituent; 15 may be bonded to each other to form a ring. The Two R's 15 When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. 15 are preferably alkylene groups and are bonded to each other to form a ring structure. Z - represents an anion.

[0287] In formula ZI-4, R 13 , R 14 and R 15 The alkyl group is linear or branched and preferably has 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.

[0288] [Cations in compounds represented by formula ZII or ZIII] Next, formulas ZII and ZIII will be explained. In formulas ZII and ZIII, R 204 ~R 207each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 ~R 207 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group having a heterocyclic structure containing 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. R 204 ~R 207 The alkyl group and cycloalkyl group preferably include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).

[0289] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 ~R 207 Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Z - represents an anion.

[0290] [Anions in compounds represented by formulas ZI to ZIII] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - , and Z in formula ZI-4 - is preferably an anion represented by the following formula An-1.

[0291] [ka]

[0292] 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, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and when rf is an integer of 2 or more, multiple -C(Xf)2- may be the same or different, and 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, and when pf is an integer of 2 or more, a plurality of -CR 4f R 5f - may be the same or different, and L f represents a divalent linking group, and when qf is an integer of 2 or more, a plurality of L f may be the same or different, and W represents an organic group containing a cyclic structure.

[0293] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this 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. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF3. It is particularly preferred that both Xf's are fluorine atoms.

[0294] R 4f and R 5f R 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 may be the same or different. R 4f and R5f The alkyl group represented by R may have a substituent and preferably has 1 to 4 carbon atoms. 4f and R 5f is preferably a hydrogen atom. 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.

[0295] L f represents a divalent linking group, and when there are multiple L f may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, and -NHCO-alkylene group- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, and -OCO-alkylene group- are more preferred.

[0296] W represents an organic group containing a cyclic structure, and among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. 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, tetracyclododecanyl, and adamantyl. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl, are preferred.

[0297] The aryl group may be monocyclic or polycyclic and includes, for example, phenyl, naphthyl, phenanthryl, and anthryl. The heterocyclic group may be monocyclic or polycyclic. Polycyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of aromatic heterocycles include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of non-aromatic heterocycles include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of lactone rings and sultone rings include the lactone structures and sultone structures exemplified for the resins described above. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

[0298] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0299] The anion represented by formula An-1 is SO3 - -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 is preferred. f , qf, and W are the same as in formula An-1. q' represents an integer of 0 to 10.

[0300] In one embodiment, Z in formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - , and Z in formula ZI-4 - The anion represented by the following formula 4 is also preferred.

[0301] [ka]

[0302] In formula 4, X B1 and X B2Each of X independently represents a monovalent organic group that does not contain a hydrogen atom or a fluorine atom. B1 and X B2 is preferably a hydrogen atom. X B3 and X B4 Each of X independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is preferably a fluorine atom or a monovalent organic group having a fluorine atom, B3 and X B4 It is more preferable that both of X and X are fluorine atoms or monovalent organic groups having a fluorine atom. B3 and X B4 It is more preferable that both of the above are alkyl groups substituted with fluorine. L f , qf and W are the same as in Equation 3.

[0303] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - , and Z in formula ZI-4 - As the anion, an anion represented by the following formula 5 is preferred.

[0304] [ka]

[0305] In Formula 5, each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and each Xb independently represents a hydrogen atom or an organic group having no fluorine atom. 4f , R 5f , L f The definitions and preferred embodiments of W are the same as those in Formula 3.

[0306] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - , and Z in formula ZI-4 -may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl or cycloalkyl group.

[0307] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - , and Z in formula ZI-4 - As the anion, an aromatic sulfonate anion represented by the following formula SA1 is also preferred.

[0308] [ka]

[0309] In Formula SA1, Ar represents an aryl group, and the sulfonate anion and -(DR B The substituents that may be further introduced include a fluorine atom and a hydroxyl group.

[0310] n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and particularly preferably 3.

[0311] D represents a single bond or a divalent linking group. Examples of this divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0312] R B represents a hydrocarbon group.

[0313] Preferably, D is a single bond and R B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

[0314] Preferred examples of the sulfonium cation in formula ZI and the sulfonium or iodonium cation in formula ZII are shown below.

[0315] [ka]

[0316] Anion Z in Formula ZI and Formula ZII - , Zc in formula ZI-3 - , and Z in formula ZI-4 - Preferred examples are shown below.

[0317] [ka]

[0318] Any combination of the above cations and anions can be used as a photoacid generator. In particular, it is preferable that the photoacid generator is an ionic compound containing a cation and an anion, and the anion contains an ion represented by any one of the above formula An-1, the following formula An-2, and the following formula An-3.

[0319] [ka]

[0320] In formula An-2 and formula An-3, Rfa each independently represents a monovalent organic group having a fluorine atom, and multiple Rfa may be bonded to each other to form a ring.

[0321] Rfa is preferably an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this 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. In addition, it is preferable that a plurality of Rfa groups are bonded to each other to form a ring.

[0322] In addition, compounds C-1 to C-42 used in the examples are also preferred as photoacid generators, but the invention is not limited thereto.

[0323] The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer, or may be in the form of a low molecular weight compound and a form of being incorporated into a part of a polymer in combination. The photoacid generator is preferably in the form of a low molecular weight compound. 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. When the photoacid generator is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the above-mentioned resin (A), or may be incorporated into a resin different from the resin (A). The photoacid generator may be used alone or in combination of two or more kinds. The content of the photoacid generator in the composition (the total content if multiple types are present) is preferably 0.1% by mass to 35% by mass, more preferably 0.5% by mass to 25% by mass, even more 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. When the photoacid generator contains a compound represented by the above formula ZI-3 or ZI-4, the content of the photoacid generator contained in the composition (the total content if multiple types are present) is preferably 5% by mass to 35% by mass, more preferably 7% by mass to 30% by mass, based on the total solid content of the composition.

