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

Abstract

Provided is an active-light-sensitive or radiation-sensitive resin composition with which it is possible to form a pattern having exceptional LWR performance and which also has exceptional resolution. Also provided are a resist film, a pattern formation method, and an electronic device production method that involve the active-light-sensitive or radiation-sensitive resin composition. Additionally provided are a polymerizable compound and a resin that are suitably used in the active-light-sensitive or radiation-sensitive resin composition.　The active-light-sensitive or radiation-sensitive resin composition contains a photoacid generator and a resin having repeating units derived from a polymerizable compound having an acid-decomposable group, the polymerizable compound being such that the glass transition temperature of a homopolymer thereof is 220°C or higher, and the molar amount of acid-decomposable groups relative to the mass of the polymerizable compound being 3.40 mmol / g or greater.

Description

[Technical Field]

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

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

[0003] For example, Patent Document 1 discloses a resist composition containing a resin including a structural unit derived from a compound represented by formula (I) and a structural unit of a predetermined structure, and an acid generator. 1 and R 2 each independently represents a group having an acid labile group, and W represents an alicyclic hydrocarbon group having 5 to 18 carbon atoms which may have a substituent.

[0004] [ka] [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-154322 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have prepared and examined resist compositions with reference to Patent Document 1, and have found that there is room for further improvement in resolution and line width roughness (LWR) performance of the formed patterns. Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern with excellent LWR performance and also has excellent resolution. Another object of the present invention is to provide a resist film, a pattern forming method, and a method for producing an electronic device, which are related to the actinic ray-sensitive or radiation-sensitive resin composition. Another object of the present invention is to provide a polymerizable compound and a resin that are suitable for use in the actinic ray-sensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit derived from a polymerizable compound having an acid-decomposable group and a photoacid generator, the polymerizable compound is a polymerizable compound whose homopolymer has a glass transition temperature of 220°C or higher, The actinic ray-sensitive or radiation-sensitive resin composition, wherein the molar amount of the acid-decomposable group relative to the mass of the polymerizable compound is 3.40 mmol / g or more. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the polymerizable compound contains at least one of an aromatic ring and an aliphatic heterocycle. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the polymerizable compound has a polycyclic structure. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the polymerizable compound is a polymerizable compound having an aliphatic heterocycle with a polycyclic structure, or a polymerizable compound having an aromatic ring. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the polymerizable compound has at least two acid-decomposable groups. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the polymerizable compound is an acrylic compound or a methacrylic compound. [7] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit derived from a polymerizable compound represented by general formula (1) described below and a photoacid generator. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the general formula (3) described below. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the general formula (4) described below.

[10] R X1 ~R X4 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [7] to [9], wherein at least two of the above represent an acid-decomposable group.

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [7] to

[10] , wherein the polymerizable compound is a polymerizable compound represented by general formula (5) described later.

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

[11] .

[13] A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] ; exposing the resist film to light; and developing the exposed resist film using a developer.

[14] A method for manufacturing an electronic device, comprising the pattern forming method according to

[13] .

[15] A polymerizable compound represented by the general formula (1) described below.

[16] A resin having a repeating unit derived from a polymerizable compound represented by the general formula (1) described below. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern having excellent LWR performance and also has excellent resolution. Furthermore, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for producing an electronic device, which are related to the actinic ray-sensitive or radiation-sensitive resin composition. Furthermore, the present invention can provide a polymerizable compound and a resin that are suitable for use in the actinic ray-sensitive or radiation-sensitive resin composition. [Brief explanation of the drawings]

[0010] [Figure 1] This is the 1H-NMR chart of M-55 synthesized in the synthesis example section. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, electron beams (EB), etc. As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, the term "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light typified by an excimer laser, extreme ultraviolet light (EUV light), and X-rays, but also drawing using particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. 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 "XYZ", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-OZ" or "XO-CO-Z".

[0012] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (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).

[0013] 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.

[0014] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0015] On the other hand, pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + 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, such as Gaussian 16.

[0016] As described above, the pKa in this specification refers to a value calculated using the software package 1 based on a database of Hammett's substituent constants and known literature values. However, 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 mentioned above, the pKa in this specification refers to the "pKa in aqueous solution," but when the pKa in aqueous solution cannot be calculated, the "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0017] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0018] [First embodiment of actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as the "resist composition of the first embodiment") contains a resin (hereinafter also referred to as the "specific acid-decomposable resin A") having a repeating unit derived from a polymerizable compound having an acid-decomposable group (hereinafter also referred to as the "specific monomer A"), and a photoacid generator. Here, the above-mentioned specific monomer A is a polymerizable compound whose homopolymer has a glass transition temperature of 220°C or higher, and the molar amount of acid-decomposable groups relative to the mass of the polymerizable compound (hereinafter also referred to as "protecting group value") is 3.40 mmol / g or higher. In this specification, the glass transition temperature of the homopolymer of specific monomer A refers to a value measured by the method described below. Due to the above-described configuration, the resist composition of the first embodiment is capable of forming a pattern with excellent resolution and LWR.

[0019] The mechanism of action of the resist composition of the first embodiment is not clear, but the inventors of the present invention speculate as follows. The specific acid-decomposable resin A contained in the resist composition of the first embodiment has a repeating unit derived from the specific monomer A. Because the homopolymer of the specific monomer A has a high glass transition temperature, the resist composition of the first embodiment containing the specific acid-decomposable resin A can form a pattern with high film strength. As a result, it is believed that the resist composition of the first embodiment exhibits high resolution (in other words, a small limiting resolution (nm)). Furthermore, because the specific monomer A has a high protecting group value, a pattern formed using the resist composition of the first embodiment containing the specific acid-decomposable resin A can exhibit excellent dissolution contrast. As a result, it is believed that the pattern formed using the resist composition of the first embodiment exhibits excellent LWR performance. In other words, it is presumed that due to the properties of the specific monomer A, the resist composition of the first embodiment exhibits excellent high resolution, and the formed pattern exhibits excellent LWR performance. Hereinafter, a resist composition that has higher resolution and / or a pattern formed using the resist composition that has better LWR performance may also be referred to as "the effects of the present invention being better."

[0020] The resist composition of the first embodiment will be described in detail below. The resist composition of the first embodiment may be a positive resist composition or a negative resist composition, and may also be a resist composition for alkali development or a resist composition for organic solvent development. The resist composition of the first embodiment is typically a chemically amplified resist composition. First, the various components of the resist composition of the first embodiment will be described in detail below.

[0021] [Specified acid-decomposable resin A] The resist composition of the first embodiment contains a resin having a repeating unit derived from a specific monomer A (specific acid-decomposable resin A). The specific acid-decomposable resin A is a resin that decomposes under the action of an acid and has an increased polarity. That is, in the pattern formation method using the resist composition of the first embodiment, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0022] <<Specific Monomer A>> First, the specific monomer A will be described below. The specific monomer A is a polymerizable compound having an acid-decomposable group, and the glass transition temperature of the homopolymer thereof is 220° C. or higher, and the protecting group value is 3.40 mmol / g or higher.

[0023] The acid-decomposable group means a group that decomposes under the action of an acid and has an increased polarity. The specific acid-decomposable resin A formed from the specific monomer A having an acid-decomposable group has a repeating unit having an acid-decomposable group (hereinafter also referred to as an "acid-decomposable repeating unit"). Due to the presence of this acid-decomposable repeating unit, the specific acid-decomposable resin A exhibits the property of increasing its polarity under the action of acid, thereby increasing its solubility in alkaline developers and decreasing its solubility in organic solvents.

[0024] The acid-decomposable group generally refers to 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 a polar group is protected by a leaving group that is released under the action of an acid. The acid-decomposable group can be decomposed under the action of an acid to generate a polar group. The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups. Among these, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred, a phenolic hydroxyl group or a carboxyl group is more preferred, and a carboxyl group is even more preferred, in terms of better effects of the present invention.

[0025] Examples of the leaving group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0026] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group, or an alkenyl group (linear or branched). If possible, these groups preferably have a fluorine atom or a group having a fluorine atom as a substituent. When all of Rx1 to Rx3 are alkyl groups (straight-chain or branched-chain), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to each other to form a ring (monocyclic or polycyclic).

[0027] The alkyl groups of Rx1 to Rx3 are preferably alkyl groups 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. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group or a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The aryl group of Rx1 to Rx3 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. The aralkyl groups of Rx1 to Rx3 are preferably aralkyl groups having 7 to 20 carbon atoms. The alkenyl groups of Rx1 to Rx3 are preferably vinyl groups. The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by bonding two of Rx1 to Rx3 together, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in such a cycloalkyl group, one or more (for example, one or two) ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1) or formula (Y2), for example, an embodiment in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group is also preferred. In addition, in formula (Y1) or formula (Y2), when two of Rx1 to Rx3 are bonded to form a cycloalkenyl group, and in the cycloalkenyl group, a vinylene group is present at a position adjacent to C (carbon atom) specified in "C(Rx1)(Rx2)(Rx3)" in formula (Y1) or formula (Y2), the remaining one of Rx1 to Rx3 may be a hydrogen atom.

[0028] In formula (Y3), R36 ~R 38 R each independently represents a hydrogen atom or an organic group. 37 and R 38 may be bonded to each other to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 is also preferably a hydrogen atom. R in formula (Y3) 36 ~R 38 Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by Rx1 to Rx3 in formula (Y1) and formula (Y2) include the same groups as those described above as the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by Rx1 to Rx3 in formula (Y1) and formula (Y2). R 37 and R 38 may be bonded to each other to form a ring. Also, R 38 In the acid-decomposable repeating unit, R may be bonded to the main chain of the repeating unit. 38 is preferably an alkylene group such as a methylene group.

[0029] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0030] [ka]

[0031] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5- or 6-membered ring). Q may be bonded to a part of the acid group protected by the group represented by formula (Y3-1) to form a ring. Furthermore, Q may be bonded to the main chain of the acid-decomposable repeating unit to form a ring in the acid-decomposable repeating unit. From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0032] In formula (Y4), 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.

[0033] In terms of achieving better acid decomposability of the acid-decomposable group 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 preferred 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.

[0034] Other leaving groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0035] In terms of achieving better effects of the present invention, a preferred embodiment of the acid-decomposable group is an acid-decomposable group represented by the following general formula (O1).

[0036] [ka]

[0037] In formula (O1), R 11 ~R 13 each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. The alkyl group and the alkenyl group may be linear or branched. The cycloalkyl group and the aryl group may be monocyclic or polycyclic. In addition, R 11 ~R 13 Two of these may be bonded to each other to form a ring, but it is preferable that they do not form a ring in order to obtain better effects of the present invention. * denotes a binding site. R 11 ~R 13 In particular, it is preferable that all of R are alkyl groups (linear or branched). 11 ~R 13 When all of R are alkyl groups (linear or branched), 11 ~R 13At least two of these are preferably methyl groups.

[0038] R 11 ~R 13 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. R 11 ~R 13 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. R 11 ~R 13 The aryl group is preferably an aryl group having 6 to 10 carbon atoms. R 11 ~R 13 The alkenyl group is preferably a vinyl group. R 11 ~R 13 The cycloalkyl group formed by combining these two may be either a monocyclic or polycyclic group, but among these, a monocyclic cycloalkyl group is preferred, and a 5- or 6-membered monocyclic cycloalkyl group is more preferred. 11 ~R 13 In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having 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.

[0039] Also, R 11 ~R 13 The alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by the formula (I) may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).

[0040] The number of acid-decomposable groups in the specific monomer A is not limited as long as it is 1 or more, but is preferably 2 or more in terms of better effects of the present invention. The upper limit is not particularly limited, but is, for example, 8 or less, preferably 6 or less, and more preferably 4 or less.

[0041] Specific monomer A is a polymerizable compound whose homopolymer has a glass transition temperature of 220° C. or higher. In this specification, the glass transition temperature of the homopolymer of specific monomer A refers to a value measured by the following method.

