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

Abstract

The present invention provides: an actinic ray-sensitive or radiation-sensitive resin composition with which a pattern having excellent resolution can be formed; a resist film; a pattern forming method; and a method for producing an electronic device. An actinic ray-sensitive or radiation-sensitive resin composition according to the present invention comprises a resin having a repeating unit A1 represented by general formula (I) and a repeating unit A2 represented by general formula (II).

Description

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

[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.

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using actinic ray- or radiation-sensitive resin compositions (hereinafter simply referred to as "resist compositions"). In recent years, with the increasing integration density of integrated circuits, there has been a demand for ultrafine pattern formation in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as a light source have been developed. Furthermore, as a technique for further improving resolution, the so-called immersion method, in which a high refractive index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0004] For example, Patent Document 1 discloses a radiation-sensitive composition containing a polymer having an acid-dissociable group and a compound represented by formula (1) as a "radiation-sensitive composition capable of forming a resist film having high sensitivity, a wide process window, and excellent LWR performance." ５ is a group obtained by removing (m+n+2) hydrogen atoms from a monocyclic or fused aromatic hydrocarbon ring having r carbon atoms. － is -SO ３ － or -COO －r is an integer from 6 to 14. １ is a single bond, —O—, —S— or —NR ３ - is. R １ is a hydrogen atom or a monovalent organic group. １ is a chlorine atom, a bromine atom, or an iodine atom. m is an integer from 1 to (r-2). n is an integer from 0 to (r-3). R ２ is a substituted or unsubstituted monovalent hydrocarbon group. ＋ is a monovalent cation.

[0005]

[0006] International Publication No. 2024 / 057701

[0007] The above-mentioned document discloses a composition using a specific polymer. When a pattern is formed using this composition, the conventional resolution requirement is satisfied. However, there is a recent demand for further improvement in resolution, and the above-mentioned composition does not satisfy this requirement, so further improvement is necessary.

[0008] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern with excellent resolution. Another object of the present invention is to provide a resist film, a pattern forming method, and a device manufacturing method.

[0009] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, they have found that the above problems can be solved by the following configuration.

[0010] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit A1 represented by general formula (I) described later and a repeating unit A2 represented by general formula (II) described later. １ [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein L is an aromatic hydrocarbon ring group having one or more substituents selected from a fluorine atom, a fluoroalkyl group, and an iodine atom. １[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein X is an oxygen atom. [5] L ２ is -Y-C(=O)-*1 or a divalent aromatic ring group which may have a substituent, Y represents a single bond or a divalent linking group, and *1 represents the position at which it bonds to the oxygen atom as shown in general formula (II). [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the repeating unit A2 is a repeating unit represented by general formula (IIa) described below. [7] L ３ is -Y-C(=O)-*2, Y represents a single bond or a divalent linking group, and *2 represents a carbon atom bonded to the oxygen atom specified in the general formula (IIa). [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein at least one of the repeating unit A1 and the repeating unit A2 contains an iodine atom, or the resin further has a repeating unit containing an iodine atom other than the repeating unit A1 and the repeating unit A2. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the repeating unit A1 contains an iodine atom.

[10] Z ＋ is a sulfonium cation represented by general formula (III) described later.

[11] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to

[10] .

[12] A pattern forming method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to

[10] ; exposing the resist film; and developing the exposed resist film using a developer.

[13] A method for producing an electronic device, comprising the pattern forming method described in

[12] .

[0011] According to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern with excellent resolution. The present invention also provides a resist film, a pattern forming method, and a device manufacturing method.

[0012] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0013] The meaning of each description in this specification is explained below. In this specification, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits. In this specification, a hydrogen atom may be a protist atom (a normal hydrogen atom) or a deuterium atom (e.g., a deuterium atom, etc.). In the description of a group (atomic group) in this specification, a description that does not specify whether it is substituted or unsubstituted includes both a group that has a substituent and a group that has a substituent. For example, an "alkyl group" includes not only an alkyl group that has no substituent (an unsubstituted alkyl group) but also an alkyl group that has a substituent (a substituted alkyl group). In this specification, an "organic group" refers to a group containing at least one carbon atom.

[0014] Unless otherwise specified, the "substituent" in this specification is preferably a monovalent substituent. Examples of the substituent 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; Examples of the substituent include alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; 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; alkylthio groups; and combinations thereof. In the specification, these substituent groups are also referred to as "substituent K."

[0015] The bonding direction of divalent groups represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. In addition, the compound may be "X-CO-O-Z" or "X-O-CO-Z".

[0016] In this specification, with respect to a compound that may have geometric isomers (cis-trans isomers), the formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

[0017] In this specification, "(meth)acrylic" is a generic term including acrylic and methacrylic, and means "at least one of acrylic and methacrylic." Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid."

[0018] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, "exposure" as used herein includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers (such as ArF excimer lasers), extreme ultraviolet rays, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams.

[0019] In this specification, unless otherwise specified, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by Gel Permeation Chromatography (GPC) measurement 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).

[0020] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package.

[0021] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0022] On the other hand, pKa can also be determined by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0023] As described above, the pKa in this specification refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and publicly known literature values, but if the pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. Furthermore, as described above, the pKa in this specification refers to "pKa in aqueous solution," but if the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0024] As used herein, "ppm" means "parts per million (10 －６ ) and "ppb" stands for "parts per billion (10 －９ "ppt" means "parts per trillion (10 －１２ ")" means "parts per quadrillion (10 －１５ )"

[0025] In this specification, the term "solid content" refers to components that form a resist film and does not include solvents. Furthermore, any component that forms a resist film is considered to be a solid content even if it is in a liquid state.

[0026] [Actinic ray- or radiation-sensitive resin composition] The actinic ray- or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition") contains a resin having a repeating unit A1 represented by general formula (I) and a repeating unit A2 represented by general formula (II) described below. The mechanism by which the resist composition of the present invention can solve the problems of the present invention by adopting the above-mentioned configuration is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effects are obtained. In other words, even if the effects are obtained by a mechanism other than the one described below, it is still included in the scope of the present invention.

[0027] The repeating unit A1 and repeating unit A2 contained in the resin contained in the resist composition of the present invention exhibit an excellent balance between the acid strength of the arylsulfonic acid generated from repeating unit A1 and the reactivity during deprotection of the tertiary ester protecting group contained in repeating unit A2, and it is presumed that this allows for good control of acid diffusion in the resist composition, resulting in excellent resolution of the resist pattern obtained using the resist composition. Each component that may be contained in the resist composition will be described in detail below. In addition, excellent resolution of the pattern formed using the resist composition is also referred to as "excellent effects of the present invention."

[0028] [Resin Having Repeating Unit A1 and Repeating Unit A2] The resist composition of the present invention contains a resin (hereinafter also simply referred to as "resin P") having a repeating unit A1 represented by general formula (I) and a repeating unit A2 represented by general formula (II). In resin P, the repeating units A1 and A2 may be in any form, such as a random copolymer, a block copolymer, or an alternating copolymer (ABAB...). Resin P may also have a repeating unit A3 other than the repeating unit A1 and the repeating unit A2.

[0029] Preferably, at least one of the repeating units A1 and A2 contains an iodine atom, or the resin further contains a repeating unit other than the repeating units A1 and A2 that contains an iodine atom (in other words, the repeating unit A3 contains an iodine atom), more preferably, at least one of the repeating units A1 and A2 contains an iodine atom, and even more preferably, the repeating unit A1 contains an iodine atom. Each repeating unit will be described in detail below.

[0030] <Repeating Unit A1> The repeating unit A1 is a repeating unit represented by the following general formula (I).

[0031]

[0032] In general formula (I), R １ａ ~R １ｃ each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group, or an alkoxycarbonyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. The monovalent aliphatic hydrocarbon ring group preferably has 3 to 20 carbon atoms, more preferably 3 to 10. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxycarbonyl group may be linear, branched, or cyclic. The alkoxycarbonyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6.

[0033] R １ａ Among these, R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １ｂ and R １ｃ is preferably a hydrogen atom. １ｃ and L １ may be bonded to each other to form a ring. １ｃ and Ar １may be bonded to each other to form a ring. The ring may be either an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferred, and an aliphatic hydrocarbon ring is more preferred. The number of ring atoms in the ring is preferably 3 to 10, more preferably 3 to 6.

[0034] In the above general formula (I), L １ represents a single bond or a divalent linking group. １ The divalent linking group is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, —O—, —CO—, —NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.), and groups formed by combining two or more of these groups. Examples of linking groups formed by combining two or more of the above groups include -O-divalent aliphatic hydrocarbon group-, -divalent aromatic ring group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic ring group-, -CONH-divalent aromatic ring group-, -COO-divalent aliphatic hydrocarbon group-, -divalent aliphatic hydrocarbon group-O-divalent aliphatic hydrocarbon group-, and -CONH-divalent aliphatic hydrocarbon group-.

[0035] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the divalent aliphatic hydrocarbon group include alkylene groups, alkenylene groups, and alkynylene groups, with alkylene groups being preferred. The divalent aliphatic hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 24, and even more preferably 6 to 18.

[0036] The divalent aromatic ring group may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group), with an arylene group being preferred. The aromatic ring constituting the divalent aromatic ring group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the divalent aromatic ring group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10. The number of substituents that the divalent aromatic ring group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0037] The divalent aliphatic hydrocarbon group and the divalent aromatic ring group may have a substituent. Examples of the substituent that the divalent aliphatic hydrocarbon group may have include a halogen atom. Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. L １ Among these, a divalent aromatic ring group which may have a substituent is preferable, a phenylene group which may have a substituent is more preferable, and an alkoxy group having 1 to 6 carbon atoms or a phenylene group which may have an iodine atom is even more preferable.

[0038] In the above general formula (I), X is a single bond, —O— (oxygen atom), —S— (sulfur atom), —CO— (carbonyl group), —CS— (thiocarbonyl group), or —SO ２ - (sulfonyl group), and X is -O-, -S-, -CO-, or -SO ２ - is preferred, -O- or -CO- is more preferred, and -O- is even more preferred.

[0039] In the above general formula (I), Ar １ represents an aromatic ring group which may have a substituent. The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, with an aromatic hydrocarbon ring group being preferred. The aromatic ring constituting the aromatic ring group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the aromatic ring group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10. The number of substituents which the aromatic ring group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Examples of substituents which the aromatic ring group may have include a hydroxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

[0040] Ar １Among these, an aromatic hydrocarbon ring group having one or more substituents selected from a fluorine atom, a fluoroalkyl group, and an iodine atom is preferred, an aromatic hydrocarbon ring group having one or more fluorine atoms and / or iodine atoms is more preferred, and a benzene ring group having one or more fluorine atoms and / or iodine atoms is even more preferred.

[0041] In the above general formula (I), Z ＋ represents a sulfonium cation having an acid-decomposable group or a sulfonium cation having four or more fluorine atoms. Among the sulfonium cations having an acid-decomposable group and the sulfonium cations having four or more fluorine atoms, the sulfonium cation is preferably a cation represented by formula (ZaI) described later, and more preferably cation (ZaI-1) described later or cation (ZaI-4b) described later.