[0324] <Acid diffusion control agent> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains an acid diffusion controller (also referred to as "acid diffusion controller (D)"). The acid diffusion controller (D) acts as a quencher that traps the acid generated from the acid generator or the like upon exposure and suppresses the reaction of the acid-decomposable resin in the unexposed areas due to excess generated acid. For example, the acid diffusion controller may be 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 a weaker acid than the acid generator, a low-molecular-weight compound (DD) that has a nitrogen atom and a group that is cleaved by the action of an acid, or an onium salt compound (DE) that has a nitrogen atom in the cation moiety. In particular, from the viewpoint of linearity of a pattern obtained after aging, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a nitrogen-containing compound, and more preferably contains a nitrogen-containing basic compound, as an acid diffusion controller. In the actinic ray-sensitive or radiation-sensitive resin composition according to 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 suitably used as the acid diffusion controller (D).

[0325] [Basic compounds (DA)] Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulae A to E.

[0326] [ka]

[0327] In Formula A and Formula E, R 200 , R 201 and R 202may 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). R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0328] The alkyl group in formula A and formula E may be substituted or unsubstituted. With regard to the alkyl group, the alkyl group having a substituent is preferably 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. More preferably, the alkyl groups in formulae A and E are unsubstituted.

[0329] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or the like, and more preferably a compound having an imidazole structure, a diazabicyclo 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.

[0330] [Basic compounds (DB) whose basicity is reduced or eliminated by exposure to actinic rays or radiation] The basic compound (DB) (hereinafter also referred to as "compound (DB)") whose basicity is reduced or eliminated upon irradiation with actinic rays or radiation is a compound that has a proton-accepting functional group and is decomposed upon irradiation with actinic rays or radiation, thereby reducing or eliminating its proton-accepting property, or changing from proton-accepting property to acidic property.

[0331] A proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having electrons, and examples thereof include a functional group having a macrocyclic structure such as a cyclic polyether, and a functional group having a nitrogen atom having a non-bonding electron pair that does not contribute to π-conjugation. The nitrogen atom having a non-bonding electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[0332]

Chemical formula

[0333] Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amines, pyridine, imidazole, and pyrazine structures.

[0334] Compound (DB) decomposes upon irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property decreases or disappears, or changes from a proton acceptor property to an acidic property. Here, the decrease or disappearance of the proton acceptor property, or the change from a proton acceptor property to an acidic property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, it means that the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by performing pH measurement.

[0335] The acid dissociation constant pKa of the compound generated by the decomposition of compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa < -1, more preferably -13 < pKa < -1, and still more preferably -13 < pKa < -3.

[0336] The acid dissociation constant pKa refers to the acid dissociation constant pKa in aqueous solution, and is defined, for example, in Chemistry Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). The lower the acid dissociation constant pKa value, the greater the acid strength. Specifically, the acid dissociation constant pKa in aqueous solution can be measured by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, values ​​can be calculated using the following software package 1 based on a database of Hammett's substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0337] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0338] [Onium salts (DC) that are weak acids relative to photoacid generators] In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, an onium salt (DC) that is a relatively weak acid compared to the photoacid generator can be used as another acid diffusion controller. When a photoacid generator is used in combination with an onium salt that generates an acid that is weaker than the acid generated by the photoacid generator, the acid generated by the photoacid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, releasing the weak acid through salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with lower catalytic activity, apparently deactivating the acid and enabling control of acid diffusion.

[0339] From the viewpoints of depth of focus tolerance and pattern linearity, it is preferable that the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention further contains at least one compound selected from the group consisting of compounds represented by formulas d1-1 to d1-3.

[0340] [ka]

[0341] 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, and a fluorine atom is not bonded to the carbon atom adjacent to the S atom; R 52 represents an organic group, and Y 3 represents a linear, branched or cyclic alkylene group 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.

[0342] M + Preferred examples of the sulfonium cation or iodonium cation represented by the formula ZI and the iodonium cation represented by the formula ZII can be mentioned.

[0343] The onium salt (DC) that is a weak acid relative to the photoacid generator may be a compound (hereinafter also referred to as "compound (DCA)") that has a cationic moiety and an anionic moiety in the same molecule, and the cationic moiety and the anionic moiety are linked by a covalent bond. The compound (DCA) is preferably a compound represented by any one of the following formulae C-1 to C-3.

[0344] [ka]

[0345] In formulas C-1 to C-3, R 1 , R 2 , and R 3 each independently represents a substituent having one or more carbon atoms. L 1 represents a divalent linking group or a single bond that links a cationic moiety and an anionic moiety. -X- -COO - , -SO3 - , -SO2 - , and -N - -R 4 R represents an anionic moiety selected from 4 represents a monovalent substituent having at least one of a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)-), and a sulfinyl group (-S(=O)-) at the bonding site to the adjacent N atom. R 1 , R 2 , R 3 , R 4 , and L 1 may be bonded to each other to form a ring structure. 1 ~R 3 Two of these may be combined to represent one divalent substituent, which may be bonded to the N atom via a double bond.

[0346] R 1 ~R 3 Examples of the substituent having one or more carbon atoms in the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and an arylaminocarbonyl group. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

[0347] L as a divalent linking group 1 Examples of L include a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and a group formed by combining two or more of these. 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0348] [Low molecular weight compound (DD) having a nitrogen atom and a group that is cleaved by the action of an acid] The low molecular weight compound (DD) having a nitrogen atom and a group that is cleaved by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having, on the nitrogen atom, a group that is cleaved by the action of an acid. The group that is eliminated 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. The molecular weight of the compound (DD) is preferably 100-1,000, more preferably 100-700, and even more preferably 100-500. Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following formula d-1.

[0349] [ka]

[0350] In formula d-1, R b R 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 may be linked to each other to form a ring. R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R may each independently be substituted with a functional group such as a hydroxy group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group, an alkoxy group, or a halogen atom. b The same applies to the alkoxyalkyl group represented by the formula:

[0351] R bAs the alkyl group, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. The Two R's b Examples of the ring formed by mutually linking include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. Specific examples of the group represented by formula d-1 include, but are not limited to, the structures disclosed in paragraph 0466 of US Patent Application Publication No. 2012 / 0135348.

[0352] The compound (DD) preferably has a structure represented by the following formula 6.

[0353] [ka]

[0354] In Equation 6, l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied. R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R a can be the same or different, and two R a may be linked together to form a heterocycle together with the nitrogen atom in the formula, and this heterocycle may contain heteroatoms other than the nitrogen atom in the formula. R b is R in the above formula d-1 b The same applies to preferred examples. In Equation 6, R a The alkyl group, cycloalkyl group, aryl group, and aralkyl group as R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the same groups as those mentioned above as optionally substituted groups.