[0042] <<Method for measuring the glass transition temperature (Tg (℃)) of a homopolymer of a specific monomer A>> <1> A copolymer P1 having a weight average molecular weight of 60,000 or more (preferably, a weight average molecular weight of 60,000 to 100,000) is obtained by synthesizing a copolymer P1 using a feed composition of 30 mass % of specific monomer A and 70 mass % of cyclohexyl methacrylate. (2) The Tg of the obtained copolymer P1 is evaluated using a differential scanning calorimeter (DSC). <3> Using the following formula (1) based on the Fox formula, the Tg of the homopolymer of specific monomer A is calculated, assuming that the Tg of the homopolymer of cyclohexyl methacrylate is 98°C.

[0043] Formula (1)1 / Tg=w1 / Tg1+w2 / Tg2 In formula (1), Tg represents the Tg(K) of the copolymer P1. Tg1 represents the Tg(K) of the homopolymer of specific monomer A. Tg2 represents the Tg(K) of the homopolymer of cyclohexyl methacrylate. w1 represents the mass fraction of repeating units derived from specific monomer A relative to all repeating units in copolymer P1. w2 represents the mass fraction of repeating units derived from the homopolymer of cyclohexyl methacrylate relative to all repeating units in copolymer P1. When calculating the Tg of the homopolymer of specific monomer A, w1 is set to 0.3 and w2 is set to 0.7.

[0044] As a differential scanning calorimeter, for example, a differential scanning calorimeter "DSC-60 Plus Measurement System" manufactured by Shimadzu Corporation can be used.

[0045] The glass transition temperature of the homopolymer of specific monomer A is preferably 220° C. or higher, more preferably 250° C. or higher, even more preferably 280° C. or higher, and particularly preferably 300° C. or higher, in order to obtain better effects of the present invention. The upper limit is not particularly limited, but is preferably 400° C. or lower.

[0046] The protecting group value of the specific monomer A is 3.40 mmol / g or more. The protecting group value represents the molar amount (mmol / g) of the acid-decomposable group relative to the mass of the specific monomer A (polymerizable compound). The upper limit is not particularly limited, but is preferably 6.0 mmol / g or less. The protecting group value is preferably 3.50 mmol / g or more, and more preferably 3.60 mmol / g or more, in terms of achieving better effects of the present invention.

[0047] The molecular weight of the specific monomer A is not particularly limited, but is preferably, for example, 400 or more. The upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 700 or less.

[0048] The specific monomer A has a polymerizable group. The type of polymerizable group is not particularly limited, and examples thereof include radically polymerizable groups and cationically polymerizable groups, with radically polymerizable groups being preferred and ethylenically unsaturated groups being more preferred. Examples of the ethylenically unsaturated group include a vinyl group, a maleimide group, and a CH═CR group. T -(R T represents a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), CH2=CR Q -CO-O-(R Qrepresents an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), or a hydrogen atom. Q represents a methyl group or a hydrogen atom, CH2=CR Q -CO-O- corresponds to a (meth)acrylic group, and R Q represents a chlorine atom, CH2=CR Q (-CO-O- corresponds to an α-chloroacrylic group), and the polymerizable group is preferably a (meth)acrylic group in that the effects of the present invention are more excellent. In other words, the specific monomer A is preferably a (meth)acrylic compound. Among them, the polymerizable group is more preferably a methacrylic group in that the effects of the present invention are more excellent. The specific monomer A is preferably a monofunctional monomer.

[0049] The specific monomer A preferably contains at least one of an aromatic ring and an aliphatic heterocycle, from the viewpoint of setting the glass transition temperature at a predetermined value or higher. The aromatic ring may be monocyclic or polycyclic, and the number of ring atoms is preferably 5 to 20. The aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (such as oxygen atoms, sulfur atoms, and nitrogen atoms) as ring atoms. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a tolylene ring, an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring, and a benzene ring is preferred.

[0050] The aliphatic heterocycle may be monocyclic or polycyclic, and may be bridged. A bridged aliphatic heterocycle refers to a compound having a bridged structure such as norbornene. The number of ring atoms in the aliphatic heterocycle is preferably 5 to 20. The aliphatic heterocycle contains one or more (e.g., 1 to 5) heteroatoms as ring atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. In the aliphatic heterocycle, at least one of the ring atoms may be substituted with a carbonyl carbon. Examples of the aliphatic heterocycle include the aliphatic hydrocarbon rings (1) to (50) shown below, in which at least one ring member atom is substituted with a heteroatom such as an oxygen atom. In addition, at least one ring member atom in the aliphatic hydrocarbon rings (1) to (50) shown below may be substituted with a carbonyl carbon.

[0051] [ka]

[0052] Among these, the aliphatic heterocycle is preferably a polycyclic aliphatic heterocycle (aliphatic heterocycle with a polycyclic structure), more preferably a bridged one, from the viewpoint of achieving a glass transition temperature of a predetermined value or higher.

[0053] The specific polymer A may contain only one or more aromatic rings, only one or more aliphatic heterocycles, or one or more aromatic rings and one or more aliphatic heterocycles. When the specific polymer A contains one or more aromatic rings and one or more aliphatic heterocycles, the aromatic rings and the aliphatic heterocycles may form a polycyclic structure. The aromatic ring and the aliphatic heterocycle may further have a substituent.

[0054] A preferred embodiment of the specific polymer A is a polymerizable compound having an aliphatic heterocycle with a polycyclic structure, or a polymerizable compound having an aromatic ring.

[0055] Specific examples of the specific polymer A include compounds represented by the following general formula (A1). General formula (A1): YLZ-(R) p In the formula, Y represents a polymerizable group. L represents a single bond or a divalent linking group. Z represents a (p+1)-valent cyclic structural moiety containing one or more selected from aromatic rings and aliphatic heterocycles. R represents an acid-decomposable group. p represents an integer of 1 or more.

[0056] Examples of the polymerizable group represented by Y include the polymerizable groups described above. In terms of achieving better effects of the present invention, a maleimide group or a (meth)acrylic group is preferred, a maleimide group or a methacrylic group is more preferred, and a methacrylic group is even more preferred. Examples of the divalent linking group represented by L include -CO- and -NR d Examples of the -NR include -, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, divalent aromatic hydrocarbon ring groups, and divalent linking groups formed by combining a plurality of these. The above-mentioned alkylene groups, cycloalkylene groups, alkenylene groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, and divalent aromatic hydrocarbon ring groups may further have a substituent. The above-mentioned -NR d -R in d represents a hydrogen atom or an organic group, and the organic group is preferably an alkyl group (for example, having 1 to 6 carbon atoms).

[0057] The alkylene group may be linear or branched, and preferably has 1 to 6 carbon atoms. The cycloalkylene group preferably has 3 to 15 carbon atoms. The alkenylene group preferably has 2 to 6 carbon atoms. The divalent aliphatic heterocyclic group is preferably a ring having 5 to 10 ring atoms and containing a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. Examples of the divalent aliphatic heterocyclic group include groups represented by the following formula: In the formula, each Rg independently represents a hydrogen atom or a substituent (preferably, the substituent is a hydroxyl group), and * represents a bonding position.

[0058] [ka]

[0059] The divalent aromatic heterocyclic group is preferably a ring having 5 to 10 ring atoms and containing a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring atom. The divalent aromatic hydrocarbon ring group includes a ring having 6 to 10 ring atoms.

[0060] When the divalent linking group represented by L contains a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or a divalent aromatic hydrocarbon ring group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, or the divalent aromatic hydrocarbon ring group is preferably located at a position adjacent to Z shown in general formula (A1). In other words, the position adjacent to Z shown in general formula (A1) is preferably a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or a divalent aromatic hydrocarbon ring group.

[0061] The divalent linking group represented by L is, among others, -CO-, -NR d Preferred are -, -O-, -S-, -SO-, -SO2-, an alkylene group, a divalent aliphatic heterocyclic group, a divalent aromatic hydrocarbon ring group, and a divalent linking group formed by combining two or more of these. Examples of the "divalent linking group formed by combining a plurality of these" include -alkylene group-O-alkylene group-phenylene group-.

[0062] Z represents a cyclic structural moiety containing one or more rings selected from aromatic rings and aliphatic heterocycles. The aromatic ring and the aliphatic aromatic ring are as described above. The cyclic structural moiety is a (p+1) valent group constituted by a ring which may have a substituent. The ring may be a monocycle or a polycycle, and examples thereof include an aromatic ring, an aliphatic heterocycle, and a polycycle formed by an aromatic ring and an aliphatic heterocycle. The cyclic structural portion may have a substituent. The substituent referred to here refers to a substituent other than the group represented by YL- in general formula (A1) and R. The substituent is not particularly limited, and examples thereof include a hydroxyl group, a phenyl group, a cyano group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, and a carboxy group. These substituents may further have a substituent.

[0063] Specific examples of the ring constituting the cyclic structure moiety represented by Z include the rings exemplified in the upper part as specific examples of the aromatic ring and the aliphatic aromatic ring, as well as the rings shown below. Note that the rings exemplified in the upper part as specific examples of the aromatic ring and the aliphatic aromatic ring, and the rings shown below, form the cyclic structure moiety represented by Z by removing p+1 hydrogen atoms possessed by the ring member atoms. That is, for example, in the case of formula (AT1-2) described later, Rg, Rg 1 and Rg 1 At least p+1 of these represent hydrogen atoms, and by removing these hydrogen atoms, a cyclic structural moiety represented by Z is formed. In the case of formula (AT1-1) described later, the hydrogen atoms that can be bonded to carbon atoms of the two benzene rings specified in the formula (in the formula, when n3 is not 4, the benzene ring has a hydrogen atom) and Rg 1 and Rg 2 (In other words, Rg 1 and Rg 2 p+1 hydrogen atoms are removed from the hydrogen atoms in the formula (wherein n3 is not 4, the benzene ring has a hydrogen atom) to form a cyclic structure moiety represented by Z. In the case of formula (AT1-3) described later, p+1 hydrogen atoms are removed from the hydrogen atoms in the formula (wherein n3 is not 4, the benzene ring has a hydrogen atom) to form a cyclic structure moiety represented by Z. 1 , and Rg 2 (In other words, Rg, Rg 1 , and Rg 2 A ring structure portion represented by Z is formed by removing p+1 hydrogen atoms from the ring (representing hydrogen atoms among the rings). Specific examples of the ring constituting the cyclic structure moiety represented by Z are not limited to these.

[0064] Monocyclic or polycyclic 5- to 7-membered lactone rings; for example, those represented by the following formulae (LC1-1) to (LC1-21). Examples of the substituent (Rb2) include a hydroxyl group, a phenyl group, a cyano group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, and a carboxy group. n2 represents, for example, an integer of 0 to 4 (preferably an integer of 0 to 2). When n2 is 2, multiple Rb2s may be different from each other, or multiple Rb2s may be bonded to each other to form a ring. Furthermore, one or more (for example, 1 to 2) methylene groups not adjacent to -COO- or -O- among the ring-member atoms of the lactone ring below may be replaced with a heteroatom such as -O- or -S-.

[0065] [ka]

[0066] A monocyclic or polycyclic 5- to 7-membered sultone ring, for example, those represented by the following formulae (SL1-1) to (SL1-3): The substituents (Rb2) and n2 can be explained in the same way as the substituents (Rb2) and n2 in the lactone structure. Furthermore, one or more (for example, 1 to 2) methylene groups that are not adjacent to —COO— or —O— among the ring member atoms of the sultone ring may be replaced with a heteroatom such as —O— or —S—.

[0067] [ka]

[0068] Other examples: Examples other than the lactone ring and sultone ring mentioned above include the following formulae (AT1-1) to (AT1-3). Rf represents a substituent, and examples thereof include the same as the substituent (Rb2) in the lactone structure. n3 represents, for example, an integer of 0 to 4 (preferably an integer of 0 to 2). When n3 is 2 or greater, multiple Rfs may be different from each other, or multiple Rfs may be bonded to each other to form a ring. Rg, Rg 1 , and Rg 2 Rg and Rg each independently represent a hydrogen atom or a substituent. 1 , and Rg 2 Examples of the substituent represented by the formula: include the same as the substituent (Rb2) in the lactone structure. In the following formulas (AT1-1) to (AT1-3), Rg 1 It is preferable that one or more (preferably two or more) of Rg represents a hydrogen atom, and that a bond with R in general formula (A1) is formed by removing this hydrogen atom. 2 represents a hydrogen atom, and removal of this hydrogen atom preferably forms a bond with the group represented by YL- in general formula (A1). The ring represented by the following general formula (AT1-1) has a 9,10-dihydroanthracene skeleton.