[0042] Z ＋ The number of acid-decomposable groups that the sulfonium cation represented by Z may have is preferably 1 to 3, and more preferably 1 or 2. ＋ The number of fluorine atoms that the sulfonium cation represented by the following formula (I) can have is preferably 4 to 20, and more preferably 4 to 15.

[0043] The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity, and typically decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a group (leaving group) that is released under the action of an acid. Examples of the polar group include a carbonyl group, a formyl group, a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, a (alkylsulfonyl) (alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tris(alkylcarbonyl) methylene group, a tris(alkylsulfonyl) methylene group, and an alcoholic hydroxy group. Specific examples of the acid-decomposable group include an acetal-type acid-dissociable group, a tertiary alkyl ester-type acid-dissociable group, and a tertiary alkyloxycarbonyl acid-dissociable group, with an acetal-type acid-dissociable group being preferred.

[0044] Z ＋ Among these, sulfonium cations represented by the following general formula (III) are preferred.

[0045] Ar ３ａ ~Ar ３ｃ each independently represents an aryl group which may have a substituent, Ar ３ａ ~Ar ３ｃ Two of Ar may be bonded to each other to form a ring. ３ａ ~Ar ３ｃ satisfies at least one of requirements 3 and 4.

[0046] (Requirement 3) Ar ３ａ ~Ar ３ｃ At least one of Ar has an acid-decomposable group. Specific examples of the acid-decomposable group are as described above. ３ａ ~Ar ３ｃ It is preferable that any one of Ar has an acid-decomposable group. ３ａ ~Ar ３ｃThe total number of fluorine atoms contained in the aryl group which may have a substituent is 4 or more. The total number of fluorine atoms contained in the aryl group which may have a substituent is preferably 4 to 20, and more preferably 4 to 15.

[0047] In the aryl group which may have a substituent, the aromatic ring constituting the aryl group may be either a monocyclic or polycyclic ring. The number of ring atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The number of substituents which the aryl group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Examples of the substituent include a fluorine atom, a fluoroalkyl group, an oxyfluoroalkyl group, and an iodine atom. The number of carbon atoms in the fluoroalkyl group and the oxyfluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.

[0048] <Repeating Unit A2> The repeating unit A2 is a repeating unit represented by the following general formula (II).

[0049]

[0050] In general formula (II), R ２ａ ~R ２ｃ Each of the groups independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Specific examples and preferred embodiments of the above-mentioned groups are shown in the general formula (I) above, R １ａ ~R １ｃ As detailed above, ２ａ Among these, R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ｂ and R ２ｃ is preferably a hydrogen atom. ２ｃ and L ２ may be bonded to each other to form a ring.

[0051] In general formula (II), L ２ represents a single bond or a divalent linking group. ２The divalent linking group is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, —O—, —CO—, —NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) and groups formed by combining two or more of these groups. Specific examples and preferred embodiments of each of the above groups are given in L １ The divalent linking group represented by the formula (I) is as described in detail above.

[0052] L ２ Among these, -Y-C(=O)-*1 or a divalent aromatic ring group which may have a substituent is preferred. Specific examples and suitable aspects of the divalent aromatic ring group which may have a substituent are as described above. Among these, a phenylene group which may have a substituent is preferred, and a phenylene group is more preferred. In -Y-C(=O)-*1, Y represents a single bond or a divalent linking group, and *1 represents the position of bonding to the oxygen atom specified in the above general formula (II). Y is preferably a single bond. Examples of the divalent linking group represented by Y include a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, -O-, -CO-, -NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) and groups formed by combining two or more of these groups. Specific examples and preferred embodiments of each of the above groups are given in L １ The divalent linking group represented by the formula (I) is as described in detail above.

[0053] In the above general formula (II), R ３ ~R ５ each independently represents a monovalent organic group; R ３ ~R ５ Two of R may be bonded to each other to form a ring. ３ ~R ５ satisfies at least one of the requirements 1 and 2 described below. Examples of the monovalent organic group include groups containing one or more carbon atoms from among the groups exemplified above as the substituent K, and among these, an alkyl group, a cycloalkyl group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent is preferred, and an alkyl group is more preferred.

[0054] The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The aromatic ring constituting the aryl group and heteroaryl group may be either monocyclic or polycyclic. The number of ring-membering atoms in the aromatic ring is preferably 5 to 20, more preferably 5 to 15, and even more preferably 5 to 10. The number of substituents that the aromatic ring may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Examples of the substituent include a hydroxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

[0055] As mentioned above, R ３ ~R ５ satisfies at least one of requirements 1 and 2. ３ ~R ５ It is preferable that at least requirement 1 be satisfied.

[0056] (Requirement 1) R ３ ~R ５ Two of these are bonded to each other to form a ring.

[0057] R ３ ~R ５ The ring formed by bonding two of these may be either an aromatic ring or a non-aromatic ring, but is preferably a non-aromatic ring, and more preferably an aliphatic hydrocarbon ring or an aliphatic heterocycle. The ring may be an unsaturated ring. The number of ring atoms in the ring is preferably 3 to 10, more preferably 5 to 10, and even more preferably 5 or 6. Examples of heteroatoms contained in the aliphatic heterocycle include an oxygen atom, a sulfur atom, or a nitrogen atom, and an oxygen atom is preferred. Among these, cyclopentane, cyclohexane, cyclopentene, or cyclohexene is preferred as the ring.

[0058] (Requirement 2) R ３ ~R ５ At least one of the above is a group represented by general formula (IIx) or general formula (IIy).

[0059]

[0060] In general formulas (IIx) and (IIy), R ｘ and R ｙ each independently represents a hydrogen atom or a monovalent substituent. ｘ Two of these may be bonded to each other to form a ring. * indicates a bonding position. Examples of the monovalent substituent include the groups exemplified above as the substituent K, and among these, a halogen atom or an alkyl group is preferred, and an iodine atom or an alkyl group is more preferred. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0061] Multiple Rs ｘ When two of these bond to each other to form a ring, the ring may be either an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferred, and an aliphatic hydrocarbon ring or an aliphatic heterocycle is more preferred. The number of ring atoms in the ring is preferably 3 to 10, more preferably 5 to 10, and even more preferably 5 or 6. Examples of heteroatoms contained in the aliphatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Of these, cyclopentene or cyclohexene is preferred as the ring.

[0062] The repeating unit A2 is preferably a repeating unit represented by general formula (IIa).

[0063]

[0064] In general formula (IIa), R ２ａ ~R ２ｃ , and R ５ represents R in the above general formula (II). ２ａ ~R ２ｃ , and R ５ The meanings and preferred embodiments thereof are also the same. n represents an integer of 1 or more. n is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0065] In general formula (IIa), L ３ represents a single bond or a divalent organic group. ３The divalent linking group is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, —O—, —CO—, —NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) and groups formed by combining two or more of these groups. Specific examples and preferred embodiments of each of the above groups are given in L １ The divalent linking group represented by the formula (I) is as described in detail above.

[0066] L ３ Among these, -Y-C(=O)-*2 is preferred. In -Y-C(=O)-*2, Y represents a single bond or a divalent linking group, and *2 represents the position of bonding to the oxygen atom as specified in the above general formula (IIa). Y is preferably a single bond. Examples of the divalent linking group represented by Y include a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, -O-, -CO-, -NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) and groups formed by combining two or more of these groups. Specific examples and preferred embodiments of each of the above groups are given in L １ The divalent linking group represented by the formula (I) is as described in detail above.

[0067] <Repeating Unit A3> As described above, the resin P may have a repeating unit A3 other than the repeating unit A1 and the repeating unit A2. Examples of the repeating unit A3 include a repeating unit derived from an α-alkyl aromatic vinyl compound and a repeating unit derived from an α-halogenoacrylic acid. The repeating unit A3 preferably has a group selected from the following Substituent Group I. (Substituent Group I) Hydroxy groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), carboxy groups, carbonate groups, amino groups, alkylcarbonylamino groups, imide groups (such as -CO-NH-CO-), thiol groups, alkoxycarbonyl groups, alkyloxysulfonyl groups, sulfo groups, and alkylsulfonyl groups (-S(=O) ２ -CH ３ etc.).

[0068] The repeating unit A3 is preferably a repeating unit represented by the following general formula (3): In general formula (3), * represents the bonding position.

[0069]

[0070] In general formula (3), R ３ａ represents a hydrogen atom or a monovalent substituent. ３ａ The monovalent substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified above as the substituent K. ３ａ is preferably a hydrogen atom.

[0071] In general formula (3), R ３ｂ represents a hydrogen atom or a monovalent organic group. ３ｂ The monovalent organic group represented by the formula (I) is not particularly limited, but is preferably an alkyl group which may have a substituent. The substituent which the alkyl group may have is not particularly limited, and examples thereof include the groups exemplified above as the substituent K.

[0072] The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 or 2 carbon atoms. ３ｂ Among these, a linear alkyl group is preferred, a linear alkyl group having 1 to 5 carbon atoms is more preferred, and a linear alkyl group having 1 or 2 carbon atoms is even more preferred.

[0073] In the general formula (3), Ar represents a benzene ring or a naphthalene ring. ３ｃ Each independently represents a monovalent substituent. k represents an integer of 0 to 7. k is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably 1 or 2. R ３ｃ Friends or R ３ｃ and R ３ｃ may be bonded via a single bond or a divalent linking group to form a ring.

[0074] R ３ｃ The monovalent substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified above as the substituent K. ３ｃAmong the monovalent substituents represented by the formula (I), a halogen atom, an alkyl group, or an acyloxy group is preferred. Among the groups selected from the formula (I), a carboxy group or a hydroxy group is preferred. As the halogen atom, a fluorine atom is preferred. As the R ３ｃ The alkyl group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. ３ｃ The acyloxy group represented by the formula: ａｌ (R ａｌ represents an alkyl group. The alkyl moiety in the alkylcarbonyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl moiety is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0075] The content of repeating unit A1 in resin P is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 5 to 25 mol%, relative to the total content of repeating units in resin P. The content of repeating unit A2 in resin P is preferably 15 to 90 mol%, more preferably 30 to 80 mol%, and even more preferably 35 to 70 mol%, relative to the total content of repeating units in resin P. The content of repeating unit A3 (more preferably, a repeating unit represented by general formula (3)) in resin P is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 50 mol%, relative to the total content of repeating units in resin P. Each of the above repeating units in resin P may be one type or two or more types. When two or more types of each repeating unit are used, it is preferable that the total content falls within the above numerical range.

[0076] Resin P can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight of Resin P is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 80,000. The dispersity (molecular weight distribution) of Resin P is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.3.

[0077] The content of resin P in the resist composition is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total solid content of the resist composition. The upper limit is preferably 100% by mass or less, more preferably 98% by mass or less. Resin P may be used alone or in combination. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0078] [Other Resins] The resist composition of the present invention may contain a resin other than the above-described resin P (hereinafter also referred to as "other resins"). Examples of other resins include a resin whose polarity increases under the action of acid (hereinafter also simply referred to as "acid-decomposable resin") and a hydrophobic resin. Acid-decomposable resins are described in detail below.