[0355] Above R aSpecific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (which may be substituted with the above groups) include R b Examples of the groups include the same as the specific examples given above. Specific structures of particularly preferred compounds (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph 0475 of U.S. Patent Application Publication No. 2012 / 0135348.

[0356] The onium salt compound (DE) having a nitrogen atom in the cation moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is further preferable that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly bonded to the nitrogen atom. Preferred specific structures of compound (DE) include, but are not limited to, the compounds disclosed in paragraph 0203 of US Patent Application Publication No. 2015 / 0309408.

[0357] Other preferred examples of the acid diffusion controller are shown below.

[0358] [ka]

[0359] [ka]

[0360] [ka]

[0361] [ka]

[0362] [ka]

[0363] [ka]

[0364] In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, the other acid diffusion controllers may be used alone or in combination of two or more. The content of the acid diffusion controller in the composition (the total content if multiple types 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.

[0365] <Solvent> In the following, among the solvents shown as specific examples, those corresponding to the compounds represented by the above general formula (1) or (2) are excluded. 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. In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, known resist solvents can be appropriately used. 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 suitably used. Examples of solvents 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 pyruvates.

[0366] As the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure with a solvent not containing a hydroxyl group may be used. The solvent containing a hydroxyl group and the solvent not containing a hydroxyl group can be appropriately selected from the above-mentioned exemplary compounds, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate, and more preferably propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate. In addition, as a solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, or an alkyl acetate is preferred. Among these, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate is more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone is even more preferred. As a solvent not containing a hydroxyl group, propylene carbonate is also preferred. Among these, from the viewpoint of uniformity of the layer to be formed, it is particularly preferred that the solvent contains γ-butyrolactone. The mixing ratio (mass ratio) of the solvent containing a hydroxyl group to the solvent not containing a hydroxyl group is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50 mass % or more of the solvent not containing a hydroxyl group is preferred in terms of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a solvent containing propylene glycol monomethyl ether acetate alone, or a mixed solvent containing two or more kinds of propylene glycol monomethyl ether acetate.

[0367] The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, but is preferably 0.5% by mass to 50% by mass, more preferably 1.0% by mass to 45% by mass, and even more preferably 1.0% by mass to 40% by mass. The solid content concentration is the mass percentage of the mass of the resist components other than the solvent relative to the total mass of the composition.

[0368] <Crosslinking agent> 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 a crosslinking agent (G)). As the crosslinking agent (G), known compounds can be appropriately used. For example, 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 suitably used as the crosslinking agent (G). The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking a resin, and examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, and an oxetane ring. The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring, or an oxetane ring. The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinkable groups. The crosslinking agent (G) is more preferably a phenol derivative, a urea-based compound (a compound having a urea structure), or a melamine-based compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group. The crosslinking agent may be used alone or in combination of two or more kinds. The content of the crosslinking agent (G) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, and even more preferably from 5 to 30% by mass, based on the total solid content of the composition.

[0369] <Surfactant> 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)"). When a surfactant is contained, it is preferable that the composition contains at least one of a fluorine-based 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).

[0370] By including a surfactant in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a resist pattern with good sensitivity and resolution, excellent adhesion, and few development defects can be obtained when an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less, is used. Examples of fluorine-based or silicone-based surfactants include surfactants described in paragraph 0276 of US Patent Application Publication No. 2008 / 0248425. Furthermore, surfactants other than fluorine-based or silicone-based surfactants described in paragraph 0280 of US Patent Application Publication No. 2008 / 0248425 can also be used.

[0371] These surfactants may be used alone or in combination of two or more. When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass%, and more preferably 0.0005 to 1 mass%, based on the total solid content of the composition. On the other hand, by setting the content of the surfactant to 0.0001% by mass or more based on the total solid content of the composition, the hydrophobic resin is more unevenly distributed on the surface, which makes the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic and improves water tracking during immersion exposure.

[0372] <Other additives> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain other known additives. Other additives include acid amplifiers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution promoters.

[0373] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the solution through a filter, and then coating the solution on a predetermined support (substrate). The pore size (hole diameter) of the filter used for filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. Furthermore, when the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is high (for example, 25 mass % or more), the pore size of the filter used for filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as disclosed in JP-A-2002-62667, cyclic filtration may be performed, or filtration may be performed by connecting multiple types of filters in series or parallel. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment or the like before or after filter filtration.

[0374] The thickness of the resist film made of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, but from the viewpoint of improving resolution, it is preferably 90 nm or less, more preferably 85 nm or less. Such a thickness can be achieved by setting the solids concentration in the composition within an appropriate range to provide an appropriate viscosity and improve coatability or film-forming properties.

[0375] <Application> 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 reaction upon irradiation with light. More specifically, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs (integrated circuits), manufacturing circuit boards such as liquid crystal or thermal heads, preparing imprint mold structures, other photofabrication processes, or manufacturing lithographic printing plates or acid-curable compositions. Resist patterns formed using 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, MEMS (microelectromechanical systems), and the like.

[0376] (resist film) The resist film according to the present invention is a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The resist film according to the present invention is a solidified product of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The solidified product in the present invention may be any product obtained by removing at least a part of the solvent from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. Specifically, the resist film according to the present invention can be obtained, for example, by applying the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention onto a support such as a substrate, and then drying the applied composition. The above-mentioned drying refers to removing at least a part of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The drying method is not particularly limited, and known methods can be used, including drying by heating (for example, 70°C to 130°C, for 30 seconds to 300 seconds). The heating method is not particularly limited, and known heating means can be used, such as a heater, oven, hot plate, infrared lamp, or infrared laser.

[0377] The components contained in the resist film according to the present invention are the same as the components contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention excluding the solvent, and preferred embodiments are also the same. The content of each component contained in the resist film according to the present invention corresponds to the content of each component other than the solvent in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, where the term "total solids content" is replaced with "total mass of the resist film."