[0069] [ka]

[0070] R represents an acid-decomposable group. Examples of the acid-decomposable group represented by R include the acid-decomposable groups described above, and preferred embodiments are also the same.

[0071] p represents an integer of 1 or greater. p is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2, in that the effects of the present invention are more excellent.

[0072] Specific examples (Group A and Group B) of the specific monomer A are shown below, but the specific monomer A is not limited thereto. All of the compounds belonging to (Group A) of the specific monomer A shown below correspond to compounds having 9,10-dihydroanthracene as a basic skeleton. (Group A)

[0073] [ka] JPEG0007821782000010.jpg43135

[0074] [ka]

[0075] (Group B)

[0076] [ka]

[0077] [ka]

[0078] [ka] JPEG0007821782000015.jpg5055

[0079] <<Repeating unit of specific acid-decomposable resin A>> <Repeating unit derived from specific monomer A (acid-decomposable repeating unit)> The specific acid-decomposable resin A contains a repeating unit derived from the specific monomer A as the acid-decomposable repeating unit. The repeating unit derived from the specific monomer A may be used alone or in combination of two or more kinds. The lower limit of the content of the repeating units derived from the specific monomer A is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total repeating units of the specific acid-decomposable resin A. The upper limit is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0080] <Other Acid-Decomposable Repeating Units> The specific acid-decomposable resin A may contain, as the acid-decomposable repeating unit, an acid-decomposable repeating unit other than the repeating unit derived from the specific monomer A. Examples of the other acid-decomposable repeating unit include the repeating unit derived from the above-mentioned (meth)acrylic compound having an acid-decomposable group.

[0081] <Repeating Unit Having an Acid Group> The specific acid-decomposable resin A may have a repeating unit having an acid group. The repeating unit having an acid group is preferably a repeating unit different from the repeating units described above. The acid group is preferably an acid group having a pKa of not more than 13. The acid dissociation constant of the acid group is preferably not more than 13, more preferably 3 to 13, and even more preferably 5 to 10, as described above. When the specific acid-decomposable resin A has an acid group with a pKa of 13 or less, the content of the acid group in the specific acid-decomposable resin A is not particularly limited, but is often 0.2 to 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. When the acid group content is within the above range, development proceeds well, and the formed pattern shape is excellent, and resolution is also excellent. The acid group is preferably, for example, a carboxyl group, a hydroxyl group, an aromatic hydroxyl group (phenolic hydroxyl group), a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In addition, one or more (preferably one to two) fluorine atoms of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The -C(CF3)(OH)-CF2- thus formed is also preferred as an acid group. In addition, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0082] The repeating unit having an acid group is preferably a repeating unit represented by formula (B).

[0083] [ka]

[0084] R3 represents a hydrogen atom or an organic group which may have a fluorine atom or an iodine atom. The organic group which may have a fluorine atom or an iodine atom is preferably a group represented by -L4-R8. L4 represents a single bond or an ester group. R8 may be 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 formed by combining these.

[0085] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0086] L2 represents a single bond, an ester group, or a divalent group formed by combining -CO-, -O-, and an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched, and in which -CH2- may be substituted with a halogen atom). L3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include a cycloalkyl ring group, a norbornene ring group, and an adamantane ring group.

[0087] R6 represents a hydroxyl group or a fluorinated alcohol group. The fluorinated alcohol group is preferably a group represented by the following formula (3L). *-L 6X -R 6X (3L) L 6X represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, and -NR A -, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), and divalent linking groups formed by combining a plurality of these groups. A Examples of R include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkylene group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom) and a hydroxyl group. 6X represents a hexafluoroisopropanol group. When R6 is a hydroxyl group, L3 is also preferably an (n+m+1)-valent aromatic hydrocarbon ring group.

[0088] R7 represents a halogen atom. m represents an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably an integer of 1 or 2. n represents an integer of 0 or greater than 1. n is preferably an integer of 1 to 4. It is preferable that (n+m+1) is an integer of 1 to 5.

[0089] The repeating unit having an acid group is also preferably a repeating unit represented by formula (A2). The repeating unit represented by formula (A2) is a repeating unit having an aromatic hydroxyl group as the acid group.

[0090] [ka]

[0091] In general formula (A2), R 101 , R 102 , and R 103 each independently represents a hydrogen atom, an alkyl group (which may be linear or branched, for example, having 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic, for example, having 3 to 15 ring atoms), a halogen atom, a cyano group, or an alkoxycarbonyl group (which may be linear or branched, for example).

[0092] In general formula (A2), L A represents a single bond or a divalent linking group. L in general formula (A2) A Examples of the divalent linking group represented by the formula (I) include -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably a ring having 5 to 10 ring atoms and containing at least one nitrogen atom, oxygen atom, sulfur atom, or selenium atom as a ring atom), divalent aromatic heterocyclic groups (preferably a ring having 5 to 10 ring atoms and containing at least one nitrogen atom, oxygen atom, sulfur atom, or selenium atom as a ring atom), divalent aromatic hydrocarbon ring groups (preferably a ring having 6 to 10 ring atoms), and divalent linking groups formed by combining two or more of these. R in the -NR- represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group (for example, having 1 to 6 carbon atoms).

[0093] Ar A represents an aromatic ring group (such as a benzene ring group). The aromatic ring group may be monocyclic or polycyclic, and may or may not have one or more (for example, 1 to 3) heteroatoms as ring member atoms. The number of ring member atoms in the aromatic ring group is preferably 5 to 15.

[0094] In the general formula (A2), k represents an integer of 1 to 5.

[0095] However, R 102 Ar A may be combined with R 102 represents a single bond or an alkylene group (which may be linear or branched and has, for example, 1 to 6 carbon atoms). In this case, Ar A The aromatic ring group represented by the formula (I) is a group in which the carbon atom (R 101 It bonds to the carbon atom to which it is bonded.

[0096] Examples of repeating units having an acid group are shown below.

[0097] [ka]

[0098] In the following examples, a represents 1 or 2 in the formula.

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] Among the above repeating units, the repeating units specifically described below are preferred: In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] The repeating unit having an acid group may be used alone or in combination of two or more. The content of the repeating unit having an acid group is preferably 5 to 80 mass %, more preferably 5 to 60 mass %, still more preferably 10 to 50 mass %, and particularly preferably 15 to 50 mass %, based on all repeating units of the specific acid-decomposable resin A.

[0108] <Repeating Unit Having a Lactone Group> The specific acid-decomposable resin A also preferably has a repeating unit having a lactone group. The repeating unit having a lactone group is preferably a repeating unit different from the repeating units described above. Furthermore, the repeating unit having a lactone group may also serve as the repeating unit described above (for example, a repeating unit having an acid-decomposable group).

[0109] The lactone group may have a lactone structure. The lactone structure is preferably a 5- to 7-membered ring lactone structure. Among these, a 5- to 7-membered ring lactone structure to which another ring structure is condensed to form a bicyclo structure or a spiro structure is more preferred. The specific acid-decomposable resin A preferably has a repeating unit having a lactone group formed by abstracting one or more (for example, one or two) hydrogen atoms from a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-21). Furthermore, the lactone group may be directly bonded to the main chain. For example, the ring atoms of the lactone group may constitute the main chain of the specific acid-decomposable resin A.

[0110] [ka]

[0111] The lactone structure may have a substituent (Rb2). Examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, a group containing an acid-decomposable group (which may be the acid-decomposable group itself), and groups formed by a combination thereof. n2 represents an integer of 0 to 4. When n2 is 2 or greater, multiple Rb2s may be different from each other, or multiple Rb2s may be bonded to form a ring. Among the ring atoms of the lactone structure, one or more (for example, 1 to 2) methylene groups that are not adjacent to -COO- or -O- may be replaced with a heteroatom such as -O- or -S-.

[0112] Examples of repeating units having a lactone group include repeating units represented by the following general formula (AI).

[0113] [ka]

[0114] In general formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among these, a single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring atom of a lactone structure represented by any one of formulae (LC1-1) to (LC1-21).

[0115] The repeating unit having a lactone group may be, for example, a repeating unit represented by general formula (AII) or (AIII).

[0116] [ka]

[0117] In formulae (AII) and (AIII), each RIII independently represents a hydrogen atom or a substituent. RIII is preferably a hydrogen atom. In general formula (AII), ahd1 represents a group obtained by removing one hydrogen atom from each of adjacent ring atoms in a lactone structure represented by any one of formulae (LC1-1) to (LC1-21). In general formula (AIII), ahd2 represents a group obtained by removing two hydrogen atoms from one of the ring atoms of the lactone structure represented by any one of formulae (LC1-1) to (LC1-21).

[0118] Examples of repeating units having a lactone group are shown below.

[0119] [ka]

[0120] [ka]

[0121] When optical isomers exist in the repeating unit having a lactone group, any optical isomer may be used. In addition, one optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0122] The repeating unit having a lactone group may be used alone or in combination of two or more. The content of the repeating unit having a lactone group is preferably 1 to 50 mass %, more preferably 3 to 40 mass %, still more preferably 5 to 30 mass %, and particularly preferably 5 to 20 mass %, based on all repeating units in the specific acid-decomposable resin A.

[0123] The specific acid-decomposable resin A may also contain other repeating units. Examples of such repeating units include those listed in paragraphs

[0074] to

[0079] ,

[0090] to

[0100] , and

[0103] to

[0133] of International Publication No. 2018 / 193954, those listed in paragraphs

[0152] to

[0173] of International Publication No. 2020 / 004306, and those listed in paragraphs

[0042] to

[0059] of International Publication No. 2019 / 167481.

[0124] In addition to the repeating structural units described above, the specific acid-decomposable resin A 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.

[0125] The specific acid-decomposable resin A can be synthesized according to a conventional method (for example, radical polymerization). The weight-average molecular weight of the specific acid-decomposable resin A, as measured by the GPC method in terms of polystyrene, is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By adjusting the weight-average molecular weight of the specific acid-decomposable resin A to fall within the above ranges, deterioration in heat resistance and dry etching resistance can be further suppressed. In addition, deterioration in developability and deterioration in film-formability due to increased viscosity can be further suppressed. The dispersity (molecular weight distribution) of the specific acid-decomposable resin A is typically 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and further the smoother the sidewalls of the resist pattern and the better the roughness.

[0126] The specific acid-decomposable resin A may be used alone or in combination of two or more. In the resist composition of the first embodiment, the content of the specific acid-decomposable resin A is preferably 10 to 99.9 mass %, more preferably 60 to 99.5 mass %, even more preferably 70 to 99 mass %, and particularly preferably 80 to 99 mass %, relative to the total solid content of the composition. The term "solids" refers to components that form the resist film and does not include solvents. In addition, components that form the resist film are considered to be solids even if they are in liquid form.

[0127] [Photoacid generator] The resist composition of the first embodiment contains a photoacid generator. A photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation.

[0128] The photoacid generator is preferably a low molecular weight compound, and its molecular weight is preferably not more than 3000, more preferably not more than 2000, and even more preferably not more than 1000. The lower limit of the molecular weight is, for example, 100 or more. The photoacid generator is not particularly limited, but is preferably a compound that generates an organic acid when irradiated with actinic rays or radiation (preferably electron beams or extreme ultraviolet rays) or when heated. The organic acid is preferably, for example, at least one of sulfonic acid, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide.

[0129] The photoacid generator may be an ionic compound or a nonionic compound.

[0130] <Photoacid generators, which are ionic compounds> The photoacid generator that is an ionic compound may be a photoacid generator that is an onium salt, or may be a photoacid generator that is an inner salt (betaine compound).