[0079] <Acid-Decomposable Resin> (Repeating Unit Having Acid-Decomposable Group) The acid-decomposable resin contains a repeating unit having an acid-decomposable group (hereinafter also simply referred to as "repeating unit B1"). The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity, and is typically a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a group that leaves under the action of an acid (leaving group). It is preferable that the polarity of the acid-decomposable resin increases under the action of an acid, and the solubility in organic solvents decreases. Examples of the polar group include acidic groups such as a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group, a sulfonic acid group, a phosphate 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 hydroxy groups.

[0080] Examples of the group that is eliminated by the action of an acid include groups represented by any one of formulas (Y1), (Y2), and (Y3). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y3): -C(Rn)(H)(Ar)

[0081] In formula (Y1), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an alkynyl group, or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring. １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 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. １ ~Rx ３ The cycloalkyl group of Rx 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. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The alkynyl group of Rx is preferably an ethynyl group or a propargyl group. １ ~Rx ３ 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.

[0082] Rx １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by bonding the two 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, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx３ In the cycloalkyl group formed by bonding these two, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0083] When the resist composition of the present invention is used as an EUV resist, Rx １ ~Rx ３ an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and Rx １ ~Rx ３ The ring formed by bonding these two groups preferably further has a fluorine atom or an iodine atom as a substituent.

[0084] In formula (Y2), 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, an alkenyl group, and an alkynyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl group may contain a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８The group formed by bonding together R and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. When the resist composition of the present invention is used as an EUV resist, ３６ ~R ３８ and a monovalent organic group represented by R ３７ and R ３８ It is also preferable that the ring formed by bonding these groups together further has a fluorine atom or an iodine atom as a substituent.

[0085] In formula (Y3), Ar represents an aromatic ring 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 preferably an aryl group. When the resist composition of the present invention is used as an EUV resist, it is also preferable that the aromatic ring group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.

[0086] In terms of excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the leaving group protecting the polar group, it is also preferable that the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.

[0087] The group that is eliminated by the action of an acid may also be a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0088] The repeating unit B1 is also preferably a repeating unit represented by formula (A).

[0089]

[0090] L １ represents a divalent linking group which may have a fluorine atom or an iodine atom, R １represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; R ２ represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. １ , R １ and R ２ At least one of L has a fluorine atom or an iodine atom. １ Examples of the divalent linking group which may have a fluorine atom or an iodine atom and is represented by the formula: ２ -, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. １ As the alkylene group, -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0091] R １ The alkyl group represented by R may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by the formula (I), is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by the formula (I) may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0092] R ２ Examples of the leaving group represented by the formula (Y1), (Y2), or (Y3) above, which may have a fluorine atom or an iodine atom, include leaving groups represented by the formula (Y1), (Y2), or (Y3) above, which have a fluorine atom or an iodine atom.

[0093] The repeating unit B1 is also preferably a repeating unit represented by formula (AI).

[0094]

[0095] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an alkynyl group, or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0096] Xa １ Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group or a —CH ２ -R １１ Examples of the group include a group represented by R １１ represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group. １１ Examples of the monovalent organic group represented by the formula (I) include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred.１ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0097] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH ２ -, -(CH ２ ) ２ - or -(CH ２ ) ３ - is more preferable.

[0098] Rx １ ~Rx ３ The alkyl group of Rx 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. １ ~Rx ３ The cycloalkyl group of Rx 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. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The alkynyl group of Rx is preferably an ethynyl group or a propargyl group. １ ~Rx ３ 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.

[0099] Rx １ ~Rx ３As the cycloalkyl group formed by bonding the two above, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Rx １ ~Rx ３ In the cycloalkyl group formed by bonding the two above, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the formula (AI), for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0100] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0101] The repeating unit represented by formula (AI) may be an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (Xa １ represents a hydrogen atom or a methyl group, and T represents a single bond).

[0102] The repeating unit B1 may have an acid-decomposable group containing an unsaturated bond. As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by formula (B) is preferred.

[0103]

[0104] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry１ ~Ry ３ each independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ At least one of R represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0105] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or —CH ２ -R １１ Examples of the group include a group represented by R １１ represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0106] Examples of the divalent linking group represented by L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group. Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable. Rt may have a substituent such as a halogen atom, a hydroxy group, or an alkoxy group. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group.

[0107] Ry １ ~Ry ３The alkyl group represented by the formula (I) 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. １ ~Ry ３ The cycloalkyl group represented by the formula (I) 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. １ ~Ry ３ The alkenyl group represented by Ry is preferably a vinyl group. １ ~Ry ３ The alkynyl group represented by the formula (I) is preferably an ethynyl group. １ ~Ry ３ The cycloalkenyl group represented by the formula (I) is preferably a cyclopentyl group or a monocyclic cycloalkyl group such as a cyclohexyl group, which has a double bond in part thereof. １ ~Ry ３ The aryl group represented by the formula (I) 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.

[0108] Ry １ ~Ry ３ The cycloalkyl group formed by combining the above two groups 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. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ The cycloalkyl group or cycloalkenyl group formed by bonding two of the above is, for example, a group in which one of the methylene groups constituting the ring is substituted with a heteroatom such as an oxygen atom, a carbonyl group, or —SO ２ - group and -SO ３The repeating unit represented by formula (B) may be substituted with a group containing a hetero atom such as a - group, a vinylidene group, or a combination thereof. In addition, in these cycloalkyl groups or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with a vinylene group. １ is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry ２ and Ry ３ and are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0109] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0110] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —CO— group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —Rt—CO— group (Rt is an aromatic group)).

[0111] Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond include the repeating units described in paragraphs

[0067] to

[0071] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[0112] Specific examples of the repeating unit B1 (a repeating unit having an acid-decomposable group) are shown below, but are not limited to these. For specific examples of the repeating unit B1, see, for example, paragraphs

[0029] to

[0071] of WO 2022 / 024928, which is incorporated herein by reference.

[0113]

[0114] The content of the repeating unit B1 is preferably 15 mol% or more, more preferably 40 mol% or more, and even more preferably 60 mol% or more, based on the total repeating units in the acid-decomposable resin. The content of the repeating unit B1 is preferably less than 100 mol%, more preferably 95 mol% or less, and even more preferably 90 mol% or less, based on the total repeating units in the acid-decomposable resin. The repeating unit B1 contained in the acid-decomposable resin may be one type or two or more types. When the acid-decomposable resin contains two or more types of repeating units B1, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0115] (Repeating unit having an acid group) The acid-decomposable resin preferably contains a repeating unit having an acid group (hereinafter also simply referred to as "repeating unit B2"). The repeating unit B2 is preferably a repeating unit different from the repeating unit B1 (repeating unit having an acid-decomposable group). The repeating unit B2 may also contain a fluorine atom or an iodine atom. The acid group is preferably a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. Among these, the repeating unit B2 is preferably a repeating unit having a phenolic hydroxy group. In the hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group may be a -C(CF ３ )(OH)—CF ２ In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom to form -C(CF ３ )(OH)—CF ２ A ring containing - may be formed.

[0116] The repeating unit B2 is preferably a repeating unit represented by the following formula (Pa1), and the acid-decomposable resin preferably contains a repeating unit represented by the following formula (Pa1).

[0117]

[0118] In formula (Pa1), R ａ１ and R ａ２ each independently represents a hydrogen atom or a substituent. ａ１ represents a single bond or a divalent linking group. ａ１ represents an (m+n+1)-valent aromatic ring group. ａ１ And, R ａ２ or L ａ１ may be bonded via a single bond or a linking group. Ｘ represents a substituent other than a hydroxy group. n represents an integer of 1 or more and 9 or less. m represents an integer of 0 or more and 8 or less.

[0119] In the above formula (Pa1), R ａ１ and R ａ２ R each independently represents a hydrogen atom or a substituent. ａ１ and R ａ２ The substituent represented by R is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ and R ａ２ The alkyl group represented by the formula (I) may be either linear or branched, and may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the alkyl group 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. R ａ１ and R ａ２ The number of carbon atoms in the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have a substituent. R ａ１ and R ａ２Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. ａ１ and R ａ２ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. The alkoxycarbonyl group may have a substituent.

[0120] In the above formula (Pa1), L ａ１ represents a single bond or a divalent linking group. ａ１ Examples of the divalent linking group represented by the formula: ａ３ -, an alkylene group, or a group formed by combining two or more of these groups. ａ３ represents a hydrogen atom or an alkyl group. 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. The alkylene group may have a substituent. R ａ３ When represents an alkyl group, examples of the alkyl group include alkyl groups 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, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0121] In the above formula (Pa1), Ar ａ１ represents an (m+n+1)-valent aromatic ring group. ａ１The aromatic ring group represented by the formula (I) may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic hydrocarbon group is preferably a group containing an aromatic hydrocarbon having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or naphthacene. The aromatic heterocyclic group preferably contains at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The aromatic heterocyclic group is preferably a group containing an aromatic heterocycle having 4 to 20 ring atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0122] Ar ａ１ And, R ａ２ or L ａ１ may be bonded to via a single bond or a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have a substituent.

[0123] In the above formula (Pa1), R Ｘ represents a substituent other than a hydroxy group. Ｘ Examples of the substituent represented by R include a carboxy group, a sulfo group, a cyano group, a halogen atom, a hydrocarbon group, an amino group, a nitro group, and a group formed by combining two or more of these. Ｘ Examples of the hydrocarbon group represented by R include an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 15 carbon atoms), and an alkenyl group (preferably having 2 to 10 carbon atoms). Ｘ The hydrocarbon group represented by R may have a substituent. Ｘ The hydrocarbon group represented by is -CH ２ When it contains -, -CH ２ At least one of - is -O-, -CO-, -S- and -SO ２- may be replaced with at least one selected from the group consisting of Ｘ The substituent represented by the formula (I) preferably has a halogen atom, and the halogen atom is preferably a fluorine atom or an iodine atom.

[0124] In the above formula (Pa1), n ​​represents an integer of 1 or more and 9 or less, preferably an integer of 1 or more and 5 or less, and more preferably an integer of 1 or more and 4 or less. m represents an integer of 0 or more and 8 or less, preferably an integer of 0 or more and 4 or less, and more preferably an integer of 0 or more and 3 or less.

[0125] The repeating unit B2 is also preferably a repeating unit represented by the following formula (Pa2), and the acid-decomposable resin preferably contains a repeating unit represented by the following formula (Pa2).

[0126]

[0127] In formula (Pa2), R ａ４ represents a hydrogen atom or an alkyl group. ａ２ represents a single bond or —COO—. r represents an integer of 0 or more and 3 or less. R Ｘ１ represents a halogen atom or a hydrocarbon group. n1 represents an integer of 1 or more and 5 or less. m1 represents an integer of 0 or more and 4 or less.

[0128] In the above formula (Pa2), R ａ４ represents a hydrogen atom or an alkyl group. ａ４ The alkyl group represented by the formula (I) may be either linear or branched, and may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group 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.