[0378] The thickness of the resist 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. Furthermore, when it is desired to form a thick resist film in association with the three-dimensionalization of memory devices, the thickness is preferably, for example, 2 μm or more, more preferably 2 μm to 50 μm, and even more preferably 2 μm to 20 μm.

[0379] (Pattern formation method) The pattern forming method according to the present invention comprises: a step of exposing the resist film of the present invention to actinic rays or radiation (exposure step); and The method includes a step of developing the resist film after the exposure step using a developer (development step). The pattern forming method according to the present invention includes a step of forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (film formation step); a step of exposing the resist film to actinic rays or radiation (exposure step); and The method may also include a step of developing the resist film after the exposure step using a developer (development step).

[0380] <Film forming process> The pattern forming method according to the present invention may include a film forming step. Examples of the method for forming a resist film in the film forming step include the method for forming a resist film by drying, as described above in the section on resist film.

[0381] [Support] The support is not particularly limited, and may be a substrate generally used in the manufacturing process of semiconductors such as ICs, or circuit boards such as liquid crystal or thermal heads, as well as other photofabrication lithography processes, etc. Specific examples of the support include inorganic substrates such as silicon, SiO2, and SiN.

[0382] <Exposure process> The exposure step is a step of exposing the resist film to light. The exposure method may be immersion exposure. The pattern formation method according to the present invention may include the exposure step multiple times. The type of light (actinic rays or radiation) used for exposure may be selected in consideration of the properties of the photoacid generator, the desired pattern shape, and the like. Examples of light 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. For example, actinic rays with a wavelength of 250 nm or less are preferred, 220 nm or less is more preferred, and 1 to 200 nm is even more preferred. Specific examples of light that can be used include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), and electron beams, with ArF excimer laser, EUV, and electron beams being preferred. In particular, the exposure in the exposure step is preferably performed by immersion exposure using an argon fluoride laser. The exposure dose is 5 mJ / cm 2~200mJ / cm 2 and preferably 10 mJ / cm 2 ~100mJ / cm 2 It is more preferable that:

[0383] <Developing process> 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), and is preferably an alkaline aqueous solution.

[0384] [Alkaline developer] As the alkaline developer, a quaternary ammonium salt such as tetramethylammonium hydroxide is preferably used, but other alkaline aqueous solutions such as inorganic alkali, primary to tertiary amines, alkanolamines, and cyclic amines can also be used. Furthermore, the alkaline developer may contain an appropriate amount of at least one of alcohols and surfactants. The alkaline developer preferably has an alkali concentration of 0.1% by mass to 20% by mass. The alkaline developer preferably has a pH of 10 to 15. The time for development using an alkaline developer is preferably 10 seconds to 300 seconds. The alkali concentration, pH and development time of the alkaline developer can be adjusted appropriately depending on the pattern to be formed.

[0385] [Organic Developer] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0386] -Ketone-based solvents- 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, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0387] -Ester-based solvents- Examples of ester-based solvents 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 butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0388] -Other solvents- As the alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent, the solvents disclosed in paragraphs 0715 to 0718 of US Patent Application Publication No. 2016 / 0070167 can be used.

[0389] The developer may contain a mixture of two or more of the above solvents, or may contain water or a solvent other than the above solvents. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably substantially no water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0390] -Surfactants- The organic developer may contain an appropriate amount of a known surfactant, if necessary. 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.

[0391] -Acid diffusion control agent- The organic developer may contain the acid diffusion controller described above.

[0392] [Developing method] Examples of development methods that can be applied include a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of piling up developer on the surface of the substrate by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying developer onto the surface of the substrate (spray method), and a method of continuously discharging developer while scanning a developer discharging nozzle at a constant speed onto a substrate that is rotating at a constant speed (dynamic dispense method).

[0393] A step of developing using an alkaline aqueous solution (alkaline developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined, which allows pattern formation without dissolving only the region of intermediate exposure intensity, thereby enabling the formation of finer patterns.

[0394] <Pre-baking process, post-exposure baking process> The pattern formation method according to the present invention preferably includes a pre-bake (PB) step prior to the exposure step. The pattern formation method according to the present invention may include the pre-heating step multiple times. The pattern formation method according to the present invention preferably includes a post-exposure bake (PEB) step after the exposure step and before the development step. The pattern formation method according to the present invention may include the post-exposure baking step multiple times. The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C in both the pre-baking step and the post-exposure baking step. The heating time in both the pre-baking step and the post-exposure baking step is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and even more preferably 30 seconds to 90 seconds. Heating can be carried out by means provided in the exposure device and the development device, and may also be carried out using a hot plate or the like.

[0395] <Resist underlayer film formation process> 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. 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), anti-reflective film, etc.) between the resist film and the support. Known organic or inorganic materials can be used as the resist underlayer film.

[0396] <Protective film formation process> 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. The protective film forming step is a step of forming a protective film (top coat) on the upper layer of the resist film. Known materials can be used as the protective film. For example, protective film-forming compositions disclosed in U.S. Patent Application Publication No. 2007 / 0178407, U.S. Patent Application Publication No. 2008 / 0085466, U.S. Patent Application Publication No. 2007 / 0275326, U.S. Patent Application Publication No. 2016 / 0299432, U.S. Patent Application Publication No. 2013 / 0244438, and International Publication No. 2016 / 157988 can be suitably used. The protective film-forming composition preferably contains the acid diffusion controller described above. A protective film may be formed on the resist film containing the hydrophobic resin.

[0397] <Rinse process> The pattern forming method according to the present invention preferably includes a step of washing with a rinse liquid (rinsing step) after the development step.

[0398] [In the case of a development process using an alkaline developer] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of surfactant. In this case, after the development step or the rinse step, a treatment may be added in which the developer or rinse liquid adhering to the pattern is removed using a supercritical fluid. Furthermore, after the rinse treatment or the treatment with a supercritical fluid, a heat treatment may be performed to remove moisture remaining in the pattern.

[0399] [In the case of a development process using an organic developer] The rinse liquid used in the rinse step after 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 solution containing a general organic solvent can be used. As the rinse liquid, it is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include those similar to those described in the developer containing an organic solvent. In this case, the rinse liquid used in the rinse step is more preferably a rinse liquid containing a monohydric alcohol.