[0131] (Photoacid generators that are onium salts) Photoacid generators that are onium salts typically have a cationic moiety and an anionic moiety. The onium salt photoacid generator is, for example, p+ m X q- n " is an example of a compound represented by the formula: "M p+ m X q- n In the formula, p, q, m, and n each independently represent an integer of 1 or more (preferably 1 to 8). M p+ represents an organic cation having a charge of p. The organic cation may contain a cationic moiety as a part thereof, or may be the cationic moiety itself. Preferably, the organic cation is the cationic moiety itself. X q- represents an organic anion having a charge of q. The organic anion may contain an anionic moiety as a part thereof, or may be the anionic moiety itself. The organic anion preferably contains an anionic moiety as a part thereof. M when there are multiple p+ and X q- may be the same or different. There can be multiple M p+ The average value of p in q- is the same as the average value of q multiplied by n. Among these, p is preferably 1. For example, it is preferable that p, q, m, and n are all 1. In addition, it is also preferable that p is 1, q is 2 to 8, m is the same as q, and n is 1.

[0132] Organic cations The cationic moiety is a structural moiety containing a positively charged atom or atomic group, and is preferably, for example, a monovalent organic cation. The organic cations are preferably each independently an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)).

[0133] [ka]

[0134] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group represented by R is usually 1 to 30, and preferably 1 to 20. 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0135] Suitable embodiments of the organic cation in formula (ZaI) include the cation (ZaI-1), the organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0136] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 one of which is an aryl group, and R 201 ~R 203 The remaining two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. R 201 ~R 203 Examples of groups formed by combining two of these groups include alkylene group AL, -aromatic ring group-alkylene group AL-aromatic ring group-, -aromatic ring group-aromatic ring group-, and -aromatic ring group-O-aromatic ring group-. The alkylene group AL is a linear or branched alkylene group. One or more methylene groups constituting the alkylene group AL may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group. Examples of alkylene group AL include a butylene group, a pentylene group, and -CH2-CH2-O-CH2-CH2-. Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations. Two of the aryl groups in the triarylsulfonium cation, diarylalkylsulfonium cation, and diarylcycloalkylsulfonium cation may be bonded via a single bond or a divalent linking group (such as -O-, -S-, an alkylene group, or a group formed by a combination thereof).

[0137] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0138] R 201 ~R 203The substituents which the aryl group, alkyl group and cycloalkyl group may have are each independently preferably an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylsulfonyl group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxyl group, a carboxyl group, a group having an ester group, a group having a sulfinyl group, a group having a sulfonyl group, an alkylthio group, a phenylthio group, and the like. The above-mentioned substituent may further have a substituent if possible. For example, it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents are combined in any desired manner to form an acid-decomposable group. The acid-decomposable group is intended to be a group that decomposes under the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected with a leaving group that is released under the action of an acid. The polar group and leaving group are as described above.

[0139] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0140] [ka]

[0141] In the formula (ZaI-3b), R 1c ~R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R7c each independently represents a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. Also, R 1c ~R 7c , and R x and R y It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0142] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0143] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R5c 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.

[0144] R 1c ~R 5c , R 6c , R 7c , R x , R y , and R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The ring formed by bonding together may have a substituent.

[0145] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0146] [ka]

[0147] In the formula (ZaI-4b), l represents an integer of 0 to 2. r represents an integer of 0 to 8. R 13 represents a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14represents a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 When a plurality of groups are present, each independently represents the above group such as a hydroxyl group. R 15 Each of R independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 may be bonded to each other to form a ring. 15 When they 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. In one embodiment, two R 15 are preferably alkylene groups and bonded to each other to form a ring structure. 15 The ring formed by bonding together may have a substituent.

[0148] In formula (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. Also, R 13 ~R 15 , and R x and R y It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0149] Next, formula (ZaII) will be explained. In formula (ZaII), R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0150] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 and R 205 Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0151] Organic anions Examples of organic anions include phenolic hydroxyl anions, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, formate anions, hydrogen carbonate anions, etc.), carbonylsulfonylimide anions, bis(sulfonyl)imide anions (bis(alkylsulfonyl)imide anions, etc.), bis(carbonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0152] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom; it may also be a perfluoroalkyl group). The cycloalkyl group may be monocyclic or polycyclic, and one or more (preferably one to two) -CH2- groups constituting the ring structure may be replaced with a heteroatom (such as -O- or -S-), -SO2-, -SO3-, an ester group, or a carbonyl group.

[0153] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0154] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but specific examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0155] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0156] An example of the sulfonylimide anion is a saccharin anion.

[0157] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure.

[0158] Preferred organic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom (such as an aliphatic sulfonate anion in which one or two fluorine atoms are substituted at the α-position), aliphatic sulfonate anions in which the α-position of the sulfonic acid is not substituted with a fluorine atom (such as an aliphatic sulfonate anion in which no fluorine atom is substituted at the α-position and 0 to 3 fluorine atoms or perfluoroalkyl groups are substituted at the β-position), aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom.

[0159] Furthermore, the organic anion is preferably an anion represented by the following formula (AN):

[0160] [ka]

[0161] In formula (AN), o represents an integer of 0 to 5. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0162] In formula (AN), AX is -SO3 - or -COO - Represents.

[0163] In formula (AN), Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and particularly preferably both Xf are fluorine atoms.

[0164] In formula (AN), R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R4 and R5 are present, R4 and R5 may be the same or different. The alkyl group represented by R4 and R5 may have a substituent other than a fluorine atom, and preferably has 1 to 4 carbon atoms. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf. R4 and R5 are preferably hydrogen atoms. It is also preferred that one of R4 and R5 bonded to the same carbon atom is a hydrogen atom, and the other is a fluorine atom or an alkyl group substituted with at least one fluorine atom. In particular, it is also preferred that in the -C(R4)(R5)- located first and / or second closest to AX, one of R4 and R5 bonded to the same carbon atom is a hydrogen atom, and the other is a fluorine atom or an alkyl group substituted with at least one fluorine atom. It is also preferred that in the -C(R4)(R5)- located first and / or second closest to AX, R4 and R5 are each independently a hydrogen atom or an alkyl group (which may have a substituent other than a fluorine atom).

[0165] In formula (AN), L represents a divalent linking group, and when a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -alkylene group-O-CO-O-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, and -NHCO-alkylene group- are preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -alkylene group-O-CO-O-, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, and -OCO-alkylene group- are more preferred.

[0166] In formula (AN), W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0167] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

[0168] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0169] The anion represented by formula (AN) is preferably AX-CF2-CH2-OCO-(L)q'-W, AX-CF2-CHF-CH2-OCO-(L)q'-W, AX-CF2-COO-(L)q'-W, AX-CF2-CF2-CH2-CH2-(L)qW, or AX-CF2-CH(CF3)-OCO-(L)q'-W. Here, AX, L, q, and W are the same as in formula (AN). q' represents an integer of 0 to 10.

[0170] (Photoacid generator that is an inner salt) The photoacid generator that is an inner salt preferably has a sulfonate anion or a carboxylate anion (preferably an aromatic sulfonic acid or aromatic carboxylate anion), and further preferably has a sulfonium cation or an iodine cation. Examples of photoacid generators that are inner salts include compound (ZbI) and compound (ZbII). The compound (ZbI) can be prepared by the general formula (ZaI) where R 201 ~R 203 One of them is -SO3 - or -COO - The compound is represented by a newly defined general formula, which defines that the compound is an aryl group having a group containing the following as a substituent: The compound (ZbII) is a compound represented by the general formula (ZaII) above, wherein R 204 and R 205 One of them is -SO3 - or -COO - The compound is represented by a newly defined general formula, which defines that the compound is an aryl group having a group containing the following as a substituent: In the above compound (ZbI) and the above compound (ZbII), -SO3 - or -COO - The group containing the formula (Xf) is, for example, a group obtained by removing W from the organic anion represented by formula (AN) described in the explanation of the organic anion ("AX-[C(Xf)(Xf)] o -〔C(R4)(R5)〕 p -(L) q -").

[0171] Examples of photoacid generators that are inner salts are given below. In the photoacid generators below, the numerical values ​​shown near the sites where the hydrogen atoms of the acid groups are substituted with cations (anionic functional groups) indicate the pKa values ​​of the acid groups when the hydrogen atoms are not substituted with cations. In other words, the pKa values ​​shown below are the pKa values ​​of the acid group (the group formed by bonding an anionic functional group to a hydrogen atom) in the compound (acid) assumed to be formed by bonding an anionic functional group of the intramolecular salt to a hydrogen atom.

[0172] [ka]

[0173] Regarding photoacid generators, paragraphs

[0368] to

[0377] of JP 2014-41328 A and paragraphs

[0240] to

[0262] of JP 2013-228681 A (corresponding paragraph

[0339] of the specification of U.S. Patent Application Publication No. 2015 / 004533) can be cited, the contents of which are incorporated herein by reference.

[0174] Furthermore, the following compounds can also be used as photoacid generators.

[0175] [ka]

[0176] The photoacid generator may be used alone or in combination of two or more. In the resist composition of the first embodiment, the content of the photoacid generator is preferably from 0.5 to 40 mass %, more preferably from 0.5 to 30 mass %, and even more preferably from 1 to 30 mass %, relative to the total solid content of the resist composition.

[0177] [Hydrophobic resin] The resist composition of the first embodiment may contain, in addition to the specific acid-decomposable resin A, a hydrophobic resin different from the specific acid-decomposable resin A. The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include control of the static and dynamic contact angle of the resist film surface with water, and suppression of outgassing.

[0178] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more of "fluorine atoms," "silicon atoms," and "CH3 partial structures contained in the side chain portion of the resin," and more preferably has two or more of them. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0179] When the resist composition of the first embodiment contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, even more preferably 0.1 to 10 mass%, and particularly preferably 0.1 to 5.0 mass%, relative to the total solid content of the resist composition.

[0180] [Surfactant] The resist composition of the first embodiment may contain a surfactant. When a surfactant is contained, a pattern with superior adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. As the fluorine-based and / or silicone-based surfactant, for example, the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 19395 can be used. When the resist composition of the first embodiment contains a surfactant, the content thereof is preferably from 0.0001 to 2 mass %, and more preferably from 0.0005 to 1 mass %, relative to the total solid content of the composition. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0181] 〔solvent〕 The resist composition of the first embodiment may contain a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0182] The present inventors have found that the use of such a solvent in combination with the above-mentioned resin improves the coatability of the composition and enables the formation of a pattern with fewer development defects. Although the reason for this is not entirely clear, the present inventors believe that this is due to the fact that these solvents have a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, making it possible to suppress unevenness in the film thickness of the composition and the occurrence of precipitates during spin coating. Details of the component (M1) and the component (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306.

[0183] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % relative to the total amount of the solvent.

[0184] The solvent may be used alone or in combination of two or more. The content of the solvent in the resist composition of the first embodiment is preferably set so that the solids concentration is 30% by mass or less, more preferably 10% by mass or less, and even more preferably 2% by mass or less. The lower limit is preferably set so that it is 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. This further improves the coatability of the resist composition. In other words, the content of the solvent in the resist composition of the first embodiment is preferably from 70 to 99.95 mass %, more preferably from 90 to 99.9 mass %, and even more preferably from 98 to 99.5 mass %, relative to the total mass of the resist composition.

[0185] [Other additives] The resist composition of the first embodiment may further contain an acid diffusion controller, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (an alicyclic or aliphatic compound containing a carboxylic acid group).

[0186] The resist composition of the first embodiment may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes under the action of an acid and thereby reduces its solubility in an organic developer.

[0187] The resist composition of the first embodiment can also be suitably used as a photosensitive composition for EUV exposure or a photosensitive composition for electron beam exposure.

[0188] EUV light and electron beams are significantly affected by "photon shot noise," which is the stochastic variation in the number of photons, and are prone to causing deterioration of LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose and the number of incident photons, but this tends to be a trade-off with the demand for higher sensitivity. When the value A calculated by the following formula (1) is high, the resist film formed from the resist composition has a high absorption efficiency of EUV and electron beams, which is effective in reducing photon shot noise. The value A represents the absorption efficiency of EUV and electron beams by mass of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) The value A is preferably 0.120 or more. Although there is no particular upper limit, if the value A is too large, the EUV and electron beam transmittance of the resist film decreases, deteriorating the optical image profile in the resist film and, as a result, making it difficult to obtain a good pattern shape. Therefore, the value A is preferably 0.240 or less, and more preferably 0.220 or less.