[0129] In the above formula (Pa2), L ａ２represents a single bond or -COO-, with a single bond being preferred. r represents an integer of 0 or more and 3 or less, with an integer of 0 or more and 2 or less being preferred, 0 or 1 being more preferred, and 0 being even more preferred. The aromatic ring in formula (Pa2) becomes benzene when r represents 0, naphthalene when r represents 1, anthracene when r represents 2, and naphthacene when r represents 3. n1 represents an integer of 1 or more and 5 or less, with an integer of 1 or more and 4 or less being preferred. m1 represents an integer of 0 or more and 4 or less, with an integer of 0 or more and 3 or less being preferred.

[0130] In the above formula (Pa2), R Ｘ１ represents a halogen atom or a hydrocarbon group. Ｘ１ The halogen atom represented by R is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom or an iodine atom. Ｘ１ Examples of the hydrocarbon group represented by R include an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 15 carbon atoms), and an alkenyl group (preferably having 2 to 10 carbon atoms). Ｘ１ The hydrocarbon group represented by R may have a substituent. Ｘ１ The hydrocarbon group represented by -CH ２ When it contains -, -CH ２ At least one of - is -O-, -CO-, -S- and -SO ２ - may be replaced with at least one selected from the group consisting of Ｘ１ The hydrocarbon group represented by the formula (I) preferably has a halogen atom, and the halogen atom is preferably a fluorine atom or an iodine atom.

[0131] Specific examples of the repeating unit B2 (a repeating unit having an acid group) are shown below, but are not limited to these. １ and G ２each independently represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxy group, or a hydroxymethyl group. f1 represents an integer of 1 to 3. Specific examples of the repeating unit B2 include the repeating units described in paragraphs

[0079] to

[0110] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[0132] When the acid-decomposable resin contains the repeating unit B2, the content of the repeating unit B2 is preferably 10 mol % or more, more preferably 15 mol % or more, based on the total repeating units in the acid-decomposable resin, and preferably less than 40 mol % or more, more preferably 35 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0133] (Repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the repeating unit B1 and the repeating unit B2, the acid-decomposable resin may have a repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter, also simply referred to as "repeating unit X"). The repeating unit X is preferably different from the repeating unit Y and the repeating unit P described below. The repeating unit X is preferably a repeating unit represented by formula (C).

[0134]

[0135] In formula (C), L ５ represents a single bond or an ester group. ９ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these.

[0136] The content of the repeating unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total repeating units in the acid-decomposable resin, and the upper limit thereof is preferably less than 40 mol% and more preferably 35 mol% or less, based on the total repeating units in the acid-decomposable resin.

[0137] The acid-decomposable resin may also have a repeating unit having at least one of a fluorine atom, a bromine atom, and an iodine atom. Examples of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom. Of the repeating units of the acid-decomposable resin, the total content of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total repeating units of the acid-decomposable resin. The upper limit is not particularly limited, but is, for example, 100 mol% or less based on the total repeating units of the acid-decomposable resin.

[0138] Specific examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs

[0116] to

[0117] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[0139] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The acid-decomposable resin may have a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, also simply referred to as "repeating unit Y"). It is also preferable that the repeating unit Y does not have a hydroxy group or an acid group such as a hexafluoropropanol group.

[0140] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among these, a 5- to 7-membered lactone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, is more preferred. For units containing a lactone group or a sultone group, see, for example, paragraphs

[0119] to

[0126] and

[0132] to

[0133] of WO 2022 / 024928, and the above descriptions are incorporated herein.

[0141] The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928, which is incorporated herein by reference.

[0142] When the acid-decomposable resin contains the repeating unit Y, the content of the repeating unit Y is preferably 1 mol % or more, more preferably 10 mol % or more, based on the total repeating units in the acid-decomposable resin, and the upper limit thereof is preferably less than 40 mol %, more preferably 35 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0143] (Repeating unit having a photoacid generating group) The acid-decomposable resin may contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group"). However, it is also preferable that the acid-decomposable resin does not contain a repeating unit having a photoacid generating group (hereinafter simply referred to as a "repeating unit P"). Examples of the repeating unit P include a repeating unit represented by formula (4).

[0144]

[0145] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0146] L ４１ represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—). ４２ represents an alkylene group, a cycloalkylene group, an arylene group, —O—, —CO—, —S—, —SO—, —SO ２ Preferably, the linking group is at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but preferably 3 to 20, more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but preferably 6 to 20, more preferably 6 to 10. The alkylene group, cycloalkylene group, and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0147] R ４０ is preferably a group represented by the following formula (S4-1).

[0148]

[0149] In formula (S4-1), Q － represents an acid residue, M ＋ represents a cation. * represents L ４１ The bond position of the acid residue is a group formed by dissociating a proton from an acid. － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), or a sulfonamide group (N － -SO ２ R Ｎ１ It is expressed as: R Ｎ１represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ) is preferred, and a sulfonate anion group is more preferred. ＋ The explanation, specific examples and preferred ranges of M in the explanation of the photoacid generator to be described later ３ ＋ is the same as

[0150] Specific examples of the repeating unit P include the repeating units described in

[0094] to

[0105] of JP 2014-041327 A, the repeating units described in

[0094] of WO 2018 / 193954 A, and the repeating units described in

[0138] of WO 2022 / 024928 A, the above descriptions are incorporated herein. Further, examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP 2014-041327 A, and the repeating units described in paragraph

[0094] of WO 2018 / 193954 A, the above descriptions are incorporated herein.

[0151] When the acid-decomposable resin contains the repeating unit P, the content of the repeating unit P is preferably 1 mol % or more, more preferably 3 mol % or more, and even more preferably 5 mol % or more, based on the total repeating units in the acid-decomposable resin. The content of the repeating unit P is preferably less than 40 mol %, more preferably 30 mol % or less, and even more preferably 20 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0152] (Repeating unit represented by formula (V-1) or formula (V-2)) The acid-decomposable resin may have a repeating unit represented by the following formula (V-1) or formula (V-2). The repeating units represented by formula (V-1) and formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

[0153]

[0154] In formula (V-1) and the following formula (V-2), R ６ and R ７each independently represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxy group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954, the description of which is incorporated herein by reference.

[0155] (Repeating unit for reducing the mobility of the main chain) The acid-decomposable resin preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of the generated acid or pattern collapse during development. Regarding the repeating unit for reducing the mobility of the main chain, the contents of

[0144] to

[0160] of WO 2022 / 024928 are incorporated by reference.

[0156] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy group, a cyano group, and an alkali-soluble group) The acid-decomposable resin may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the acid-decomposable resin include the repeating units described above for repeating unit Y. The preferred content is also as described for repeating unit Y.

[0157] The acid-decomposable resin may have a repeating unit having a hydroxy group or a cyano group. This improves substrate adhesion. The repeating unit having a hydroxy group or a cyano group is preferably a repeating unit having a saturated hydrocarbon group having a hydroxy group or a cyano group (substituted with a hydroxy group or a cyano group). Alternatively, it may be a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group. The repeating unit having a hydroxy group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxy group or a cyano group include repeating units described in paragraphs

[0081] to

[0084] of JP 2014-098921 A, and the above descriptions are incorporated herein by reference.

[0158] The acid-decomposable resin may have a repeating unit having an alkali-soluble group. When the acid-decomposable resin contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved. Examples of the alkali-soluble group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxy group being preferred. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs

[0085] and

[0086] of JP 2014-098921 A, the disclosures of which are incorporated herein by reference.

[0159] (Repeating Unit Having an Alicyclic Hydrocarbon Structure and Not Exhibiting Acid Decomposability) The acid-decomposable resin may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate.

[0160] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxy Group nor a Cyano Group) The acid-decomposable resin may have a repeating unit represented by formula (III) having neither a hydroxy group nor a cyano group.

[0161]

[0162] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxy group nor a cyano group, and Ra represents a hydrogen atom, an alkyl group, or —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxy group or a cyano group include the repeating units described in paragraphs

[0087] to

[0094] of JP 2014-098921 A, the descriptions of which are incorporated herein by reference.

[0163] (Other Repeating Units) Furthermore, the acid-decomposable resin may have other repeating units in addition to the repeating units described above. For example, see paragraphs

[0141] to

[0143] and

[0169] to

[0170] of WO 2022 / 024928, which are incorporated herein by reference.

[0164] In addition to the above repeating structural units, the acid-decomposable resin may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0165] In a preferred embodiment of the present invention, the acid-decomposable resin has at least one group selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a saturated hydrocarbon group having a hydroxy group, which further improves etching resistance and LWR performance.

[0166] In a preferred embodiment of the present invention, the acid-decomposable resin contains a repeating unit having an iodine atom, which increases the absorption rate of EUV light and the like, reduces the effect of shot noise, and further improves LWR performance.

[0167] The acid-decomposable resin can be synthesized according to a conventional method (e.g., radical polymerization). The weight-average molecular weight (Mw) of the acid-decomposable resin, as measured by GPC in terms of polystyrene, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0168] The content of the acid-decomposable resin in the resist composition is preferably 0.5 to 20.0 mass%, more preferably 1.0 to 10.0 mass%, and even more preferably 1.0 to 5.0 mass%, based on the total solids content of the resist composition. The acid-decomposable resin may be used alone, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0169] <Hydrophobic Resin> The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in the molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances.

[0170] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３It is preferable to have one or more of the partial structures, and more preferably two or more. In addition, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306, and the above descriptions are incorporated herein.

[0171] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 10.0 mass%, and even more preferably 0.1 to 5.0 mass%, relative to the total solids content of the resist composition. Only one type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0172] [Photoacid Generator] The resist composition of the present invention may contain a photoacid generator. The photoacid generator is often an onium salt. An onium salt is a compound that forms an ion pair with a cation and an anion and generates an acid upon irradiation (exposure) with actinic rays or radiation. The anion is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction). When the anion is a non-nucleophilic anion, it is likely to form a photodecomposable onium salt structure.

[0173] The onium salt is preferably a compound comprising an organic cation and an organic anion and capable of generating an organic acid. The acid dissociation constant (pKa) of the acid generated upon exposure is not particularly limited, but is preferably from -5.00 to 15.00, more preferably from 0.00 to 15.00, even more preferably from 2.00 to 10.00, and particularly preferably from 2.00 to 6.00. The onium salt may be in the form of a low molecular weight compound or may be incorporated into a polymer. The onium salt may be in the form of a low molecular weight compound and in the form of a polymer in combination. The molecular weight of the onium salt is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. While the lower limit is not particularly limited, a molecular weight of 100 or more is preferred.

[0174] The onium salt is preferably a compound represented by the following formula (6):

[0175]

[0176] In formula (6), M ３ ＋ represents an organic cation that decomposes when irradiated with actinic rays or radiation. ３ － represents an anionic group. ａ represents a hydrogen atom or a monovalent organic group. ａ represents a single bond or a divalent linking group.