[0400] The monohydric alcohol used in the rinsing step may be a linear, branched, or cyclic monohydric alcohol. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 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.

[0401] A plurality of each component may be mixed, or each component may be mixed with an organic solvent other than those mentioned above. 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 keeping the water content at 10% by mass or less, good development characteristics can be obtained.

[0402] The rinse liquid may contain an appropriate amount of a surfactant. In the rinsing step, the substrate developed using an organic developer is cleaned with a rinse solution containing an organic solvent. The cleaning method is not particularly limited, but examples include a method in which the rinse solution is continuously sprayed onto a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed for a certain period of time in a tank filled with the rinse solution (dipping method), or a method in which the rinse solution is sprayed onto the substrate surface (spray method). Among these, the spin coating method is preferably used for the cleaning process, and after cleaning, the substrate is rotated at a speed of 2,000 to 4,000 rpm (revolutions per minute) to remove the rinse solution from the substrate. It is also preferable to include a heating step (post-bake) after the rinsing step. This heating step removes the developer and rinse solution remaining between and within the patterns. In the heating step after the rinsing step, the heating temperature is preferably 40 to 160°C, more preferably 70 to 95°C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 to 90 seconds.

[0403] <Improvement of surface roughness> A method for improving the surface roughness of a pattern formed by the pattern formation method according to the present invention may be applied. Examples of methods for improving the surface roughness of a pattern include a method for treating a resist pattern with a plasma of a gas containing hydrogen, as disclosed in U.S. Patent Application Publication No. 2015 / 0104957. Other known methods may also be applied, such as those described in Japanese Patent Laid-Open 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." Furthermore, the resist pattern formed by the above method can be used as a core in the spacer process disclosed in, for example, JP-A-3-270227 and US Patent Application Publication No. 2013 / 0209941.

[0404] (Electronic device manufacturing method) The method for manufacturing an electronic device according to the present invention includes the pattern formation method according to the present invention. The electronic device manufactured by the method for manufacturing an electronic device according to the present invention is suitable for use in electrical and electronic equipment (e.g., home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). [Example]

[0405] The following examples further illustrate the embodiments of the present invention. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0406] <Resin (A)> The structures of the resins (A-1 to A-37) used are shown below. The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). The composition ratio (mol %) of the resin was: 13 Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0407] [ka]

[0408] [ka]

[0409] [ka]

[0410] [ka]

[0411] [ka]

[0412] The content ratio of each repeating unit in the resin is expressed in mol %.

[0413] In the present specification and examples, the glass transition temperature (Tg) of a homopolymer of a monomer a1 corresponding to a repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature (Tg) of 50°C or less when made into a homopolymer can be determined by reference to the description in PCT / JP2018 / 018239.

[0414] <Photoacid generator> The structures of the photoacid generators (C-1 to C-42) used are shown below.

[0415] [ka]

[0416] [ka]

[0417] [ka]

[0418] [ka]

[0419] [ka]

[0420] [ka]

[0421] <Acid diffusion control agent> The structures of the acid diffusion controllers used are shown below.

[0422] [ka]

[0423] [ka]

[0424] [ka]

[0425] The structure of the crosslinking agent used is shown below.

[0426] [ka]

[0427] [ka]

[0428] The structure of the hydrophobic resin used is shown below. The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). The composition ratio (mol %) of the resin was: 13 Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0429] [ka]

[0430] [ka]

[0431] The structures and molecular weights of the compounds (P) (also referred to as specific additives) used are shown in Table 1 below.

[0432] [Table 1]

[0433] [Table 2]

[0434] The structures and molecular weights of compounds AEC-1 to AEC-4 and AAC-1 used in the comparative examples are shown in Table 2 below.

[0435] [Table 3]

[0436] The surfactants (E) used are shown below.

[0437] [ka]

[0438] E-2: Megafac R-41 (DIC Corporation) E-3: KF-53 (Shin-Etsu Chemical Co., Ltd.) E-4: Megafac F176 (DIC Corporation) E-5: Megafac R08 (DIC Corporation) E-6: Troysol S366 (manufactured by Troy Corporation)

[0439] The compounds (H-1) to (H-4) used are shown below.

[0440] [ka]

[0441] The solvents used are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Ethyl lactate S-4: Ethyl 3-ethoxypropionate S-5: 2-heptanone S-6: methyl 3-methoxypropionate S-7: 3-Methoxybutyl acetate S-8: Butyl acetate S-9: Cyclohexanone S-10: Propylene carbonate S-11: Cycloheptanone S-12: Propylene glycol monoethyl ether

[0442] (Examples 1 to 318 and Comparative Examples 1 to 10) <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (KrF exposure) (Examples 1 to 7, 15 to 18, 23 to 29, 36, 127 to 246, Comparative Examples 1, 2, 5 to 10) Solutions were obtained by mixing the components shown in Tables 3 and 4 to give solid concentrations (% by mass) shown in Tables 3 and 4. The resulting solutions were then filtered through a polyethylene filter with a pore size of 3 μm to prepare actinic ray-sensitive or radiation-sensitive resin compositions (resist compositions). In the resist composition of the present invention, the solid content refers to all components other than the solvent and specific additives. The resist composition obtained was used in the examples and comparative examples. In the tables, the content (% by mass) of each component other than the solvent means the content ratio relative to the total solid content. The table also lists the content (% by mass) of the solvent used relative to the total solvent.

[0443] <Measurement of the Content of Specific Additives in Actinic Ray- or Radiation-Sensitive Resin Composition> The specific additives in the actinic ray-sensitive or radiation-sensitive resin compositions shown in Tables 3 and 4 were added in the amounts shown in Tables 3 and 4. The content of the specific additives was measured as follows. (Compound represented by general formula (1)) A 10% by mass solution of the resist solution in acetonitrile was prepared and filtered through a 0.20 μm pore size PTFE filter (DISMIC-25JP, Advantec). The solution was then analyzed using a gas chromatograph (GC) (Agilent-6890A, Agilent Technologies) equipped with a wax column (DB-HeavyWAX (#123-7162), Agilent Technologies) and an FID detector (Agilent-6890A, Agilent Technologies). The content of the compound represented by general formula (1) was quantified using the absolute calibration curve method using standard reagents for each compound. The standard reagent is a mixture of the compound represented by general formula (1) to be quantified at a known concentration and acetonitrile at a known concentration. Commercially available acetonitrile can be used as the acetonitrile. The contents of compounds (AEC-1 to AEC-4) similar to the compound represented by general formula (1) shown in Comparative Examples were also measured in the same manner.