[0189] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of 0 to 10 atoms in the actinic ray-sensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from all solids to all atoms in all solids, [F] represents the molar ratio of fluorine atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition. For example, when a resist composition contains a specific acid-decomposable resin A, a photoacid generator, and a solvent, the specific acid-decomposable resin A and the photoacid generator correspond to the solid content. In other words, the total atoms of the total solid content corresponds to the sum of all atoms derived from the specific acid-decomposable resin A and all atoms derived from the photoacid generator. For example, [H] represents the molar ratio of hydrogen atoms derived from all solid content to all atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from the resin and the photoacid generator to the sum of all atoms derived from the specific acid-decomposable resin A and all atoms derived from the photoacid generator.

[0190] The A value can be calculated by calculating the atomic ratio of the components contained in the resist composition when the structure and content of all solid components in the resist composition are known. Even when the components are unknown, the atomic ratio of the components can be calculated by analytical techniques such as elemental analysis of the resist film obtained by evaporating the solvent component of the resist composition.

[0191] [Resist film and pattern forming method] The procedure for the pattern formation method using the resist composition of the first embodiment is not particularly limited, but it is preferable that the method include the following steps. Step 1: Forming a resist film on a substrate using the resist composition of the first embodiment Step 2: Step of exposing the resist film Step 3: Developing the exposed resist film using a developer The procedure for each of the above steps will be described in detail below.

[0192] <Step 1: Resist film formation step> Step 1 is a step of forming a resist film on a substrate using the resist composition of the first embodiment. The resist composition of the first embodiment is defined as above.

[0193] An example of a method for forming a resist film on a substrate using the resist composition of the first embodiment is a method in which the resist composition of the first embodiment is applied onto a substrate. Before application, the resist composition of the first embodiment is preferably filtered as needed. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0194] The resist composition of the first embodiment can be applied to a substrate (e.g., silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit elements by a suitable application method using a spinner or coater. The application method is preferably spin coating using a spinner. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After coating the resist composition of the first embodiment, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic films, organic films, anti-reflective films) may be formed below the resist film.

[0195] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, or may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0196] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm in order to form a finer pattern with higher precision. In particular, when EUV exposure or electron beam exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.

[0197] A top coat may be formed on the resist film using a top coat composition. The top coat composition preferably does not mix with the resist film and can be uniformly applied to the upper layer of the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound such as that described in JP-A-2013-61648 on the resist film. The top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0198] <Step 2: Exposure step> Step 2 is a step of exposing the resist film. The exposure method may be a method in which the formed resist film is irradiated 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, preferably far ultraviolet light having 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), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams. Of these, the actinic rays or radiation used for exposure are preferably EUV or electron beams.

[0199] After exposure, it is preferable to bake (heat) the film before development, as this promotes the reaction of the exposed areas and improves the sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably from 10 to 1000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like. This process is also called post-exposure bake (PEB).

[0200] <Process 3: Development process> Step 3 is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0201] Examples of development methods include a method in which a substrate is immersed in a tank filled with developer for a certain period of time (dip method), a method in which developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which developer is sprayed onto the surface of the substrate (spray method), and a method in which developer is continuously dispensed by scanning a developer dispensing nozzle at a constant speed onto a substrate that is rotating at a constant speed (dynamic dispense method). After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C.

[0202] 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 quaternary ammonium salts such as tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. 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 typically 0.1 to 20% by mass. The pH of the alkaline developer is typically 10.0 to 15.0. The water content of the alkaline developer is preferably 51 to 99.95% by mass.

[0203] 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.

[0204] The developer may contain a mixture of two or more of the above solvents, or may contain water or a solvent other than the above solvents. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably substantially no water. The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total amount of the developer.

[0205] <Other processes> The pattern formation method preferably includes, after step 3, a step of washing with a rinse liquid.

[0206] The rinse liquid used in the rinse step after the development step using an alkaline developer is, for example, pure water, to which an appropriate amount of surfactant may be added. A suitable amount of a surfactant may be added to the rinse solution.

[0207] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0208] The method for the rinsing step is not particularly limited, and examples thereof include a method in which a rinsing 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 a rinsing liquid for a certain period of time (dip method), and a method in which a rinsing liquid is sprayed onto the surface of the substrate (spray method). Furthermore, the pattern formation method using the resist composition of the first embodiment may include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0209] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlying film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. Although the method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, a preferred method is to form 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. The dry etching is preferably oxygen plasma etching.

[0210] The resist composition of the first embodiment and the various materials used in the pattern formation method using the resist composition of the first embodiment (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. 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.

[0211] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0212] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0213] In addition to filtration, impurities may be removed using an adsorbent, or a combination of 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 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.

[0214] A conductive compound may be added to an organic processing liquid such as a rinse liquid to prevent breakdown of chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing properties, it is preferably 10% by mass or less, and more preferably 5% by mass or less. For example, SUS (stainless steel), or various pipes coated with antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the chemical liquid piping. Similarly, antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the filter and O-ring.

[0215] [Second embodiment of actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as the "resist composition of the second embodiment") contains a resin (hereinafter also referred to as the "specific acid-decomposable resin B") having a repeating unit derived from a polymerizable compound represented by general formula (1) described below (hereinafter also referred to as the "specific monomer B"), and a photoacid generator.

[0216] The mechanism of action of the resist composition of the second embodiment is not clear, but the inventors of the present invention speculate as follows. The specific acid-decomposable resin B contained in the resist composition of the second embodiment has a repeating unit derived from the specific monomer B. The specific monomer B has a predetermined polycyclic structure, which results in a high glass transition temperature. Therefore, the resist composition of the second embodiment containing the specific acid-decomposable resin B can form a pattern with high film strength. As a result, it is believed that the resist composition of the second embodiment has high resolution (in other words, a small limiting resolution (nm)). Furthermore, because the specific monomer B has an acid-decomposable group at a predetermined position, a pattern formed using the resist composition of the second embodiment containing the specific acid-decomposable resin B can exhibit excellent dissolution contrast. As a result, it is believed that the pattern formed using the resist composition of the second embodiment has excellent LWR performance. In other words, it is presumed that due to the structure of the specific monomer B, the resist composition of the second embodiment has excellent high resolution, and the formed pattern has excellent LWR performance. Hereinafter, a resist composition that has higher resolution and / or a pattern formed using the resist composition that has better LWR performance may also be referred to as "the effects of the present invention being better."

[0217] The resist composition of the second embodiment will be described in detail below. The resist composition of the second embodiment may be a positive resist composition or a negative resist composition, and may also be a resist composition for alkaline development or a resist composition for organic solvent development. The resist composition of the second embodiment is typically a chemically amplified resist composition. The resist composition of the second embodiment has the same configuration as the resist composition of the first embodiment except that specific acid-decomposable resin B is used instead of specific acid-decomposable resin A, and the preferred aspects are also the same. Furthermore, the method for forming a resist film and a pattern using the resist composition of the second embodiment has the same configuration as the method for forming a resist film and a pattern using the resist composition of the first embodiment, except for using the resist composition of the second embodiment instead of the resist composition of the first embodiment, and the preferred aspects are also the same.

[0218] [Specified acid-decomposable resin B] The resist composition of the second embodiment contains a resin (specific acid-decomposable resin B) that has a repeating unit derived from a polymerizable compound (specific monomer B) represented by the following general formula (1). The specific acid-decomposable resin B is a resin that decomposes under the action of an acid and has an increased polarity. That is, in the pattern formation method using the resist composition of the second embodiment, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed. The specific monomer B will be described below. The specific acid-decomposable resin B has the same configuration as the specific acid-decomposable resin A except that it contains a repeating unit derived from the specific monomer B instead of the repeating unit derived from the specific monomer A, and the preferred embodiments are also the same. Therefore, in the following description, only the specific monomer B will be described.

[0219] The specific monomer B will be described below. The specific monomer B is a polymerizable compound represented by the following general formula (1).

[0220] [ka]

[0221] In the formula, L 1 -CR3 =CR 4 -or-CR 5 R 6 -CR 7 R 8 - represents. X 1 -O-, -CR 9 R 10 - or =CR 11 - represents. X 2 are -O-, -CO-, and -CR. 12 R 13 - or =CR 14 - represents. X 1 and X 2 The bond shown by a solid line and a dotted line represents a single bond or a double bond. 1 and X 2 If the bond with represents a double bond, X 1 is =CR 11 - represents X 2 is =CR 14 -. Also, X 1 and X 2 If the bond with represents a single bond, X 1 is -O- or -CR 9 R 10 - represents X 2 is -O-, -CO-, or -CR 12 R 13 - represents. R 1 ~R 14 Each independently represents a hydrogen atom or a substituent. 3 and R 4 may be bonded to each other to form a ring. 5 and R 6 Either one of the two and R 7 and R 8 and X may be bonded to each other to form a ring. 1 GA=CR 11 - represents X 2 GA=CR 14 -, R 11 and R 14 and may be bonded to each other to form a ring. 1 Ga-CR 9R 10 - represents X 2 Ga-CR 12 R 13 -, R 9 and R 10 Either one of the two and R 12 and R 13 may be bonded to each other to form a ring. R X1 ~R X4 each independently represents a hydrogen atom or a substituent. X1 ~R X4 At least one of R represents an acid-decomposable group. X1 and R X2 Either one of the two and R X3 and R X4 may be bonded to each other to form a ring. However, the polymerizable compound represented by the above general formula (1) contains a monovalent substituent represented by the following general formula (2) in the molecule.

[0222] [ka]

[0223] In the formula, L 2 represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents the bonding position.

[0224] In formula (1), R 1 ~R 14 The substituent represented by the formula (1) is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cycloalkyl group, an aromatic ring group, and a monovalent substituent represented by the general formula (2) above.

[0225] The alkyl group may be linear or branched, and preferably has a carbon number of 1 to 5. 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. Examples of the alkyl group moiety in the alkoxy group and the alkoxycarbonyl group include the same groups as the alkyl group described above. The cycloalkyl group preferably has 3 to 15 ring atoms. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have, for example, one or more (e.g., 1 to 3) methylene groups constituting the ring replaced with a heteroatom (e.g., -O- or -S-), -SO2-, -SO3-, an ester group, a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more (e.g., 1 to 2) ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The cycloalkyl group may be condensed with an aromatic ring (such as a benzene ring). The aromatic ring group may be monocyclic or polycyclic, and preferably has 5 to 15 ring atoms. The aromatic ring group may have one or more (e.g., 1 to 5) heteroatoms (e.g., oxygen atoms, sulfur atoms, nitrogen atoms, etc.) as ring atoms. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, an anthracene ring group, a thiazole ring group, and a benzothiazole ring group.

[0226] The alkyl group, alkoxy group, alkoxycarbonyl group, and alkenyl group may further have a substituent, for example, a halogen atom (such as a fluorine atom), a hydroxyl group, a nitro group, a cyano group, a cycloalkyl group, and an aromatic ring group. The cycloalkyl group and the aromatic ring group may further have a substituent, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkenyl group, an aromatic ring group (which may be monocyclic or polycyclic and, for example, having 5 to 15 ring atoms), and a cycloalkyl group (which may be monocyclic or polycyclic and, for example, having 3 to 15 ring atoms).

[0227] The ring (R 1 carbon atom to which R is attached 2 the carbon atom to which L is attached 1 , X 1 , and X 2 The ring consisting of is a six-membered ring. where L 1 Ga-CR 3 =CR 4 -, R 3 and R 4 and may be bonded to each other to form a ring. 1 GA=CR 11 - represents X 2 GA=CR 14 -, R 11 and R 14 and may be bonded to each other to form a ring. The ring formed here includes L 1 and X 1 and X 2 Preferably, the ring is an alicyclic ring containing an unsaturated bond corresponding to the bonding site, or an aromatic ring.