[0177] R ａ The monovalent organic group represented by the formula (I) is not particularly limited, but preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms. ａ Examples of the monovalent organic group represented by the formula (I) include an aliphatic hydrocarbon group and an aromatic ring group. The aliphatic hydrocarbon group and the aromatic ring group may further have a substituent. The substituent is not particularly limited, and examples thereof include the groups exemplified above as the substituent K. Among these, the substituent is preferably a halogen atom or a hydroxy group.

[0178] The aliphatic hydrocarbon group may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 3. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, and among these, linear alkyl groups having 1 to 3 carbon atoms, which may have a substituent, are preferred.

[0179] The aromatic ring group may be either an aryl group or a heteroaryl group, and the number of ring members of the aromatic ring constituting the aromatic ring is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The aromatic ring constituting the aromatic ring group may be either a monocyclic ring or a polycyclic ring (condensed ring). The condensed ring may be a structure in which a plurality of aromatic rings are condensed together, or a structure in which one or more aromatic rings are condensed with one or more non-aromatic rings. An example of a condensed ring of one or more aromatic rings and one or more non-aromatic rings is a phthalimide structure. Among these, a phenyl group which may have a substituent is preferred as the aromatic ring group.

[0180] L ａ The divalent linking group represented by the formula (I) is not particularly limited, but may be —COO—, —CO— (carbonyl group), —O—, —S—, —SO—, —SO ２ Examples of such groups include sulfonyl groups, alkylene groups, alkenylene groups, aromatic ring groups, and linking groups in which a plurality of these groups are linked together.

[0181] The alkylene group and the aromatic ring group may further have a substituent. ３ － and R ａ may be bonded to each other to form a ring.

[0182] <Organic cation> M ３ ＋ Although there are no particular limitations on the cation, an organic cation represented by the following formula (ZaI) (cation (ZaI)) or an organic cation represented by the following formula (ZaII) (cation (ZaII)) is preferred.

[0183]

[0184] In the formula (ZaI), R ２０１ ~R ２０３ R each independently represents an organic group. ２０１ ~R ２０３ The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３Two of the organic groups represented by the formula (I) may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of the group formed by bonding two of the organic groups represented by the formula (I) include an alkylene group (e.g., a butylene group and a pentylene group), and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0185] In formula (ZaII), R ２０４ and R ２０５ each independently represents a monovalent aromatic ring group which may have a substituent, or an alkyl group which may have a substituent, and a monovalent aromatic ring group is preferred in that the effects of the present invention are more excellent.

[0186] R ２０４ and R ２０５ Examples of the monovalent aromatic ring group include an aryl group and a heteroaryl group. As the aryl group, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The heteroaryl group has a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the ring constituting the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring. R ２０４ and R ２０５ The alkyl group is preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), or a cyclic alkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).

[0187] R ２０４ and R ２０５The monovalent aromatic ring group and alkyl group may further have another substituent, and examples of the other substituent include an alkyl group (e.g., having 1 to 15 carbon atoms), a monovalent aromatic ring 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.

[0188] As the above-mentioned cation (ZaI), cation (ZaI-1), cation (ZaI-2), or an organic cation represented by formula (ZaI-3b) or formula (ZaI-4b) is particularly preferred.

[0189] First, the cation (ZaI-1) will be described. In the cation (ZaI-1), R ２０１ ~R ２０３ At least one of R represents a monovalent aromatic ring group which may have a substituent. ２０１ ~R ２０３ may all be monovalent aromatic ring groups, or R ２０１ ~R ２０３ A part of R may be a monovalent aromatic ring group, and the rest may be an alkyl group which may have a substituent. ２０１ ~R ２０３ one of which is a monovalent aromatic ring group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the formed ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of the group formed by combining two of the above include an alkylene group in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., a butylene group, a pentylene group, or a -CH ２ -CH ２ -O-CH ２ -CH ２ -) are listed.

[0190] In the cation (ZaI-1), examples of the monovalent aromatic ring group include an aryl group and a heteroaryl group. The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The heteroaryl group has a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of rings constituting the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring. In the cation (ZaI-1), R ２０１ ~R ２０３ When two or more of the above are monovalent aromatic ring groups, the two or more monovalent aromatic ring groups may be the same or different.

[0191] In the cation (ZaI-1), the alkyl group is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl 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.

[0192] R ２０１ ~R ２０３ The monovalent aromatic ring group and the alkyl group may each independently have a substituent, such as an alkyl group (e.g., having 1 to 15 carbon atoms), a monovalent aromatic ring group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. The above substituents may further have other substituents, and for example, the alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.

[0193] Examples of the cation (ZaI-1) include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation. In terms of obtaining superior effects of the present invention, a triarylsulfonium cation is preferred.

[0194] Next, the cation (ZaI-2) will be described. In the cation (ZaI-2), R ２０１ ~R ２０３ Each of R independently represents an organic group that does not have an aromatic ring. Here, the aromatic ring also includes a heterocycle containing a heteroatom. ２０１ ~R ２０３ The organic group having no aromatic ring represented by the formula (I) generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. ２０１ ~R ２０３ are each independently preferably an alkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0195] In the cation (ZaI-2), examples of the alkyl group include linear alkyl groups having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), branched alkyl groups having 3 to 10 carbon atoms, and cyclic alkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ The alkyl group represented by the formula (I) 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.

[0196] Next, the organic cation represented by formula (ZaI-3b) will be described.

[0197]

[0198] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each independently represents a hydrogen atom, an alkyl group, a monovalent aromatic ring group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃR each independently represents a hydrogen atom, an alkyl group (such as a t-butyl group), a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ each independently represents an alkyl group, a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[0199] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ may be bonded to each other to form a ring, and the formed rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester group, or an amide bond. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0200] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0201] Next, the organic cation represented by formula (ZaI-4b) will be described.

[0202]

[0203] In formula (ZaI-4b), l represents an integer of 0 to 2, and R represents an integer of 0 to 8. １３ represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ represents a hydroxyl group, a linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ Each of R independently represents an alkyl group or a naphthyl group. These groups may have a substituent. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and are bonded to each other to form a ring structure.

[0204] In formula (ZaI-4b), R １５ The alkyl group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.

[0205] <Organic anion> A ３ － The anionic group represented by the formula (I) is a group having an anionic atom, and is not particularly limited. ３ － Examples of the anionic group represented by the formula (I) include a group in which a proton (H ＋As the anionic group, particularly, groups represented by the following formulae (B-1) to (B-14) and *-O － (a group obtained by removing a proton from a hydroxy group), and more preferably a group selected from the group consisting of a group represented by formula (B-6), a group represented by formula (B-9), and a group represented by formula (B-14).

[0206]

[0207] In formulas (B-1) to (B-14), * represents a bonding position. Ｘ１ Each independently represents a monovalent organic group. Ｘ２ Each of the two R in formula (B-7) independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group. Ｘ２ may be the same or different. ＸＦ１ represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. ＸＦ１ At least one of R represents a fluorine atom or a perfluoroalkyl group. Ｘ３ represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer of 0 to 4. When n1 represents an integer of 2 to 4, a plurality of R Ｘ３ may be the same or different. ＸＦ２ represents a fluorine atom or a perfluoroalkyl group. Ｘ４ represents a hydrogen atom, a halogen atom, or a monovalent organic group. n2 represents an integer of 0 to 4. When n2 represents an integer of 2 to 4, a plurality of R Ｘ４ may be the same or different.

[0208] In formulas (B-1) to (B-5) and (B-12), R Ｘ１is preferably an alkyl group (which may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms) or an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms). Ｘ１ Inside, N － The atoms directly bonded to are the carbon atoms in —CO— and —SO ２ It is also preferred that neither of the sulfur atoms in - is present.

[0209] R Ｘ１ Examples of the cyclic alkyl group (cycloalkyl group) in R include a norbornyl group and an adamantyl group. Ｘ１ The substituent that the cycloalkyl group in R may have is not particularly limited, but examples thereof include the above-mentioned substituent K, and an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms) is preferred. Ｘ１ The alkyl group in R preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Ｘ１ The aryl group in is preferably a benzene ring group.

[0210] In formula (B-7) and formula (B-11), R Ｘ２ The substituent other than the fluorine atom and the perfluoroalkyl group represented by the formula (I) is preferably an alkyl group other than a perfluoroalkyl group, or a cycloalkyl group.

[0211] In formula (B-8), R ＸＦ１ each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. ＸＦ１ At least one of R represents a fluorine atom or a perfluoroalkyl group. ＸＦ１ The perfluoroalkyl group represented by the formula (I) preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0212] In formula (B-9), R Ｘ３ represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer of 0 to 4. n1 is preferably an integer of 0 to 2, and more preferably 0 or 1. When n1 represents an integer of 2 to 4, a plurality of R Ｘ３ may be the same or different.Ｘ３ The halogen atom as R is preferably a fluorine atom. Ｘ３ Examples of the monovalent organic group represented by the formula (I) include an alkyl group (which may be linear or branched, and preferably has 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms), and an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms).

[0213] R Ｘ３ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 10, and more preferably 1 to 5. Ｘ３ Examples of the cycloalkyl group in R include a cyclohexyl group, a norbornyl group, and an adamantyl group. Ｘ３ The substituent that the cycloalkyl group may have is not particularly limited, but examples thereof include the above-mentioned substituent K, and an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms) is preferred.

[0214] In formula (B-10), R ＸＦ２ The perfluoroalkyl group represented by the formula (I) preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0215] In formula (B-14), R Ｘ４ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Ｘ４ The halogen atom as R is preferably a fluorine atom. n2 represents an integer of 0 to 4. n2 is preferably an integer of 0 to 2, and more preferably 0 or 1. Ｘ４ Examples of the monovalent organic group represented by the formula (I) include an alkyl group (which may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms), and an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms).

[0216] R Ｘ４ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 or 2. Ｘ４ Examples of the cyclic alkyl group (cycloalkyl group) in the formula (I) include a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0217] The onium salt may be a compound having a plurality of ion pairs that decompose upon exposure to light (hereinafter also referred to as a "polyvalent onium salt"). The ion pair is composed of a cationic moiety, which is a positively charged atomic group whose total valence is W, and an anionic moiety, which is a negatively charged atomic group whose total valence is W. In other words, the ion pair is composed of a cationic moiety and an anionic moiety whose absolute valence values ​​are the same. When the onium salt has a plurality of ion pairs, the number of ion pairs is preferably 2 to 8, more preferably 2 to 4, and even more preferably 2 or 3.

[0218] <<Compound Represented by Formula (EX1)>> Examples of polyvalent onium salts include compounds represented by formula (EX1).

[0219]

[0220] In formula (EX1), X Ｅ１ is a single bond, or m Ｅ１ represents a valent linking group. Ｅ１ represents a single bond or a divalent linking group. Ｅ１ represents an integer of 2 to 4. Ｅ１ － represents an anionic moiety. Ｅ１ ＋ represents a cation. Ｅ１ , A Ｅ１ － , and M Ｅ１ ＋ may be the same or different. Ｅ１ － and M Ｅ１ ＋ and form an ion pair (salt structure). Ｅ１ When represents a single bond, m Ｅ１ represents 2. That is, X Ｅ１ represents a single bond, the above formula (EX1) is represented by the following formula (EX1-1).