[0444] (Compound represented by general formula (2)) Three mL of a 20% (by mass) acetonitrile solution of resist solution, 1 mL of a 1N acetonitrile solution of phosphoric acid, and 1 mL of a 0.1% acetonitrile solution of 2,4-dinitrophenylhydrazine (DNPH) were mixed and sonicated for 3 minutes using an ultrasonicator (a tabletop ultrasonic cleaner (#5510, Bransonic). The resulting mixture was filtered through a 0.20 μm PTFE filter (DISMIC-25JP, Advantec). The mixture was then analyzed using a liquid chromatograph (Agilent 1100 HPLC G1311A, Agilent Technologies) with a UV detector (Agilent 1100 HPLC G1315B, Shimadzu GLC) and a reverse-phase column (Shim-pack CLC-ODS(M), Shimadzu GLC). The content of the compound represented by general formula (2) was quantified using an absolute calibration curve method using standard reagents for each compound. The standard reagent is a mixture of the compound represented by general formula (2) to be quantified, the concentration of which is known, and DNPH, the concentration of which is known. The content of a compound (AAC-1) similar to the compound represented by general formula (2) shown in the comparative example was also measured in the same manner.

[0445] <Pattern formation method (1): KrF exposure, alkaline aqueous solution development> Using a Tokyo Electron spin coater "ACT-8," the resist compositions prepared above as shown in Tables 3 and 4 were dropped onto an 8-inch Si substrate (manufactured by Advanced Materials Technology Co., Ltd. (hereinafter also referred to as "substrate")) that had been treated with hexamethyldisilazane and had no anti-reflective layer, while the substrate was stationary. After dropping, the substrate was rotated, and the rotation speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, then at 500 rpm for another 3 seconds, then at 100 rpm for 2 seconds again, after which the rotation speed was increased to the film thickness setting speed (1200 rpm) and maintained for 60 seconds. The substrate was then heated and dried on a hot plate at 130°C for 60 seconds to form a 12 μm-thick positive resist film. This resist film was subjected to pattern exposure using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm) under exposure conditions of NA=0.60 and σ=0.75, with a mask having a line-and-space pattern that would result in a pattern with a space width of 4.5 μm and a pitch width of 25 μm after reduction projection exposure and development. After exposure, the resist film was baked at 120°C for 60 seconds, immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with pure water for 30 seconds, dried, and then baked at 110°C for 60 seconds to form an isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm. The pattern exposure was performed through a mask having a line and space pattern such that the space width after reduced projection exposure was 4.5 μm and the pitch width was 25 μm. The exposure dose was set to the optimum exposure dose (sensitivity) (mJ / cm) for forming an isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm. 2 In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation). By the above procedure, a patterned wafer for evaluation was obtained, which had a substrate and a pattern formed on the surface of the substrate.

[0446] <Performance evaluation> [Stability over time] The resist composition was stored at 40°C for 4 weeks, and then an isolated pattern was formed in the same manner as above. The sensitivity of the resulting isolated space pattern was determined in the same manner as above, and the difference between the sensitivity of the isolated space pattern formed using the resist composition before storage and the sensitivity of the isolated space pattern formed using the resist composition after storage (4 weeks at 40°C), i.e., the degree of sensitivity variation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 mJ / cm 2 less than B: Observed sensitivity fluctuation is 1 mJ / cm 2More than 2mJ / cm 2 less than C: Observed sensitivity fluctuation is 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity fluctuation is 3 mJ / cm 2 End

[0447] [Rectangularity] The cross-sectional shape of a line and space pattern with a line width of 20.5 μm and a film thickness of 12 μm was observed, and the line width Lb at the bottom of the resist pattern and the line width La at the top of the resist pattern were measured using a length-measuring scanning electron microscope (SEM Hitachi, Ltd. S-9380II). The results were rated as "A" if 0.95≦(La / Lb)≦1.05, "B" if 0.90≦(La / Lb)<0.95 or 1.05<(La / Lb)≦1.10, "C" if 0.85≦(La / Lb)<0.90 or 1.10<(La / Lb)≦1.15, and "D" if outside the ranges of "A", "B", and "C".

[0448] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (ArF exposure) (Examples 8 to 10, 19 to 20, 30 to 31, 247 to 318, Comparative Example 3) The various components shown in Tables 3 and 4 were mixed to obtain a solution having the solid content (% by mass) shown in Tables 3 and 4. The obtained 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, in that order. The obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the examples and comparative examples. In the resist composition, the solid content in this embodiment means all components other than the solvent and specific additives. In the tables, the content (% by mass) of each component other than the solvent means the content ratio relative to the total solid content. The table also lists the content (% by mass) of the solvent used relative to the total solvent. The content of specific additives was measured in the same manner as above.

[0449] <Patterning method (2): ArF immersion exposure, alkaline aqueous solution development (positive)> An organic antireflective coating composition SOC9110D and a Si-containing antireflective coating composition HM9825 were applied to a silicon wafer to form an antireflective coating. A resist composition was applied to the resulting antireflective coating, and the coating was baked at 100°C for 60 seconds (PB: prebake) to form a resist film with a thickness of 100 nm. The resulting wafer was exposed to light using an ArF excimer laser immersion scanner (ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6) through a 6% halftone mask with a 100 nm linewidth 1:1 line and space pattern. Ultrapure water was used as the immersion liquid. The wafer was then baked at 90°C for 60 seconds (PEB: Post Exposure Bake). The wafer was then developed by puddling with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds and rinsed with pure water to form a 100 nm linewidth 1:1 line and space (LS) pattern. The optimum exposure dose (sensitivity) for forming a 1:1 line and space (LS) pattern with a line width of 100 nm is (mJ / cm 2 In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation). By the above procedure, a patterned wafer for evaluation was obtained, which had a substrate and a pattern formed on the surface of the substrate. <Patterning method (3): ArF immersion exposure, organic solvent development (negative)> An organic antireflective coating composition SOC9110D and a Si-containing antireflective coating composition HM9825 were applied to a silicon wafer to form an antireflective coating. A resist composition was applied to the resulting antireflective coating, and the coating was baked at 100°C for 60 seconds (PB: prebake) to form a resist film with a thickness of 100 nm. The resulting wafer was exposed to light using an ArF excimer laser immersion scanner (ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6) through a 6% halftone mask with a 100 nm linewidth 1:1 line and space pattern. Ultrapure water was used as the immersion liquid. The wafer was then baked at 90°C for 60 seconds (PEB: Post Exposure Bake). The wafer was then developed by puddling with butyl acetate as the developer for 30 seconds and rinsed with methyl isobutyl carbinol (MIBC) to form a 100 nm linewidth 1:1 line and space (LS) pattern. The optimum exposure dose (sensitivity) for forming a 1:1 line and space (LS) pattern with a line width of 100 nm is (mJ / cm 2 In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation). By the above procedure, a patterned wafer for evaluation was obtained, which had a substrate and a pattern formed on the surface of the substrate.