[0228] The aromatic ring may be monocyclic or polycyclic, and the number of ring atoms is preferably 5 to 20 (more preferably 6 to 10). The aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (such as oxygen atoms, sulfur atoms, and nitrogen atoms) as ring atoms. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a tolylene ring, an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring, and a benzene ring is preferred. The aromatic ring may further have a substituent. The substituent may be R 1 ~R 14 Examples of the substituents include those exemplified as the substituents represented by the following formula:

[0229] The alicyclic ring may be a monocyclic ring or a polycyclic ring, and the number of ring atoms is preferably 5 to 20 (preferably 6 to 10). The alicyclic ring may have one or more (for example, 1 to 5) heteroatoms (oxygen atoms, sulfur atoms, nitrogen atoms, etc.) as ring atoms. The alicyclic ring is 1 and X 1 and X 2 The alicyclic ring contains an unsaturated bond at a position corresponding to the bonding site of the alicyclic ring. The alicyclic ring may further contain an unsaturated bond. Furthermore, the alicyclic ring may have a carbon atom substituted with a carbonyl carbon atom. Examples of the alicyclic ring include cyclopentene, cyclohexene, cycloheptene, and cyclooctadiene. The alicyclic ring may further have a substituent. The substituent may be R 1 ~R 14 Examples of the substituents include those exemplified as the substituents represented by the following formula:

[0230] Also, L 1 Ga-CR 5 R 6 -CR 7 R 8 -, R 5 and R 6 Either one of the two and R 7 and R 8 and X may be bonded to each other to form a ring. 1 Ga-CR 9 R 10 - represents X 2 Ga-CR 12 R 13 -, R 9 and R 10 Either one of the two and R 12 and R 13 may be bonded to either one of the rings to form a ring. The ring formed here is preferably an alicyclic ring. The alicyclic ring may be a monocyclic ring or a polycyclic ring, and the number of ring atoms is preferably 5 to 20 (preferably 6 to 10). The alicyclic ring may have one or more (for example, 1 to 5) heteroatoms (oxygen atom, sulfur atom, nitrogen atom, etc.) as ring atoms. The alicyclic ring is formed by bonding the L in the ring 1 and X 1 and X2 The alicyclic ring may contain an unsaturated bond at a position other than the bonding site. In addition, the carbon atom in the ring may be substituted with a carbonyl carbon. Examples of the alicyclic ring include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. The alicyclic ring may further have a substituent. The substituent may be R 1 ~R 14 Examples of the substituents include those exemplified as the substituents represented by the following formula:

[0231] In general formula (1), R X1 ~R X4 Examples of the substituent represented by R include an acid-decomposable group and 1 ~R 14 Examples of the substituents include those exemplified as the substituents represented by the following formula: The acid-decomposable group has the same meaning as the acid-decomposable group described for the specific acid-decomposable resin A in the first embodiment, and preferred embodiments are also the same. The specific acid-decomposable resin B formed from the specific monomer B having an acid-decomposable group has a repeating unit (acid-decomposable repeating unit) having an acid-decomposable group. Due to the presence of this acid-decomposable repeating unit, the specific acid-decomposable resin B exhibits a property in which the polarity increases under the action of acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents.

[0232] R X1 ~R X4 At least one of R represents an acid-decomposable group. X1 ~R X4 Preferably, at least two of R represent an acid-decomposable group, and R X1 ~R X4 More preferably, two of R represent acid-decomposable groups, X1 and R X3 More preferably, represents an acid-decomposable group. Also, R X1 and R X2 Either one of the two and R X3 and R X4may be bonded to either one of the rings to form a ring. The ring formed here is preferably an alicyclic ring. The alicyclic ring may be a monocyclic ring or a polycyclic ring, and preferably has 5 to 20 (preferably 5 to 10) ring atoms. The alicyclic ring may have one or more (for example, 1 to 5) heteroatoms (oxygen atoms, sulfur atoms, nitrogen atoms, etc.) as ring atoms. The alicyclic ring may contain an unsaturated bond in the ring. Furthermore, the carbon atom in the alicyclic ring may be substituted with a carbonyl carbon. In addition, R X1 ~R X4 When two of the groups represent an acid-decomposable group, the other two preferably represent a hydrogen atom, since this will result in better effects of the present invention.

[0233] In general formula (2), L 2 represents a single bond or a divalent linking group. L 2 Examples of the divalent linking group represented by the formula: d Examples of the -NR include -, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, divalent aromatic hydrocarbon ring groups, and divalent linking groups formed by combining a plurality of these. The above-mentioned alkylene groups, cycloalkylene groups, alkenylene groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, and divalent aromatic hydrocarbon ring groups may further have a substituent. The above-mentioned -NR d -R in d represents a hydrogen atom or an organic group, and the organic group is preferably an alkyl group (for example, having 1 to 6 carbon atoms).

[0234] The alkylene group may be linear or branched, and preferably has 1 to 6 carbon atoms. The cycloalkylene group preferably has 3 to 15 carbon atoms. The alkenylene group preferably has 2 to 6 carbon atoms. The divalent aliphatic heterocyclic group is preferably a ring having 5 to 10 ring atoms and containing a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. The divalent aromatic heterocyclic group is preferably a ring having 5 to 10 ring atoms and containing a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring atom. The divalent aromatic hydrocarbon ring group includes a ring having 6 to 10 ring atoms.

[0235] L 2 Among them, the divalent linking group represented by the formula: -CO-, -NR d Preferred are -, -O-, -S-, -SO-, -SO2-, an alkylene group, a divalent aromatic hydrocarbon ring group, and a divalent linking group formed by combining a plurality of these. Examples of the "divalent linking group formed by combining a plurality of these" include -alkylene group-O-alkylene group-phenylene group-. In addition, L 2 In the divalent linking group represented by the formula (I), the adjacent position to the polymerizable group represented by Y is -CO-, -NR d It is preferably not -, -O-, -S-, -SO-, or -SO2-.

[0236] Examples of the polymerizable group represented by Y include a radically polymerizable group and a cationically polymerizable group, with a radically polymerizable group being preferred and an ethylenically unsaturated group being more preferred. Examples of the ethylenically unsaturated group include a vinyl group, a maleimide group, and a CH═CR group. T -(R T represents a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), CH2=CR Q -CO-O-(R Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). Q represents a methyl group or a hydrogen atom, CH2=CR Q-CO-O- corresponds to a (meth)acrylic group, and R Q represents a chlorine atom, CH2=CR Q (-CO-O- corresponds to an α-chloroacrylic group), and the (meth)acrylic group is preferred in terms of achieving better effects of the present invention. In other words, the specific monomer B is preferably a (meth)acrylic compound. Among these, the polymerizable group is more preferably a methacrylic group in terms of achieving better effects of the present invention. The specific monomer B is preferably a monofunctional monomer.

[0237] The specific monomer B contains a monovalent substituent represented by the general formula (2) in the molecule. In the specific monomer B, the position at which the monovalent substituent represented by the general formula (2) is introduced is not particularly limited, and for example, R 1 and R 2 or R 3 and R 4 and are bonded to each other to form a ring, or R 11 and R 14 and are bonded to each other to form a ring, or R 5 and R 6 Either one of the two and R 7 and R 8 or R 9 and R 10 Either one of the two and R 12 and R 13 and the like can be bonded to each other to form a ring. The specific monomer B is preferably a monofunctional monomer, that is, the specific monomer B preferably has one monovalent substituent represented by the above general formula (2).

[0238] In addition, in formula (1), L 1 , X 1 , and X 2 A suitable combination of (L 1 , X 1 , X 2 ) as (-CR 3 =CR 4 -, =CR 11-, =CR 14 -), (-CR 3 =CR 4 -, -O-, -CO-), and (-CR 3 =CR 4 -, -CO-, -O-, etc. In addition, (L 1 , X 1 , X 2 ) is (-CR 3 =CR 4 -, =CR 11 -, =CR 14 In the case where the specific monomer B is -), a specific example of the specific monomer B is a compound represented by the following general formula (AX): The polymerizable compound represented by the following general formula (AX) has 9,10-dihydroanthracene as its basic skeleton.

[0239] [ka]

[0240] In the general formula (AX), R 1 , R 2 , R X1 ~R X4 are each independently R in general formula (1). 1 , R 2 , R X1 ~R X4 The same definition and preferred embodiments are also the same. R 22 and R 23 R each independently represents a substituent. 22 and R 23 Examples of the substituent represented by R 1 ~R 14 Examples of the substituents include those represented by the following formula: m and n each independently represent an integer of 0 to 4; However, the polymerizable compound represented by the general formula (AX) contains a monovalent substituent represented by the general formula (2) in the molecule. 1 , R 2 , R 22 , and R 23 It is preferable that the hydroxyl group is introduced into any of the positions above.

[0241] A preferred embodiment of the specific monomer B includes a polymerizable compound represented by the following general formula (3) and a polymerizable compound represented by the following general formula (4).

[0242] The polymerizable compound represented by general formula (3) is R 1 The general formula (3) has the same meaning as the general formula (1) and the preferred embodiments are also the same, except that it has a monovalent substituent represented by the general formula (2) at position 1. The polymerizable compound represented by the general formula (3) is preferably a monofunctional monomer.

[0243] [ka]

[0244] The polymerizable compound represented by general formula (4) is L 1 Ga-CR 3 =CR 4 Except for the fact that it represents -, it has the same meaning as general formula (1) and the same preferred embodiments as well. The polymerizable compound represented by general formula (4) is preferably a monofunctional monomer.

[0245] [ka]

[0246] In the general formula (4), the position at which the monovalent substituent represented by the general formula (2) is introduced can be, for example, R 1 ~R 4 or R 3 and R 4 and are preferably introduced onto a ring formed by bonding together. A preferred embodiment of the polymerizable compound represented by general formula (4) is 1 represents -O-, and X 2 represents -CO-. Another preferred embodiment of the polymerizable compound represented by general formula (4) is a compound represented by the formula (4) below: X 1 represents -O-, and X 2 represents -CO-, and R3 and R 4 and bond to each other to form an alicyclic ring. Another preferred embodiment of the polymerizable compound represented by general formula (4) is a compound represented by the general formula (4) below: X 1 represents -CO-, and X 2 represents -O-. Another preferred embodiment of the polymerizable compound represented by general formula (4) is a compound represented by the formula (4) below: X 1 represents -CO-, and X 2 represents -O-, and R 3 and R 4 and bond to each other to form an alicyclic ring.

[0247] The polymerizable compound represented by the above general formula (3) is preferably a polymerizable compound represented by the following general formula (5): The polymerizable compound represented by the following general formula (5) has a basic skeleton of 9,10-dihydroanthracene.

[0248] [ka]

[0249] In general formula (5), R 24 and R X1 ~R X4 are each independently R in general formula (1). 2 and R X1 ~R X4 The same definition and preferred embodiments are also the same. R 21 represents a hydrogen atom or a substituent. 21 Examples of the substituent represented by R include an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). 21 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. R 22 and R 23 R each independently represents a substituent. 22 and R 23 Examples of the substituent represented by R 1 ~R14 Examples of the substituents include those represented by the following formula: m and n each independently represent an integer of 0 to 4; L 21 is a single bond or a divalent linking group. L 21 Examples of the divalent linking group represented by the formula (2) include L 2 The same groups as those of the divalent linking group represented by the following formula are mentioned, and the preferred embodiments are also the same.

[0250] Specific monomer B is preferably a polymerizable compound whose homopolymer has a glass transition temperature of 220° C. or higher. The glass transition temperature of the homopolymer of specific monomer B refers to the value obtained by the measurement method described above as the glass transition temperature of the homopolymer of specific monomer A.

[0251] The glass transition temperature of the homopolymer of specific monomer B is more preferably 250° C. or higher, even more preferably 280° C. or higher, and particularly preferably 300° C. or higher, in terms of achieving better effects of the present invention. The upper limit is not particularly limited, but is preferably 400° C. or lower.

[0252] The protecting group value of specific monomer B is preferably 3.40 mmol / g or more, in terms of achieving better effects of the present invention. The protecting group value represents the molar amount (mmol / g) of acid-decomposable groups relative to the mass of specific monomer B (polymerizable compound). The upper limit is not particularly limited, but is preferably 6.0 mmol / g or less. The protecting group value is more preferably 3.50 mmol / g or more, and even more preferably 3.60 mmol / g or more, in terms of achieving better effects of the present invention.

[0253] The molecular weight of the specific monomer B is not particularly limited, but is preferably, for example, 400 or more. The upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 700 or less.