[0221]

[0222] In formula (EX1), X Ｅ１ m expressed as Ｅ１The valent linking group is not particularly limited, and examples thereof include linking groups represented by the following formulas (EX1-a1) to (EX1-a3). In the following formulas (EX1-a1) to (EX1-a3), * represents the L group specified in the formula (EX1) above. Ｅ１ represents the bonding position with

[0223]

[0224] In the above (EX1-a1), X Ｅ１１ represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, but may be an alkylene group, an arylene group, —CO—, —NR Ｎ -, -O-, -S-, or a group formed by combining two or more of these. Ｎ represents a hydrogen atom or a substituent. The substituent is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms, which may be linear or branched) is preferred. Examples of the combined group include -CO-O-, -CO-NR Ｎ -, -CO-alkylene group-, -O-alkylene group-, and -CO-O-alkylene group-. The alkylene group may be linear, branched, or cyclic. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkylene group and the arylene group may further have a substituent. The substituent is not particularly limited, but may include, for example, a fluorine atom. When the alkylene group contains a fluorine atom as a substituent, it may be a perfluoroalkylene group. The R Ｎ represents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms, which may be linear or branched).

[0225] In the above (EX1-a2), X Ｅ１２represents a trivalent linking group. The trivalent linking group is not particularly limited, but examples thereof include a nitrogen atom, a phosphorus atom, a trivalent aliphatic hydrocarbon group, and a trivalent aromatic ring group. A trivalent aliphatic hydrocarbon group is a group formed by removing three hydrogen atoms from an aliphatic hydrocarbon. A trivalent aromatic ring group is a group formed by removing three hydrogen atoms from an aromatic compound. The number of carbon atoms in the trivalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The aliphatic hydrocarbon constituting the trivalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the trivalent aromatic ring group is preferably 6 to 15, more preferably 6 to 12. Examples of aromatic rings constituting the trivalent aromatic ring group include aromatic hydrocarbon rings and aromatic heterocycles.

[0226] In the above (EX1-a3), X Ｅ１３ represents a tetravalent linking group. The tetravalent linking group is not particularly limited, but examples thereof include a carbon atom, a silicon atom, a tetravalent hydrocarbon group, and a tetravalent aromatic ring group. A tetravalent aliphatic hydrocarbon group is a group formed by removing four hydrogen atoms from an aliphatic hydrocarbon. A tetravalent aromatic ring group is a group formed by removing four hydrogen atoms from an aromatic compound. The number of carbon atoms in the tetravalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The aliphatic hydrocarbon constituting the tetravalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the tetravalent aromatic ring group is preferably 6 to 15, more preferably 6 to 12. Examples of aromatic rings constituting the tetravalent aromatic ring group include aromatic hydrocarbon rings and aromatic heterocycles.

[0227] In formula (EX1), L Ｅ１ The divalent linking group represented by X is not particularly limited, but Ｅ１１ Examples of the divalent linking group include the groups exemplified as the divalent linking group represented by the following formula:

[0228] In formula (EX1), A Ｅ１ － is not particularly limited, but is preferably A in the above general formula (6) ３ －Examples of the anionic group include the groups exemplified above as the anionic group represented by the following formula:

[0229] In formula (EX1), M Ｅ１ ＋ The organic cation represented by general formula (ZaI) (cation (ZaI)) or the organic cation represented by general formula (ZaII) (cation (ZaII)) is preferred. The organic cation represented by general formula (ZaI) (cation (ZaI)) or the organic cation represented by general formula (ZaII) below (cation (ZaII)) is as described above.

[0230] The content of the photoacid generator is preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and even more preferably 5.0 to 10 mass %, based on the total solid content of the resist composition. The photoacid generator may be used alone, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0231] [Acid Diffusion Controller] The resist composition of the present invention preferably further contains an acid diffusion controller. The acid diffusion controller is a compound different from the photoacid generator. The acid diffusion controller can act as a quencher that traps excess acid generated from the photoacid generator upon irradiation (exposure) with actinic rays or radiation, and suppresses the reaction of the acid-decomposable resin in unexposed areas due to the excess acid.

[0232] The type of acid diffusion controller is not particularly limited, and examples thereof include a compound selected from the group consisting of a basic compound (CA), a low molecular weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. The acid diffusion controller is also preferably a compound that generates an acid having a pKa of 0 or more by irradiation with actinic rays or radiation.

[0233] (Basic Compound (CA)) The basic compound (CA) is preferably a compound having a structure represented by any one of the following formulas (A) to (E): In formulas (B), (C), (D) and (E), * represents a bonding position.

[0234]

[0235] In formula (A), R ２００ ~R ２０２ R 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). ２００ ~R ２０２ At least two of R may be bonded to form a ring. ２０３ ~R ２０６ each independently represents an alkyl group having 1 to 20 carbon atoms.

[0236] R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by may have a substituent. With respect 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. ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by is preferably unsubstituted.

[0237] Examples of the basic compound (CA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (CA) may be a compound having at least one selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (CA) may be an alkylamine derivative having at least one selected from the group consisting of a hydroxy group and an ether bond, or an aniline derivative having at least one selected from the group consisting of a hydroxy group and an ether bond.

[0238] The difference between the pKa of the conjugate acid of the basic compound (CA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (CA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic compound (CA) is, for example, preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0239] Specific examples of the basic compound (CA) include the compounds described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, the disclosure of which is incorporated herein by reference. Specific examples of the low molecular weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid include the compounds described in paragraphs

[0156] to

[0163] of WO 2020 / 066824, the disclosure of which is incorporated herein by reference.

[0240] (Compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation) Specific examples of the compound (CC) include onium salt compounds (CD) of acids that are relatively weak acids compared to the photoacid generator, and basic compounds (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.

[0241] Compound (CD) may be a compound that generates an acid upon exposure to light. Compound (CD) is preferably a compound that generates an acid having a pKa value 1.00 or more higher than that of the acid generated from the photoacid generator. The difference between the pKa of the acid generated from compound (CD) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the acid generated from compound (CD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. The pKa of the acid generated from compound (CD) is, for example, preferably 0.50 to 10.00, more preferably 0.80 to 5.00, and even more preferably 1.00 to 5.00.

[0242] The compound (CD) is preferably an onium salt compound consisting of an anion and a cation. Examples of the compound (CD) include "M ＋ X － Examples of compounds include compounds (onium salts) represented by the formula "M ＋ represents a cation, and preferably represents an organic cation. ＋ As the photoacid generator, M described above can be used. ３ ＋ The same as above can be mentioned. － represents an anion, and preferably represents an organic anion. － Examples of the anion include those described above in the description of the photoacid generator.

[0243] Among these, the onium salt (CD) is preferably a compound containing an anion moiety represented by any one of the following formulae (BB-1) to (BB-7).

[0244]

[0245] Specific examples of the onium salt compound (CD) include the compounds described in paragraphs

[0305] to

[0314] of WO 2020 / 158337, the disclosures of which are incorporated herein by reference. Specific examples of the basic compound (CE) include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824 and the compound described in paragraph

[0164] of WO 2020 / 066824, the disclosures of which are incorporated herein by reference.

[0246] In addition to the above-mentioned compounds, known compounds disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

[0664] , U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0095] to

[0187] , U.S. Patent Application Publication No. 2016 / 0237190A1, paragraphs

[0403] to

[0423] , and U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0259] to

[0328] , can also be suitably used as the acid diffusion controller, and the descriptions above are incorporated herein by reference.

[0247] The molecular weight of the acid diffusion controller is not particularly limited, but is preferably from 100 to 3,000, more preferably from 150 to 2,500, and even more preferably from 200 to 2,000.

[0248] When the resist composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the resist composition. Furthermore, the content of the acid diffusion controller is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and even more preferably 15.0% by mass or less, based on the total solid content of the resist composition. Only one acid diffusion controller may be used, or two or more may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0249] [Solvent] The resist composition of the present invention preferably contains a solvent. The solvent preferably contains at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate (PGMEA)) and (M2) propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE)), lactate esters (such as ethyl lactate), acetate esters, alkoxypropionic acid esters, chain ketones (such as diacetone alcohol), cyclic ketones (such as 2-heptanone, cyclohexanone, or cyclopentanone), lactones (such as γ-butyrolactone), and alkylene carbonates (such as propylene carbonate). The solvent may further contain a solvent other than components (M1) and (M2).

[0250] The solvent preferably contains component (M1). More preferably, the solvent consists essentially of component (M1) alone or is a mixed solvent of component (M1) and other components. In the latter case, the solvent further preferably contains both component (M1) and component (M2).

[0251] The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably from 100 / 0 to 0 / 100, more preferably from 100 / 0 to 15 / 85, still more preferably from 100 / 0 to 40 / 60, and particularly preferably from 100 / 0 to 60 / 40.

[0252] As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0253] The content of the solvent in the resist composition is preferably determined so that the solids concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass.

[0254] [Other Additives] The resist composition of the present invention may contain other additives in addition to those described above. Examples of other additives include surfactants, dissolution inhibitors, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in the developer. The surfactants will be described in detail below.

[0255] [Surfactant] The surfactant is preferably a fluorine-based or silicon-based surfactant. Examples of fluorine-based surfactants and silicon-based surfactants include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954. When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%, based on the total solid content of the composition. The resist composition may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0256] The resist composition of the present invention may also contain water as an impurity. When water is contained as an impurity, the lower the content of water, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the entire resist composition. The resist composition may also contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the resin). When residual monomers are contained as impurities, the lower the content of residual monomers, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the total solid content of the resist composition.

[0257] [Pattern Forming Method] The pattern forming method of the present invention is a pattern forming method comprising the steps of: (1) forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) of the present invention; (2) exposing the resist film to light; and (3) developing the exposed resist film using a developer. Each of the steps will be described in detail below.

[0258] [Step (1)] Step (1) is a step of forming a resist film on a substrate using a resist composition of the present invention. Details of the resist composition of the present invention used in step (1) are as described above.

[0259] As a method for forming a resist film on a substrate using a resist composition, for example, a method of coating the resist composition on a substrate can be mentioned. If necessary, it is preferable to filter the resist composition before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the pore size of the filter is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited, but when it is a polymer, it preferably includes polyolefins (including high density and ultra-high molecular weight) such as polyethylene (PE) and polypropylene (PP); polyamides such as nylon 6 and nylon 66; polyimides (PI); polyamideimides; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkanes; derivatives of the above polymers; and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimides, polyesters, polysulfones, cellulose, polyfluorocarbons, and derivatives thereof. In addition to resins, diatomaceous earth, glass, etc. may also be used.

[0260] The resist composition may be filtered using one filter or a combination of two or more filters. When two or more filters are used, they may be the same or different. The resist composition may be circulated and repeatedly filtered using the same filter.

[0261] The resist composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spin application using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film, etc.) may be formed below the resist film.

[0262] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in at least one of a normal exposure machine and a developing machine, and may be performed using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0263] The present invention also includes the resist film obtained in step (1). The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Furthermore, when ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0264] A top coat may be formed on the resist film using a top coat composition. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that may be contained in the top coat include basic compounds that may be contained in the resist composition.

