Resist composition and method for forming resist pattern

Abstract

A resist composition containing: a resin component (A1) having a structural unit (a01) represented by general formula (a0-1) and a structural unit (a10) represented by general formula (a10-1); and a compound (D0) having a group represented by general formula (d0-r). In the formula, Rx01, Rx021 to Rx028 are hydrogen atoms or the like. Ra0 is an acid-dissociable group represented by general formula (a01-r-1). And Wax1 represents an optionally substituted aromatic hydrocarbon group. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resist composition and a resist pattern forming method.

[0002] This application claims priority based on Japanese Patent Application No. 2022-128064, filed in Japan on August 10, 2022, and incorporates the contents herein. Background Art

[0003] In recent years, the miniaturization of patterns in the manufacture of semiconductor devices and liquid crystal display devices has developed rapidly due to advances in photolithography technology. As a method of miniaturization, the wavelength of the exposure light source is generally shortened (higher energy). Specifically, ultraviolet rays represented by g-rays and i-rays were previously used, but now KrF excimer lasers or ArF excimer lasers are used for mass production of semiconductor devices. In addition, research is also underway on EUV (extreme ultraviolet rays), EB (electron beams), X-rays, etc., which have shorter wavelengths (higher energy) than these excimer lasers.

[0004] Resist materials are required to have photolithographic properties such as sensitivity to these exposure light sources and resolution capable of reproducing fine-scale patterns.

[0005] As a resist material that meets such requirements, a chemically amplified resist composition containing a base component whose solubility in a developer changes due to the action of an acid and an acid generator component that generates an acid upon exposure has been conventionally used.

[0006] However, with the increasing integration of LSIs and the speed of communications, the demand for increased memory capacity is rapidly advancing, and the need for further miniaturization of patterns is increasing. However, while electron beam or EUV lithography aims to form fine patterns measuring tens of nanometers, it still faces numerous technical challenges, such as low productivity, and there are limits to microfabrication technology.

[0007] In response to this, in addition to miniaturization, the development of three-dimensional structured devices has been promoted in order to achieve larger memory capacity by stacking elements in layers.

[0008] The production of these three-dimensional devices involves forming a thicker resist film than conventional films on the surface of the workpiece, forming a resist pattern, and then performing etching. When using a chemically amplified resist composition, as the resist film thickness increases, the lower layer of the resist film experiences a decrease in transmittance, leading to a decrease in acid generation. This results in a curled resist pattern, making it difficult to achieve the desired resist pattern shape.

[0009] In response to this, a chemically amplified resist composition has been proposed that contains both an acid generator component and an acid diffusion controller for controlling the diffusion of acid generated from the acid generator component by exposure.

[0010] For example, Patent Document 1 discloses a resist composition comprising a base component (A) whose solubility in a developer solution changes due to the action of an acid, and a tertiary monoamine compound (D0) having a specific structure as an acid diffusion controller, wherein the base component (A) is present in an amount of 20% by mass or more, and the compound (D0) is present in an amount of 0.01 to 0.05 parts by mass per 100 parts by mass of the base component (A). The resist composition is described as being capable of forming a pattern of good shape while maintaining high sensitivity.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent Application Publication No. 2020-008781 Summary of the Invention

[0014] Technical problem to be solved by the invention

[0015] However, in the resist composition disclosed in Patent Document 1, the tertiary monoamine compound (D0) has insufficient heat resistance and may not fully exhibit its function as an acid diffusion controller, resulting in a curled pattern.

[0016] Furthermore, conventional resist compositions that attempt to improve curling shape by increasing the transmittance of the resin and reducing the deprotection energy may result in reduced adhesion between the resist pattern and the substrate, and increased variation in CD (critical dimension), making it difficult to achieve both a good shape and improved adhesion and CD stability.

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition capable of forming a pattern having a good shape, improved adhesion, and improved CD stability, and a resist pattern forming method using the resist composition.