[0254] The specific monomer B can be synthesized by a known method, specifically, by a method in which an alkene compound is added to a conjugated diene compound by a Diels-Alder reaction to form an unsaturated six-membered ring structure.

[0255] Specific examples (Group A and Group B) of the specific monomer B are shown below, but the specific monomer B is not limited thereto. Note that all of the compounds belonging to (Group A) of the specific monomer A shown below correspond to compounds having 9,10-dihydroanthracene as a basic skeleton. (Group A)

[0256] [ka]

[0257] [ka]

[0258] [ka]

[0259] (Group B)

[0260] [ka]

[0261] [Electronic device manufacturing method] The present invention also relates to a method for manufacturing an electronic device, which includes a pattern formation method using the resist composition of the first and second embodiments described above, and to an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitably mounted in electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).

[0262] [Compound] The present invention also relates to a polymerizable compound (specific monomer B) represented by the above-mentioned general formula (1). The specific monomer B is as described above.

[0263] [resin] The present invention also relates to a resin (specific acid-decomposable resin B) having a repeating unit derived from the polymerizable compound (specific monomer B) represented by the above-mentioned general formula (1). The specific acid-decomposable resin B is as described above. [Example]

[0264] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0265] [Various Components of Actinic Ray- or Radiation-Sensitive Resin Composition] 〔resin〕 The resins (A-1 to A-23, B-1 to B-10) shown in Table 5 are as follows: Resins A-1 to A-23 and B-1 to B-10 were synthesized according to the synthesis method described below for resin A-10. Table 1 shows the mass ratios of the repeating units constituting the resins shown in Table 5 (A-1 to A-23, B-1 to B-10), the weight average molecular weights (Mw), and the dispersity (Mw / Mn). The weight average molecular weight (Mw) and dispersity (Mw / Mn) of Resins A-1 to A-23 and B-1 to B-10 were measured by GPC (carrier: tetrahydrofuran (THF)) and are shown as polystyrene equivalents.

[0266] [Table 1]

[0267] Tables 2 to 4 show the structures of the monomers (polymerizable compounds) used in the synthesis of Resins A-1 to A-23 and B-1 to B-10 shown in Table 1. Among the monomers shown below, M-55 to M-73 correspond to monomers (specific monomers A) whose homopolymer glass transition temperature is 220°C or higher and whose protecting group value is 3.40 mmol / g or higher. Among the following monomers M-55 to M-73, M-55, M-58 to M-61, and M-67 to M-72 correspond to the polymerizable compound (specific monomer B) represented by the above-mentioned general formula (1).

[0268] The monomers M-55 to M-73 used were synthesized in accordance with the synthesis method described below for resin M-55.

[0269] Tables 2 to 4 also show the glass transition temperature and protecting group value (mmol equivalent per 1 g of monomer (mmol / g)) of the homopolymer of each monomer. The glass transition temperatures of the homopolymers of each monomer shown in Tables 2 to 4 were measured by the following method.

[0270] <<Method for measuring the glass transition temperature (Tg) of the homopolymer of each monomer shown in Tables 2 to 4>> <1> Each monomer shown in Tables 2 to 4 is synthesized in a feed composition of 30 mass% and cyclohexyl methacrylate in 70 mass%, to obtain a copolymer P2 having a weight average molecular weight of 60,000 or more (specifically, a weight average molecular weight of 60,000 to 100,000). (2) The Tg of the obtained copolymer P2 is evaluated using a differential scanning calorimeter (Shimadzu Corporation's "Differential Scanning Calorimeter DSC-60 Plus Measurement System"). The Tg was measured under the following conditions. Measurement conditions: Under an air flow, the temperature was raised from room temperature to 150° C. The temperature was raised at a rate of 5° C. / min for two cycles, and the Tg of the copolymer P2 was obtained. <3> Using the following formula (1) based on the Fox formula, the Tg of the homopolymer of each monomer shown in Tables 2 to 4 is calculated, assuming that the Tg of the homopolymer of cyclohexyl methacrylate is 98°C.

[0271] Formula (1)1 / Tg=w1 / Tg1+w2 / Tg2 In formula (1), Tg represents the Tg(K) of copolymer P2. Tg1 represents the homopolymer Tg(K) of each monomer shown in Tables 2 to 4. Tg2 represents the homopolymer Tg(K) of cyclohexyl methacrylate. w1 represents the mass fraction of repeating units derived from each monomer shown in Tables 2 to 4 relative to all repeating units in copolymer P2. w2 represents the mass fraction of repeating units derived from a homopolymer of cyclohexyl methacrylate relative to all repeating units in copolymer P2. When calculating the homopolymer Tg of each monomer, w1 is set to 0.3 and w2 is set to 0.7.

[0272] The following monomers M-55, M-59 to M-61, M-67 to M-69, and M-71 to M-72 all correspond to compounds having 9,10-dihydroanthracene as a basic skeleton.

[0273] [Table 2]

[0274] [Table 3]

[0275] [Table 4]

[0276] <<Synthesis Example>> <Synthesis Example 1: Synthesis of M-55> (Step 1: Synthesis of fumaric acid ester)

[0277] [ka]

[0278] A solution of potassium t-butoxide (146.8 g) and t-butanol (1,300 g) was heated to 35° C. under a nitrogen stream. Fumarolic acid chloride (100.0 g) was added dropwise to this solution while stirring, and after the dropwise addition was completed, the temperature was raised to 50° C. and the solution was stirred for 4 hours. The resulting solution was allowed to cool to room temperature, and 200 ml of saturated aqueous sodium bicarbonate was added dropwise with stirring to quench the reaction. The remaining t-BuOH was then removed using an evaporator. Next, the solution was separated using 1200 ml of ethyl acetate and 1200 ml of water, and the separated ethyl acetate layer was dried over magnesium sulfate. After drying, the solution was filtered, and the filtered solution was concentrated using an evaporator. 50 ml of isopropanol was added to the resulting concentrated solution, which was then heated and dissolved, and 50 ml of water was added to cause crystallization. The resulting crystallized product (powder) was collected by filtration to obtain the target product (FA-TBm: yield 70.1 g, 47%).

[0279] (Step 2: Synthesis of precursor compound (M'-55))

[0280] [ka]

[0281] To toluene (250 ml), anthracenemethanol (50.0 g) and FA-TBm (65.8 g) were added, heated to 115°C in an oil bath, and reacted under reflux for 16 hours. The toluene was removed using an evaporator, and 36 ml of methanol was added. The mixture was stirred while cooling on ice. The precipitated powder was filtered to obtain the target product (M'-55: yield 80 g, 76.3%).

[0282] (Step 3: Synthesis of Compound M-55)

[0283] [ka]

[0284] M'-55 (80 g) was dissolved in tetrahydrofuran (185 ml), and methacrylic acid chloride (46 g) was added dropwise with ice cooling, followed by triethylamine (44.5 g). After the addition, the resulting reaction solution was reacted for another hour, and then this reaction solution was added to 1200 ml of ethyl acetate and 1200 ml of saturated sodium bicarbonate water and stirred overnight. The ethyl acetate layer was then extracted by a separation operation and dried over magnesium sulfate. After drying, the solution was filtered, and the filtered solution was then concentrated in an evaporator. 360 ml of methanol was added to the resulting concentrate, and the mixture was stirred to crystallize. The resulting crystallized product (powder) was collected by filtration to obtain the target product (M-55: yield 75.8 g, 82%). Figure 1 shows the obtained M-55. 1 The H-NMR chart is shown below.

[0285] <Synthesis Example 2: Synthesis of Resin A-10> Cyclohexanone (15.2 g) was heated to 85°C under a nitrogen stream. While stirring, a mixture of Monomer M-19 (31.3 g, 50.4 wt% PGMEA solution), Monomer M-60 (29.3 g), cyclohexanone (27.1 g), and a cyclohexanone solution (10 wt%) (33.8 g) of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 6 hours to obtain a reaction solution. After the addition was completed, the reaction solution was stirred at 85°C for an additional 2 hours. The resulting reaction solution was allowed to cool and then reprecipitated with a large amount of heptane / ethyl acetate (9:1 mass ratio). The mixture was then filtered, and the resulting solid was vacuum dried to obtain Resin A-10 (39 g). All of the above operations were performed under yellow light.

[0286] [ka]

[0287] [Photoacid generator] The structures of the photoacid generators (B-1 to B-11) shown in Table 5 are shown below.

[0288] [ka]

[0289] [ka]

[0290] [Hydrophobic resin] The structures, weight average molecular weights (Mw), and dispersity (Mw / Mn) of the hydrophobic resins (P-1 to P-3) shown in Table 5 are shown below. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the hydrophobic resins P-1 to P-3 were measured by GPC (carrier: THF) and are shown as polystyrene equivalents. Hydrophobic resin P-1: Polymer made from the following monomer ME-1 (Mw: 8,700, Mw / Mn: 1.56) Hydrophobic resin P-2: Polymer made from the following monomer ME-5 (Mw: 7,600, Mw / Mn: 1.62) Hydrophobic resin P-3: Polymer made from the following monomer ME-2 (Mw: 5,800, Mw / Mn: 1.55)

[0291] [ka]

[0292] [Surfactant] The surfactants shown in Table 5 are as follows: H-1: Megafac F176 (DIC Corporation, fluorine-based surfactant)

[0293] 〔solvent〕 The solvents shown in Table 5 are as follows: G-1: Propylene glycol monomethyl ether acetate (PGMEA) G-2: Propylene glycol monomethyl ether (PGME) G-5: Cyclopentanone G-8: γ-butyrolactone

[0294] [Preparation of actinic ray- or radiation-sensitive resin composition and pattern formation: EUV exposure] [Preparation of actinic ray- or radiation-sensitive resin composition] The components shown in Table 5 were mixed to a solids concentration of 1.4% by mass. The resulting mixture was then filtered by first passing it through a polyethylene filter with a pore size of 50 nm, then a nylon filter with a pore size of 10 nm, and finally a polyethylene filter with a pore size of 5 nm, to prepare actinic ray- or radiation-sensitive resin compositions (hereinafter also referred to as "resist compositions") (Re-1 to Re-23, HRe-1 to HRe-10). The solids refer to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples.

[0295] Table 5 is shown below. In the table, the "content" column for each component indicates the content (mass %) of each component relative to the total solid content. Also, the "mixing ratio" in the "solvent" column indicates the mixing ratio (mass ratio) of each solvent.

[0296] [Table 5]

[0297] [Pattern formation and evaluation (1): EUV exposure, alkaline development] <Pattern formation> An underlayer film-forming composition AL412 (manufactured by BrewerScience) was applied to a silicon wafer having a diameter of 12 inches and baked at 205°C for 60 seconds to form an underlayer film having a thickness of 20 nm. The resist composition prepared as described above was applied thereon and baked at 100°C for 60 seconds to form a resist film having a thickness of 20 nm. Exposure was performed using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 45°, outer sigma 0.87, inner sigma 0.60) through a reflective mask with a line size of 20 nm and a line:space ratio of 1:1. The wafer was then developed with a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) for 30 seconds, rinsed with water for 20 seconds, and then rotated at 2000 rpm for 40 seconds to form a positive pattern with a line size of 20 nm and a line:space ratio of 1:1.

[0298] <Evaluation> (Line width roughness (LWR performance, nm)) The pattern obtained by the above method was observed from above using a critical dimension scanning electron microscope (SEM (Hitachi S-9380II)). The line width of the pattern was observed at 250 points, and the measurement variation was evaluated at 3σ to obtain the LWR (nm). The smaller the LWR value, the better the LWR performance. The results are shown in Table 6. The LWR performance is preferably less than 4.00 nm, more preferably 3.50 nm or less, and even more preferably 3.00 nm or less.

[0299] (Resolution evaluation (limiting resolution, nm)) In the above-mentioned <pattern formation>, the exposure is performed at an optimum exposure dose Eop (μC / cm 2 ) (the exposure dose when the pattern formed using the resist composition reproduces the pattern of the mask used for exposure). Next, a test was conducted to form a line and space pattern by gradually changing the exposure dose from the optimum exposure dose Eop. The minimum dimension of the pattern that could be resolved without collapsing was determined using a critical dimension scanning electron microscope (SEM (Hitachi S-9380II)). This was defined as the "limiting resolution (nm)." The smaller the limiting resolution value, the better the resolution. The results are shown in Table 6. The resolution is preferably less than 15.0 nm, more preferably 13.0 nm or less, and even more preferably 12.0 nm or less.