[0265] [Step (2)] Step (2) is a step of exposing the resist film formed in step (1). Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and preferably far ultraviolet light with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ These include excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam.

[0266] After exposure, it is preferable to bake (heat) the film before developing. This step is also called post-exposure baking. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature for baking is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time for baking is not particularly limited, but is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using a means provided in at least one of a conventional exposure machine and a developing machine, and may be performed using a hot plate or the like.

[0267] [Step (3)] Step (3) is a step of developing the resist film exposed in step (2) using a developer. By performing step (3), a resist pattern (also simply referred to as a "pattern") is formed. The developer used in step (3) may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer). Examples of development methods include a method of immersing a substrate in a tank filled with the developer for a certain period of time (dip method), a method of piling the developer on the surface of the substrate by surface tension and leaving it to stand for a certain period of time (puddle method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method). The development time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C. In step (3), a step of stopping development by replacing the solvent with another solvent may be performed.

[0268] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0269] 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.

[0270] The organic solvents may be mixed in plural, or may be mixed with a solvent other than the organic solvents or water. The water content of the organic developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the organic developer.

[0271] The organic developer preferably contains butyl acetate (n-butyl acetate), and more preferably contains butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms. The organic treatment liquid may contain only one or more hydrocarbons having from 9 to 12 carbon atoms. The hydrocarbon having from 9 to 12 carbon atoms is preferably at least one selected from the group consisting of alkanes, alkenes, alkynes, and cycloalkanes, more preferably an alkane, still more preferably at least one selected from the group consisting of nonane, decane, undecane, and dodecane, particularly preferably at least one selected from the group consisting of undecane and dodecane, and most preferably undecane. The hydrocarbon having from 9 to 12 carbon atoms may contain a structural isomer.

[0272] The content of butyl acetate in the organic developer is preferably 65% ​​by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less, based on 100% by mass of the entire organic developer. The content of hydrocarbons having 9 to 12 carbon atoms in the organic developer (the total amount when multiple hydrocarbons having 9 to 12 carbon atoms are contained) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire organic developer.

[0273] The mass ratio of butyl acetate to hydrocarbon having from 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having from 9 to 12 carbon atoms) is preferably from 60 / 40 to 95 / 5, more preferably from 70 / 30 to 95 / 5, still more preferably from 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0274] The organic developer may contain other components in addition to butyl acetate and hydrocarbons having from 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having from 9 to 12 carbon atoms, surfactants, antioxidants, basic compounds, and the like.

[0275] [Rinsing Step] After step (3) is performed, rinsing may be performed. The rinsing solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common solvent can be used. The rinsing solution preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0276] The rinsing method is not particularly limited, and examples thereof include a method in which a rinse liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinse liquid for a certain period of time (dip method), and a method in which a rinse liquid is sprayed onto the surface of the substrate (spray method).

[0277] The pattern formation method of the present invention may also include a heating step (post-bake) after step (3). This step removes the developer and rinse solution remaining between and within the pattern. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed, for example, at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0278] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step (3) as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step (3) as a mask is preferred. The dry etching is not particularly limited, but oxygen plasma etching is preferred.

[0279] The developer, resist composition, and other various materials (e.g., solvent, rinse, anti-reflective coating-forming composition, top coat-forming composition, etc.) used in the pattern formation method of the present invention preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit of the impurity content is not particularly limited and may be 0 mass ppt or more. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0280] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions that minimize contamination. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0281] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and a content of 0 ppt by mass or more is preferred.

[0282] [Method for Manufacturing an Electronic Device] This specification also relates to a method for manufacturing an electronic device, including the pattern formation method of the present invention described above, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of this specification include those installed in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0283] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0284] <Components of Resist Composition> The components used to prepare the resist compositions used in the examples and comparative examples, or the materials used in the evaluations described below, are listed below.

[0285] [Resin] Table 1 shows the content ratios of each repeating unit in Resins P-1 to P-25 (Resins (P)) and RP-1 to RP-2 used in preparing the resist compositions, Table 2 shows the content of each repeating unit in Resins A-1 to A-5 (Resins (A)), and Table 3 shows the content of each repeating unit in Resins D-1 to D-6. In Tables 1 and 2, the content of each repeating unit corresponds to the order of the structure described in the following paragraph, from left to right. In the tables, the "mol %" column indicates the content (mol %) of each repeating unit relative to all repeating units. In the tables, the "Mw" column indicates the weight average molecular weight. In the tables, the "Mw / Mn" column indicates the dispersity. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resins were measured by GPC (carrier: tetrahydrofuran (THF)) (values ​​calculated in terms of polystyrene). The composition ratios (mol ratios) of the resins are as follows: １３ Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0286]

[0287]

[0288]

[0289] The structure of each repeating unit in the resin is shown below: Resin (P) is a resin having a repeating unit A1 represented by general formula (I) and a repeating unit A2 represented by general formula (II).

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297] Resins P-3 and P-8 were synthesized according to the synthesis examples described below, and other resins were synthesized according to the synthesis examples below or known methods.

[0298] <Synthesis of P-M-A>

[0299]

[0300] 50 g of 5-iodovanillin was dissolved in 500 g of tetrahydrofuran (THF), and then 21.8 g of triethylamine was added. 36.4 g of triisopropylsilyl chloride (TIPSCl) was added dropwise with ice cooling, and the mixture was stirred for 1 hour. Subsequently, 200 mL of saturated aqueous ammonium chloride solution was added, and the mixture was transferred to a separatory funnel and the organic layer was extracted. 300 mL of ethyl acetate was added to the organic layer, and the mixture was washed twice with 200 mL of saturated brine. The organic layer was dried over magnesium sulfate, and the solvent was distilled off to obtain 74.8 g of P-M-1.

[0301] After mixing 154 g of methyltriphenylphosphonium bromide and 1,500 g of THF, 48.8 g of potassium tert-butoxide was slowly added while cooling on ice and stirred for 30 minutes. Next, a solution of 74.8 g of P-M-1 dissolved in 748 g of THF was added dropwise over 30 minutes while cooling on ice, and then stirred at room temperature for 1 hour. Subsequently, 250 mL of saturated aqueous ammonium chloride solution was added while cooling on ice, and the mixture was transferred to a separatory funnel and the organic layer was extracted. The organic layer was washed twice with 200 mL of saturated brine, and the solvent was then distilled off. The resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 10 / 90) to obtain P-M-2.

[0302] 55 g of P-M-2 was dissolved in 165 g of THF, and then 129 mL of tetrabutylammonium fluoride (TBAF, THF solution (1 mol / L)) was added dropwise under ice cooling, followed by stirring at room temperature for 1 hour. 300 mL of ethyl acetate was added thereto, and the mixture was transferred to a separatory funnel to extract the organic layer. The organic layer was washed twice with 150 mL of water and once with 150 mL of saturated brine, then dried over magnesium sulfate, and the solvent was distilled off. The resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 20 / 80). After distilling off the developing solvent, the residue was dissolved in PGMEA (propylene glycol monomethyl ether acetate) to obtain 41.5 g of P-M-A (PGMEA 46.2 wt % solution). P-M-A １ The H-NMR data is shown below. １ H-NMR (300MHz, CDCl ３ ): δ=7.34 (d, 1H), 6.89 (d, 1H), 6.56 (dd, 1H), 6.11 (s, 1H), 5.60 (d, 1H), 5.17 (d, 1H), 3.92 (s, 3H).

[0303] [Synthesis of P-3] <Synthesis of P-3-A>

[0304]

[0305] 4.58 g of fluorinated benzenesulfonic acid isobutyl ester, 8.66 g of P-M-A (PGMEA 46.2 wt % solution), and 43.8 g of acetonitrile were mixed, and then 7.08 g of cesium carbonate was added and stirred at room temperature for 1 hour. 100 mL of water and 100 mL of ethyl acetate were added to this, and the resulting solution was transferred to a separatory funnel and the organic layer was extracted. The organic layer was washed twice with 100 mL of water and once with 100 mL of saturated brine, and then the solvent was distilled off to obtain P-3-1.

[0306] The obtained P-3-1 was dissolved in 60 g of acetonitrile, and then 3.5 g of benzyltrimethylammonium bromide was added and stirred at 60°C for 1 hour. After distilling off the solvent, the mixture was reslurried in 50 mL of diisopropyl ether and filtered to obtain 5.2 g of P-3-A. １ H-NMR, and １９The F-NMR data is shown below. １ H-NMR (300MHz, acetone-d6): δ = 7.74 (d, 2H), 7.59-7.51 (m, 4H), 7.29 (d, 1H), 6 .73 (dd, 1H), 5.91 (d, 1H), 5.32 (d, 1H), 4.86 (s, 2H), 3.80 (s, 3H), 3.35 (s, 9H). １９ F-NMR (300MHz, acetone-d6): δ=-141.1 (m, 2F), -160.3 (m, 2F).

[0307] <Synthesis of P-3>

[0308]

[0309] 4.0 g of diacetone alcohol (DAA) / water (mass ratio 4 / 1) was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, a mixed solution of 1.6 g of P-3-A, 1.7 g of P-3-B, 3.3 g of P-3-C, 14 g of diacetone alcohol / water (mass ratio 4 / 1), and 0.62 g of dimethyl 2,2'-azobisisobutyrate [V-601, Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours to obtain a reaction solution. After completion of the dropwise addition, the reaction solution was stirred for an additional 2 hours at 80 ° C. After allowing the obtained reaction solution to cool, it was reprecipitated with a large amount of diisopropyl ether and then filtered. The obtained solid was dissolved in an appropriate amount of methanol to obtain 20 g of P-3-2 (20 wt % solution in methanol).

[0310] 23 g of dichloromethane and 15 g of water were added to 0.27 g of ON-1 (sulfonium cation bromide), and then 7.5 g of P-3-2 (20 wt % solution in methanol) was added and stirred at room temperature for 15 minutes. The resulting solution was transferred to a separatory funnel, and the organic layer was extracted and then washed three times with 15 g of water. After distilling off the solvent, 5.4 g of cyclopentanone was added to the residue and dissolved. The resulting cyclopentanone solution was reprecipitated with a large amount of heptane and then filtered to obtain 1.1 g of P-3.

[0311] [Synthesis of P-8]

[0312]

[0313] 7.2 g of cyclohexanone was heated to 80°C under a nitrogen stream. While stirring this solution, a mixed solution of 19 g of P-M-A (PGMEA 46.2 wt% solution), 7.2 g of P-8-B, 19 g of cyclohexanone, and 0.71 g of dimethyl 2,2'-azobisisobutyrate [V-601, Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours to obtain a reaction solution. After completion of the dropwise addition, the reaction solution was stirred at 80°C for an additional 2 hours. The resulting reaction solution was allowed to cool and then reprecipitated with a large amount of ethyl acetate / heptane (mass ratio 1 / 9), filtered, and the resulting solid was vacuum dried to obtain 5.6 g of P-8-3.