[0450] <Performance evaluation> [Stability over time] The resist composition was stored at 40°C for 4 weeks, and then a line and space pattern was formed in the same manner as above. The sensitivity of the resulting line and space pattern was determined in the same manner as above, and the difference between the sensitivity of the line and space pattern formed using the resist composition before storage and the sensitivity of the line and space pattern formed using the resist composition after storage (4 weeks at 40°C), i.e., the degree of sensitivity variation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 mJ / cm 2 less than B: Observed sensitivity fluctuation is 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity fluctuation is 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity fluctuation is 3 mJ / cm 2 End

[0451] [Rectangularity] The cross-sectional shape of a line and space pattern with a line width of 100 nm and a film thickness of 100 nm was observed, and the line width Lb at the bottom of the resist pattern and the line width La at the top of the resist pattern were measured using a length-measuring scanning electron microscope (SEM Hitachi, Ltd. S-9380II). The results were rated as "A" if 0.95≦(La / Lb)≦1.05, "B" if 0.90≦(La / Lb)<0.95 or 1.05<(La / Lb)≦1.10, "C" if 0.85≦(La / Lb)<0.90 or 1.10<(La / Lb)≦1.15, and "D" if outside the ranges of "A", "B", and "C".

[0452] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EUV exposure) (Examples 11-12, 21, 32-33, Comparative Example 4) The various components shown in Tables 3 and 4 were mixed to obtain a solution having the solid content (% by mass) shown in Tables 3 and 4. The obtained 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, in that order. The obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the examples and comparative examples. In the resist composition, the solid content in this embodiment means all components other than the solvent and specific additives. In the tables, the content (% by mass) of each component other than the solvent means the content ratio relative to the total solid content. The table also lists the content (% by mass) of the solvent used relative to the total solvent. The content of specific additives was measured in the same manner as above.

[0453] <Patterning method (4): EUV exposure, alkaline development (positive)> AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 30 nm. A resist composition was applied thereon and baked at 120°C for 60 seconds (PB) to form a resist film with a thickness of 30 nm. This resist film was subjected to pattern irradiation using an EUV exposure system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 40 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 120°C for 60 seconds (PEB), developed in a tetramethylammonium hydroxide solution (TMAH, 2.38% by 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 to obtain a line-and-space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm). The optimum exposure dose (sensitivity) for forming a line and space (LS) pattern with a line width of 40 nm (mJ / cm 2 In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation). By the above procedure, a patterned wafer for evaluation was obtained, which had a substrate and a pattern formed on the surface of the substrate.

[0454] <Patterning method (5): EUV exposure, organic solvent development (negative)> AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 30 nm. The resist composition shown in the table was applied thereon and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 30 nm. This resist film was subjected to pattern irradiation using an EUV exposure system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 40 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 120°C for 60 seconds (PEB), then developed with butyl acetate for 30 seconds. The silicon wafer was rotated at 4000 rpm for 30 seconds and further baked at 90°C for 60 seconds, yielding a line-and-space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm). The optimum exposure dose (sensitivity) for forming a line and space (LS) pattern with a line width of 40 nm (mJ / cm 2 In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation). By the above procedure, a patterned wafer for evaluation was obtained, which had a substrate and a pattern formed on the surface of the substrate.

[0455] <Performance evaluation> [Stability over time] The resist composition was stored at 40°C for 4 weeks, and then a line and space pattern was formed in the same manner as above. The sensitivity of the resulting line and space pattern was determined in the same manner as above, and the difference between the sensitivity of the line and space pattern formed using the resist composition before storage and the sensitivity of the line and space pattern formed using the resist composition after storage (4 weeks at 40°C), i.e., the degree of sensitivity variation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 mJ / cm 2 less than B: Observed sensitivity fluctuation is 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity fluctuation is 2 mJ / cm 2More than 3mJ / cm 2 less than D: Observed sensitivity fluctuation is 3 mJ / cm 2 End

[0456] [Rectangularity] The cross-sectional shape of a line and space pattern with a line width of 40 nm and a film thickness of 30 nm was observed, and the line width Lb at the bottom of the resist pattern and the line width La at the top of the resist pattern were measured using a length-measuring scanning electron microscope (SEM Hitachi, Ltd. S-9380II). The results were rated as "A" if 0.95≦(La / Lb)≦1.05, "B" if 0.90≦(La / Lb)<0.95 or 1.05<(La / Lb)≦1.10, "C" if 0.85≦(La / Lb)<0.90 or 1.10<(La / Lb)≦1.15, and "D" if outside the ranges of "A", "B", and "C".

[0457] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EB exposure) (Examples 13, 14, 22, 34, 35, 37 to 126) Solutions were obtained by mixing the various components shown in Tables 3 and 4 to obtain the solid content concentrations (% by mass) shown in Tables 3 and 4. The resulting solutions were filtered through a polytetrafluoroethylene filter with a pore size of 0.03 μm to obtain actinic ray-sensitive or radiation-sensitive resin compositions (resist compositions). In the resist composition, the solid content in this embodiment means all components other than the solvent and specific additives. In the tables, the content (% by mass) of each component other than the solvent means the content ratio relative to the total solid content. The table also lists the content (% by mass) of the solvent used relative to the total solvent. The content of specific additives was measured in the same manner as above.