[0300] [Table 6]

[0301] The results shown in the table confirm that the resist compositions of the examples are excellent in resolution and also in the LWR performance of the patterns formed.

[0302] (Results for specific monomer A) Furthermore, by comparing the examples, it was confirmed that when the raw material monomer of the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition corresponds to a monomer having a glass transition temperature of 300°C or higher in the homopolymer and a protecting group value of 3.40 mmol / g or higher (preferably a monomer having a glass transition temperature of 300°C or higher in the homopolymer and a protecting group value of 3.50 mmol / g or higher), the resist composition exhibits superior resolution and the formed pattern also exhibits superior LWR performance. Furthermore, it was confirmed that when the polar group protected by the protecting group in the structure of the acid-decomposable repeating unit is a carboxyl group, the resist composition has superior resolution and the LWR performance of the formed pattern is also superior.

[0303] (Results for specific monomer B) Furthermore, for example, when the results of Example 4 and Example 8 are compared, it was confirmed that when the raw material monomer for the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition is a polymerizable compound represented by the general formula (1) above, particularly when it has a structure represented by the general formula (AX) above, the resist composition exhibits superior resolution and the LWR performance of the formed pattern is also superior. Furthermore, for example, by comparing the results of Examples 1, 6, and 7, it was confirmed that when the polymerizable group in the polymerizable compound represented by the above-mentioned general formula (1) is a (meth)acrylic group (preferably a methacrylic group), the resist composition has better resolution and the LWR performance of the formed pattern is also better.

[0304] Furthermore, by comparing Examples 1, 11, 21, and 22, it was found that in the polymerizable compound represented by the above-mentioned general formula (1), the type of the acid-decomposable group is a group represented by the above-mentioned general formula (O1), and R 11 ~R 13 It has been confirmed that when two of the groups do not bond to each other to form a ring, the resist composition has better resolution and the LWR performance of the formed pattern is also better.

[0305] Furthermore, a comparison between Example 1 and Example 13 confirmed that when the polymerizable compound represented by the above-mentioned general formula (1) has two acid-decomposable groups, the resist composition has superior resolution and the LWR performance of the formed pattern is also superior.

[0306] Furthermore, by comparing Examples 1, 9, and 14, it was found that in the polymerizable compound represented by the above-mentioned general formula (1), R X1 ~R X4 It has been confirmed that when two of the groups represent an acid-decomposable group and the other two represent a hydrogen atom, the resist composition exhibits superior resolution and the LWR performance of the formed pattern is also superior.

[0307] On the other hand, the resist compositions of the comparative examples did not sufficiently achieve the desired performance.

[0308] [Pattern formation and evaluation (2): EUV exposure, organic solvent development] <Pattern formation> An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer having a diameter of 12 inches and baked at 205°C for 60 seconds to form an underlayer film having a thickness of 20 nm. A resist composition shown in Table 7 was applied thereon and baked at 100°C for 60 seconds to form a resist film having a thickness of 30 nm. Using an EUV exposure tool (Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36), the silicon wafer with the resist film was irradiated with a pattern so that the average line width of the resulting pattern was 20 nm. Note that a mask with a line size of 20 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90°C for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.

[0309] <Evaluation> The obtained negative pattern was evaluated for line width roughness (LWR performance, nm) and resolution (limiting resolution, nm) using the same method as described above in [Pattern formation and evaluation (1): EUV exposure, alkaline development]. The results are shown in Table 7.

[0310] [Table 7]

[0311] The results shown in the table confirm that the resist compositions of the examples can form patterns with excellent LWR and resolution.

[0312] (Results for specific monomer A) Furthermore, by comparing the examples, it was confirmed that when the raw material monomer of the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition corresponds to a monomer having a glass transition temperature of 300°C or higher in the homopolymer and a protecting group value of 3.40 mmol / g or higher (preferably a monomer having a glass transition temperature of 300°C or higher in the homopolymer and a protecting group value of 3.50 mmol / g or higher), the resist composition exhibits superior resolution and the formed pattern also exhibits superior LWR performance. Furthermore, it was confirmed that when the polar group protected by the protecting group in the structure of the acid-decomposable repeating unit is a carboxyl group, the resist composition has superior resolution and the LWR performance of the formed pattern is also superior.

[0313] (Results for specific monomer B) Furthermore, for example, a comparison of the results of Example 24 and Example 28 confirmed that when the raw material monomer for the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition is a polymerizable compound represented by general formula (1) above, particularly when it has a structure represented by general formula (AX), the resist composition exhibits superior resolution and the formed pattern also exhibits superior LWR performance. Furthermore, for example, by comparing the results of Examples 21, 26, and 27, it was confirmed that when the polymerizable group in the polymerizable compound represented by the above-mentioned general formula (1) is a (meth)acrylic group (preferably a methacrylic group), the resist composition has better resolution and the LWR performance of the formed pattern is also better.

[0314] Furthermore, by comparing Examples 21, 31, 41, and 42, it was found that in the polymerizable compound represented by the above-mentioned general formula (1), the type of the acid-decomposable group is a group represented by the above-mentioned general formula (O1), and R 11 ~R 13 It has been confirmed that when two of the groups do not bond to each other to form a ring, the resist composition has better resolution and the LWR performance of the formed pattern is also better.

[0315] Furthermore, a comparison between Example 21 and Example 33 confirmed that when the polymerizable compound represented by the general formula (1) above has two acid-decomposable groups, the resist composition exhibits superior resolution and the LWR performance of the formed pattern is also superior.

[0316] Furthermore, by comparing Examples 21, 29, and 34, it was found that in the polymerizable compound represented by the above-mentioned general formula (1), R X1 ~RX4 It has been confirmed that when two of the groups represent an acid-decomposable group and the other two represent a hydrogen atom, the resist composition exhibits superior resolution and the LWR performance of the formed pattern is also superior.

[0317] On the other hand, the resist compositions of the comparative examples did not sufficiently achieve the desired performance.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit derived from a polymerizable compound represented by the following general formula (1) and a photoacid generator: 【Chemistry 1】 In the ceremony, L １ is -CR ３ =CR ４ -or-CR ５ R ６ -CR ７ R ８ Represents -. X １ is -O-, -CR ９ R １０ - or =CR １１ Represents -. X ２ is -O-, -CO-, -CR １２ R １３ - or =CR １４ Represents -. X １ and X ２ The bond shown by a solid line and a dotted line represents a single bond or a double bond. １ and X ２ When the bond with represents a double bond, X １ Ha = CR １１ represents -, and X ２ Ha = CR １４ -. Also, X １ and X ２ When the bond with represents a single bond, X １ is -O- or -CR ９ R １０ represents -, and X ２ is —O—, —CO—, or —CR １２ R １３ Represents -. R １ ~R １４ Each independently represents a hydrogen atom or a substituent. ３ and R ４ may be bonded to each other to form a ring. ５ and R ６ Either one of the two and R ７ and R ８ and X may be bonded to each other to form a ring. １ Ga = CR １１ represents -, and X ２ Ga = CR １４ When represents -, R １１ and R １４ and may be bonded to each other to form a ring. １ Ga-CR ９ R １０ represents -, and X ２ Ga-CR １２ R １３ When represents -, R ９ and R １０ Either one of the two and R １２ and R １３ may be bonded to each other to form a ring. R Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent. Ｘ１ ~R Ｘ４ At least one of R represents an acid-decomposable group. Ｘ１ and R Ｘ２ Either one of the two and R Ｘ３ and R Ｘ４ may be bonded to each other to form a ring. However, the polymerizable compound represented by the general formula (1) contains a monovalent substituent represented by the following general formula (2) in the molecule. 【Chemistry 2】 In the ceremony, L ２ represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents a bonding position.

2. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the polymerizable compound represented by general formula (1) is a polymerizable compound represented by the following general formula (3): 【Transformation 3】 In the ceremony, L １ is -CR ３ =CR ４ -or-CR ５ R ６ -CR ７ R ８ Represents -. X １ is -O-, -CR ９ R １０ - or =CR １１ Represents -. X ２ is -O-, -CO-, -CR １２ R １３ - or =CR １４ Represents -. X １ and X ２ The bond shown by a solid line and a dotted line represents a single bond or a double bond. １ and X ２ When the bond with represents a double bond, X １ Ha = CR １１ represents -, and X ２ Ha = CR １４ -. Also, X １ and X ２ When the bond with represents a single bond, X １ is -O- or -CR ９ R １０ represents -, and X ２ is —O—, —CO—, or —CR １２ R １３ Represents -. R ２ ~R １４ Each independently represents a hydrogen atom or a substituent. ３ and R ４ may be bonded to each other to form a ring. ５ and R ６ Either one of the two and R ７ and R ８ and X may be bonded to each other to form a ring. １ Ga = CR １１ represents -, and X ２ Ga = CR １４ When represents -, R １１ and R １４ and may be bonded to each other to form a ring. １ Ga-CR ９ R １０ represents -, and X ２ Ga-CR １２ R １３ When represents -, R ９ and R １０ Either one of the two and R １２ and R １３ may be bonded to each other to form a ring. R Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent. Ｘ１ ~R Ｘ４ At least one of R represents an acid-decomposable group. Ｘ１ and R Ｘ２ Either one of the two and R Ｘ３ and R Ｘ４ may be bonded to each other to form a ring. L ２ represents a single bond or a divalent linking group. Y represents a polymerizable group.

3. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the polymerizable compound represented by general formula (1) is a polymerizable compound represented by the following general formula (4): 【Chemistry 4】 In the formula, X １ is -O-, -CR ９ R １０ - or =CR １１ Represents -. X ２ is -O-, -CO-, -CR １２ R １３ - or =CR １４ Represents -. X １ and X ２ The bond shown by a solid line and a dotted line represents a single bond or a double bond. １ and X ２ When the bond with represents a double bond, X １ Ha = CR １１ represents -, and X ２ Ha = CR １４ -. Also, X １ and X ２ When the bond with represents a single bond, X １ is -O- or -CR ９ R １０ represents -, and X ２ is —O—, —CO—, or —CR １２ R １３ Represents -. R １ ~R ４ and R ９ ~R １４ Each independently represents a hydrogen atom or a substituent. ３ and R ４ and may be bonded to each other to form a ring. １ Ga = CR １１ represents -, and X ２ Ga = CR １４ When represents -, R １１ and R １４ and may be bonded to each other to form a ring. １ Ga-CR ９ R １０ represents -, and X ２ Ga-CR １２ R １３ When represents -, R ９ and R １０ Either one of the two and R １２ and R １３ may be bonded to each other to form a ring. R Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent. Ｘ１ ~R Ｘ４ At least one of R represents an acid-decomposable group. Ｘ１ and R Ｘ２ Either one of the two and R Ｘ３ and R Ｘ４ may be bonded to each other to form a ring. However, the polymerizable compound represented by the general formula (4) contains a monovalent substituent represented by the following general formula (2) in the molecule. 【Transformation 5】 In the ceremony, L ２ represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents a bonding position.

4. R Ｘ１ ~R Ｘ４ The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein at least two of the above represent acid-decomposable groups.

5. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the polymerizable compound represented by general formula (1) is a polymerizable compound represented by the following general formula (5): 【Transformation 6】 In the ceremony, L ２１ represents a single bond or a divalent linking group. Ｘ１ and R Ｘ３ R each independently represents an acid-decomposable group. Ｘ２ and R Ｘ４ Each independently represents a hydrogen atom or a substituent. Ｘ２ and R Ｘ４ may be bonded to each other to form a ring. ２１ represents a hydrogen atom or a substituent. ２２ and R ２３ each independently represents a substituent. m and n each independently represent an integer of 0 to 4. ２４ represents a hydrogen atom or a substituent.

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

7. 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 5; exposing the resist film to light; developing the exposed resist film using a developer; A pattern forming method comprising the steps of:

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

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