[0314] To 3.7 g of P-8-3, 68 g of THF and 38 g of water were added, followed by the addition of 0.54 g of fluorinated benzenesulfonic acid isobutyl ester and 0.51 g of potassium carbonate, followed by stirring at room temperature for 1 hour. Next, 37 mL of 0.1 N hydrochloric acid and 95 mL of ethyl acetate were added, and the mixture was transferred to a separatory funnel and the organic layer was extracted. The organic layer was washed twice with 100 mL of water and once with 100 mL of saturated brine, and then the solvent was distilled off to obtain P-8-4.

[0315] The obtained P-8-4 was dissolved in 46 g of acetonitrile, and then 0.50 g of benzyltrimethylammonium bromide was added and stirred for 1 hour at 60° C. After distilling off the solvent, an appropriate amount of methanol was added to obtain 21 g of P-8-5 (20 wt % solution in methanol).

[0316] To 0.61 g of ON-1 (sulfonium cation bromide), 30 g of dichloromethane and 20 g of water were added, followed by the addition of 10 g of P-8-5 (20 wt % solution in methanol) and stirring at room temperature for 15 minutes. The resulting solution was transferred to a separatory funnel, and the organic layer was extracted and then washed three times with 20 g of water. After distilling off the solvent, 6.9 g of cyclopentanone was added to the residue and dissolved. The resulting cyclopentanone solution was reprecipitated with a large amount of heptane and then filtered to obtain 1.3 g of P-8.

[0317] [Photoacid Generator] The structures of the photoacid generators (B-1 to B-6) used in preparing the resist compositions are shown below.

[0318]

[0319] [Acid Diffusion Controller] The structures of the acid diffusion controllers (C-1 to C-12) used in preparing the resist compositions are shown below.

[0320]

[0321] [Surfactants] E-1: Megafac F176 (manufactured by DIC Corporation, fluorosurfactant) E-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicone surfactant) E-3: PF656 (manufactured by OMNOVA, fluorosurfactant)

[0322] [Solvents] F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-heptanone F-7: Ethyl lactate F-8: γ-butyrolactone F-9: Propylene carbonate

[0323] <Preparation and Coating of Resist Compositions> The components were mixed in the blending ratios shown in Table 4 below so that the solid content concentration was 2.0 mass %. "Solid content" refers to all components other than the solvent. The resulting mixture was passed through a polyethylene filter with a pore size of 0.03 μm and filtered to prepare each resist composition.

[0324] "Table 4 (continued)" is a continuation of Table 4. For example, "Re-2" indicates a resist composition containing 97.1% by mass of "P-2," 2.9% by mass of "C-1," and the remainder being "F-1." In Table 4, descriptions separated by " / " in the "Type" column indicate that the substance contains multiple compounds, and descriptions separated by " / " in the "Wt%" column indicate the respective contents of the multiple compounds. For example, "Resin (P)" in "Re-30" contains "P-3" and "P-8," with the respective contents being 45.0% and 42.0% by mass. In Table 4, the "Wt%" column indicates the content (wt%) of each solid component relative to the total solid content. The solid content refers to the components excluding the solvent. In Table 4, the "Wt%" column for "Solvent" indicates the mixing ratio (wt%) of each solvent.

[0325]

[0326]

[0327] Using each resist composition prepared by the above-mentioned procedure, a resist pattern was formed according to the procedure described below, and the resolution of the pattern and the sensitivity of the resist composition were evaluated.

[0328] <Resist Pattern Formation (EUV Exposure, Alkali Development)> An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 5 below was applied onto the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. This resulted in a silicon wafer having a resist film. The silicon wafer having the resist film obtained by the above procedure was subjected to pattern exposure using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36). A mask with a line size (line width) of 16 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[0329] <Resist Pattern Formation (EUV Exposure, Organic Solvent Development)> Instead of the resist composition shown in Table 5, a resist composition shown in Table 6 below was applied onto the underlayer film, and in the development step, n-butyl acetate was used instead of the tetramethylammonium hydroxide aqueous solution, and development was carried out for 30 seconds. This was then spin-dried to obtain a negative pattern.

[0330] <Resolution (Limit Development, nm)> Using the above-described resist pattern formation method, the optimum exposure dose Eop (mJ / cm) at which a line and space pattern (L / S pattern) with a target size of line:space=1:1 is formed. ２) was determined. The limiting resolution at this Eop, specifically, the minimum dimension of the pattern that could be resolved without collapsing when an L / S pattern was formed by gradually increasing the exposure dose from the optimum exposure dose Eop, was determined using a critical dimension scanning electron microscope (SEM (Scanning Electron Microscope, Hitachi, Ltd. S-9380II)). This was defined as the "limiting resolution (nm)." The smaller the value of the limiting resolution, the better the resolution. The limiting resolution (nm) is preferably 15.0 nm or less, more preferably 14.0 nm or less, even more preferably 13.0 nm or less, even more preferably 12.0 nm or less, and most preferably 11.0 nm or less.

[0331] <Sensitivity (optimum exposure amount (mJ / cm ２ ))> Using a length-measuring scanning electron microscope (CG-4100 manufactured by Hitachi High-Technologies Corporation), the line width of the line and space pattern was measured while changing the exposure dose, and the exposure dose at which the line width became 20 nm was determined. This was designated as the optimum exposure dose (mJ / cm ２ The smaller the optimum exposure dose, the higher the sensitivity. The optimum exposure dose was 55 mJ / cm ２ Preferably, 50 mJ / cm or less ２ More preferably, 45 mJ / cm or less ２ The following is even more preferred:

[0332] <Results> Table 5 shows the evaluation results of the positive pattern obtained by the alkali development, and Table 6 shows the evaluation results of the negative pattern obtained by the organic solvent development.

[0333]

[0334]

[0335] The results in Tables 5 and 6 confirm that the resist compositions (actinic ray- or radiation-sensitive resin compositions) of the present invention not only provide excellent resolution for resist patterns formed using the resist compositions, but also provide excellent sensitivity for the resist compositions. On the other hand, the resins contained in resist compositions Re-40 and Re-41 used in Comparative Examples 1-1 to 1-2 and 2-1 to 2-2 did not contain either repeating unit A1 or repeating unit A2, and therefore the resolution of the resist patterns formed using the resist compositions was insufficient.

[0336] Furthermore, by comparing Example 1-21 with Examples 1-2 to 1-3, it is clear that in the repeating unit A1 represented by general formula (I), Ar １ is an aromatic hydrocarbon ring group having one or more substituents selected from a fluorine atom, a fluoroalkyl group, and an iodine atom, the resolution of the resist pattern was confirmed to be more excellent. １ is a divalent aromatic ring group which may have a substituent, the resolution of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-23 and Examples 1-2 to 1-3, it was confirmed that when X is an oxygen atom in the repeating unit A1 represented by general formula (I), the resolution of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-20 and Example 1-24, it was confirmed that when L ２ is -Y-C(=O)-*1 or a divalent aromatic ring group which may have a substituent, the resolution of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-19 and Example 1-24, it was confirmed that when the repeating unit A2 represented by general formula (II) is a repeating unit represented by general formula (IIa), the resolution of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-11 and Example 1-13, it was confirmed that when in the repeating unit represented by general formula (IIa), L ３is -Y-C(=O)-*2, the resolution of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-1 and Examples 1-4 to 1-6, it was confirmed that when at least one of the repeating unit A1 and the repeating unit A2 contains an iodine atom, or when the resin further contains a repeating unit other than the repeating unit A1 and the repeating unit A2 that contains an iodine atom, at least one of the resolution and sensitivity of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-2 to Example 1-6, it was confirmed that when the repeating unit A1 contains an iodine atom, at least one of the resolution and sensitivity of the resist pattern was confirmed to be more excellent. From a comparison between Example 1-25 and Examples 1-2 to 1-3, it was confirmed that when Z ＋ is a sulfonium cation represented by general formula (III), it has been confirmed that at least one of the resolution and sensitivity of the resist pattern is superior.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit A1 represented by general formula (I) and a repeating unit A2 represented by general formula (II). In general formula (I), R １ａ ~R １ｃ each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １ represents a single bond or a divalent linking group. X represents a single bond, —O—, —S—, —CO—, —CS—, or —SO ２ - represents. １ represents an aromatic ring group which may have a substituent. ＋ represents a sulfonium cation having an acid-decomposable group or a sulfonium cation having four or more fluorine atoms, provided that R １ｃ and L １ may be bonded to each other to form a ring. １ｃ and Ar １ and may be bonded to each other to form a ring. ２ａ ~R ２ｃ each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ２ represents a single bond or a divalent linking group. ２ｃ and L ２ may be bonded to each other to form a ring. ３ ~R ５ each independently represents a monovalent organic group; R ３ ~R ５ Two of R may be bonded to each other to form a ring. ３ ~R ５ satisfies at least one of requirements 1 and 2. (Requirement 1) R ３ ~R ５ Two of the R are bonded to each other to form a ring. (Requirement 2) ３ ~R ５ At least one of the above is a group represented by general formula (IIx) or general formula (IIy). In general formulas (IIx) and (IIy), R ｘ and R ｙ each independently represents a hydrogen atom or a monovalent substituent. ｘ Two of the groups may be bonded to each other to form a ring. * indicates the bonding position.

2. Ar １ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein is an aromatic hydrocarbon ring group having one or more substituents selected from a fluorine atom, a fluoroalkyl group, and an iodine atom.

3. L １ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein is a divalent aromatic ring group which may have a substituent.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein X is an oxygen atom.

5. L ２ is -Y-C(=O)-*1 or a divalent aromatic ring group which may have a substituent, Y represents a single bond or a divalent linking group, and *1 represents the position at which the compound is bonded to the oxygen atom shown in general formula (II).

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit A2 is a repeating unit represented by general formula (IIa). In general formula (IIa), R ２ａ ~R ２ｃ , and R ５ is R in the general formula (II). ２ａ ~R ２ｃ , and R ５ It is synonymous with L. ３ represents a single bond or a divalent organic group, and n represents an integer of 1 or more.

7. L ３ is -Y-C(=O)-*2, Y represents a single bond or a divalent linking group, and *2 represents a carbon atom bonded to the oxygen atom clearly shown in general formula (IIa).

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein at least one of the repeating unit A1 and the repeating unit A2 contains an iodine atom, or the resin further contains a repeating unit other than the repeating unit A1 and the repeating unit A2 that contains an iodine atom.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit A1 contains an iodine atom.

10. Z ＋ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein is a sulfonium cation represented by general formula (III): Ar ３ａ ~Ar ３ｃ each independently represents an aryl group which may have a substituent, Ar ３ａ ~Ar ３ｃ Two of Ar may be bonded to each other to form a ring. ３ａ ~Ar ３ｃ satisfies at least one of requirements 3 and 4. (Requirement 3) Ar ３ａ ~Ar ３ｃ (Requirement 4) At least one of Ar has an acid-decomposable group. ３ａ ~Ar ３ｃ The total number of fluorine atoms contained in the optionally substituted aryl group represented by the formula (I) is 4 or more.

11. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.

12. A pattern forming method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10; exposing the resist film; and developing the exposed resist film using a developer.

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

Images