[0018] Solutions for solving the above technical problems

[0019] In order to solve the above-mentioned technical problems, the present invention adopts the following configuration.

[0020] That is, the first embodiment of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, comprising: a resin component (A1) whose solubility in a developer changes due to the action of the acid; and a compound (D0) having a group represented by the following general formula (d0-r), wherein the resin component (A1) has a structural unit (a01) represented by the following general formula (a0-1) and a structural unit (a10) represented by the following general formula (a10-1).

[0021] [Chemistry 1]

[0022]

[0023] [Where, Rx 01 is a hydrogen atom, an alkyl group or an alkoxy group. 021 ~Rx 028 are independently a hydrogen atom or an alkyl group. nd is 0 or 1. * indicates a bonding position.]

[0024] [Chemistry 2]

[0025]

[0026] [Where R 0 Va is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 0 is a single bond or a divalent linking group. 0 It is an acid-dissociable group represented by the following general formula (a01-r-1).

[0027] [Chemistry 3]

[0028]

[0029] [Where, Ra 01 ~Ra 03 are each independently a hydrocarbon group which may have a substituent, Ra 02 and Ra 03 They can bond to each other to form a ring. * indicates the bonding position.]

[0030] [Chemistry 4]

[0031]

[0032] [wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. x1 Is a single bond or a divalent connecting group. x1 It is an aromatic hydrocarbon group which may have a substituent. ax1 is an integer greater than 1.]

[0033] A second aspect of the present invention is a resist pattern forming method comprising: forming a resist film on a support using the resist composition; exposing the resist film to light; and developing the exposed resist film to form a resist pattern.

[0034] Effects of the Invention

[0035] According to the present invention, a resist composition capable of forming a pattern having a good shape, improved adhesion, and improved CD stability, and a resist pattern forming method using the resist composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a schematic diagram for explaining the evaluation of pattern shape. DETAILED DESCRIPTION

[0037] In this specification and the claims, "aliphatic" is a relative concept relative to aromatic, and is defined to mean a group, compound, etc. that does not have aromaticity.

[0038] Unless otherwise specified, "alkyl" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.

[0039] Unless otherwise specified, the term "alkylene" includes linear, branched, and cyclic divalent saturated hydrocarbon groups.

[0040] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0041] The "structural unit" refers to a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

[0042] When it is stated that "may have a substituent", both cases of replacing a hydrogen atom (-H) with a monovalent group and replacing a methylene group (-CH2-) with a divalent group are included.

[0043] “Exposure” is a concept that includes all exposure to radiation.

[0044] The "acid-decomposable group" is an acid-decomposable group such that at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.

[0045] Examples of the acid-decomposable group whose polarity increases due to the action of an acid include a group that generates a polar group by decomposition due to the action of an acid.

[0046] Examples of the polar group include a carboxyl group, a hydroxyl group, an amino group, and a sulfonic acid group (—SO 3 H).

[0047] More specifically, the acid-decomposable group may be a group in which the polar group is protected by an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

[0048] The term "acid-dissociable group" refers to either: (i) a group having acid-dissociable properties such that the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group can be cleaved by the action of an acid; or (ii) a group such that a portion of the bond is cleaved by the action of an acid and then further undergoes a decarboxylation reaction, thereby cleaving the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group.

[0049] The acid-dissociable group constituting the acid-decomposable group must be a group with a lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Therefore, when the acid-dissociable group is dissociated by the action of an acid, a polar group with a higher polarity than the acid-dissociable group is generated, thereby increasing the polarity. As a result, the polarity of the component (A1) as a whole increases. Due to the increase in polarity, the solubility in the developer changes relatively. When the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.

[0050] "Base components" refer to organic compounds with film-forming properties. Organic compounds used as base components are broadly categorized as nonpolymers and polymers. Nonpolymers with a molecular weight of 500 to less than 4000 (hereinafter referred to as "low-molecular-weight compounds") are generally used.