[0458] <Pattern formation method (6): EB exposure, alkaline development (positive)> The resist compositions shown in Tables 3 and 4 were applied onto a 6-inch wafer using a spin coater Mark 8 manufactured by Tokyo Electron Limited, and baked on a hot plate (PB) at 110°C for 90 seconds to obtain a resist film with a thickness of 80 nm. This resist film was patterned using an electron beam lithography system (ELS-7500 manufactured by Elionix Co., Ltd., accelerating voltage 50 KeV). A mask with a line size of 100 nm and a line:space ratio of 1:1 was used as the reticle. After irradiation, the film was baked on a hot plate (PEB) at 110°C for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide 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 100 nm). The optimum exposure dose (sensitivity) for forming a line and space (LS) pattern with a line width of 100 nm (μC / cm 2 In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation). By the above procedure, a patterned wafer for evaluation was obtained, which had a substrate and a pattern formed on the surface of the substrate.

[0459] <Performance evaluation> [Stability over time] The resist composition was stored at 40°C for 4 weeks, and then a line and space pattern was formed in the same manner as above. The sensitivity of the resulting line and space pattern was determined in the same manner as above, and the difference between the sensitivity of the line and space pattern formed using the resist composition before storage and the sensitivity of the line and space pattern formed using the resist composition after storage (4 weeks at 40°C), i.e., the degree of sensitivity variation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 μC / cm 2 less than B: Observed sensitivity fluctuation is 1 μC / cm2 More than 2μC / cm 2 less than C: Observed sensitivity fluctuation is 2 μC / cm 2 More than 3μC / cm 2 less than D: Observed sensitivity fluctuation is 3 μC / cm 2 End

[0460] [Rectangularity] The cross-sectional shape of a line and space pattern with a line width of 100 nm and a film thickness of 80 nm was observed, and the line width Lb at the bottom of the resist pattern and the line width La at the top of the resist pattern were measured using a length-measuring scanning electron microscope (SEM Hitachi, Ltd. S-9380II). The results were rated as "A" if 0.95≦(La / Lb)≦1.05, "B" if 0.90≦(La / Lb)<0.95 or 1.05<(La / Lb)≦1.10, "C" if 0.85≦(La / Lb)<0.90 or 1.10<(La / Lb)≦1.15, and "D" if outside the ranges of "A", "B", and "C".

[0461] The evaluation results are shown in Table 5.

[0462] [Table 4]

[0463] [Table 5]

[0464] [Table 6]

[0465] [Table 7]

[0466] [Table 8]

[0467]

Table 9

[0468]

Table 10

[0469]

Table 11

[0470]

Table 12

[0471]

Table 13

[0472]

Table 14

[0473]

Table 15

[0474] Table 16

[0475] Table 17

[0476] Table 18

[0477] [Table 19]

[0478] [Table 20]

[0479] [Table 21]

[0480] [Table 22]

[0481] [Table 23]

[0482] [Table 24]

[0483] The results in Table 5 show that the cross-sectional shape of the pattern obtained from the composition of the present invention has excellent rectangularity, and furthermore, the composition of the present invention has excellent stability over time. It should be noted that Examples 1 to 22, 34, 37 to 58, 70, 73 to 94, 106, 109 to 130, 142, 145 to 166, 178, 181 to 202, 214, 217 to 238, 250, 253 to 274, 286, and 289 to 310 should be read as reference examples. [Industrial Applicability]

[0484] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition which achieves both excellent rectangularity of the cross-sectional shape of the obtained pattern and excellent stability over time at a high level. The present invention further provides a resist film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0485] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on December 28, 2018 (Patent Application No. 2018-248645) and a Japanese patent application filed on July 26, 2019 (Patent Application No. 2019-138319), the contents of which are incorporated herein by reference.

Claims

1. a resin (A) whose polarity increases upon the action of an acid; a compound (B) that generates an acid upon exposure to actinic rays or radiation, and An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) which is a compound represented by any one of the following: the content of the compound (P) is 1 ppm or more and 1000 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, The actinic ray-sensitive or radiation-sensitive resin composition further contains an acid diffusion controller, and the acid diffusion controller is a basic compound (provided that the composition comprises: (A) an acid generator that generates an acid upon irradiation with actinic rays or radiation; (B) a resin whose solubility in alkali increases due to the action of an acid; and (C) a compound represented by the following formula (1): HS-Y-(R)u...(1) (wherein R represents an acid-decomposable group whose solubility in alkali increases under the action of acid, Y represents a linking group with a valence of u+1, and u represents an integer of 1 to 3), a photosensitive resin composition containing an acid generator A1 described below, a resin B1 described below, an alkali-soluble resin D1 described below, an alkali-soluble resin D2 described below, and tripentylamine, a photosensitive resin composition containing an acid generator A1 described below, a resin B1 described below, an alkali-soluble resin D1 described below, an alkali-soluble resin D2 described below, tripentylamine, and 3-mercaptopropionic acid, and a photosensitive resin composition containing an acid generator A1 described below, a resin B1 described below, an alkali-soluble resin D1 described below, an alkali-soluble resin D2 described below, tripentylamine, and 1-dodecanethiol. 【Chemical 1】 【Chemistry 2】 The numbers in the brackets at the bottom right of each structural unit in the structural formula of Resin B1 represent the content (mass %) of the structural unit in the resin. D1: Polyhydroxystyrene resin (p-hydroxystyrene:styrene = 85:15 (mass ratio) copolymer, mass average molecular weight (Mw) 2500) D2: Novolak resin (m-cresol and p-cresol were mixed in a mass ratio of m-cresol / p-cresol = 60 / 40, and the mixture was subjected to addition condensation in the presence of formaldehyde and an acid catalyst. Novolak resin (mass average molecular weight (Mw) 8000))

2. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

3. 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the compound (P) is 1 ppm or more and 200 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the content of the compound (P) is 1 ppm or more and 100 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

5. A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4.

6. 6. A pattern forming method comprising the steps of: exposing the resist film according to claim 5; and developing the exposed resist film with a developer.

7. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.

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