[0051] Hereinafter, "resin," "polymer," or "polymer" refers to a polymer having a molecular weight of 1000 or greater. The molecular weight of the polymer is a weight average molecular weight calculated as polystyrene by GPC (gel permeation chromatography).

[0052] The "derived structural unit" refers to a structural unit formed by cleavage of multiple bonds between carbon atoms, such as olefinic double bonds.

[0053] The hydrogen atom bonded to the carbon atom at the α position of the "acrylate" may be substituted by a substituent. The substituent (R αx ) is an atom or group other than a hydrogen atom. In addition, it also includes a substituent (R αx ) an itaconate diester substituted with a substituent containing an ester bond, a substituent (R αx ) α-hydroxyacrylate substituted with a hydroxyalkyl group or a group modifying the hydroxyl group. In addition, unless otherwise specified, the carbon atom at the α position of the acrylate refers to the carbon atom to which the carbonyl group of the acrylic acid is bonded.

[0054] Hereinafter, an acrylate in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate.

[0055] The term "derivative" encompasses compounds in which the α-position hydrogen atom of the target compound is replaced with a substituent such as an alkyl group or a haloalkyl group, as well as derivatives thereof. Examples of derivatives include compounds in which the hydrogen atom of a hydroxyl group of the target compound in which the α-position hydrogen atom may be replaced with a substituent, and compounds in which a substituent other than a hydroxyl group is bonded to the target compound in which the α-position hydrogen atom may be replaced with a substituent. Unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group.

[0056] As the substituent for the hydrogen atom at the α-position of hydroxystyrene, there can be mentioned the following: αx Same group.

[0057] In this specification and claims, depending on the structure represented by the chemical formula, there may be an asymmetric carbon structure, and enantiomers or diastereomers may exist. In this case, these isomers are representatively represented by a single chemical formula. These isomers may be used alone or as a mixture.

[0058] (Resist composition)

[0059] The resist composition of the present embodiment generates acid by exposure, and its solubility in a developer changes due to the action of the acid.

[0060] The above-mentioned anti-etching composition contains: a base component (A) (hereinafter also referred to as "(A) component"), whose solubility in the developer changes due to the action of acid; and a compound (D0) (hereinafter also referred to as "(D0) component") having a group represented by the general formula (d0-r).

[0061] In the resist composition of this embodiment, the acid may be generated by the component (A) upon exposure, or by an additive component blended separately from the component (A) upon exposure.

[0062] Specifically, the resist composition of this embodiment can be: (1) a resist composition that further contains an acid generator component (B) (hereinafter referred to as "(B) component") that generates acid upon exposure; (2) the (A) component can be a component that generates acid upon exposure; (3) the (A) component is a component that generates acid upon exposure, and the resist composition further contains the (B) component.

[0063] That is, in the cases of (2) and (3) above, component (A) becomes a "base component that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid". In the case where component (A) is a base component that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, component (A1) described later is preferably a resin that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid. As such a resin, a polymer compound having a structural unit that generates acid upon exposure can be used. As the structural unit that generates acid upon exposure, a known structural unit can be used.

[0064] The resist composition of this embodiment is preferably the case of (1) above among the above.

[0065] That is, the resist composition of this embodiment may contain the components (A) and (D0) and not the component (B), but is preferably a resist composition containing the components (A), (B), and (D0).

[0066] When a resist film is formed using the resist composition of this embodiment and selectively exposed, for example, component (B) generates an acid in the exposed portions of the resist film. This acid changes the solubility of component (A) in the developer. Meanwhile, in the unexposed portions of the resist film, the solubility of component (A) in the developer remains unchanged, resulting in a difference in solubility in the developer between the exposed and unexposed portions. Consequently, when the resist film is developed, if the resist composition is positive-working, the exposed portions of the resist film are dissolved and removed, forming a positive-working resist pattern. If the resist composition is negative-working, the unexposed portions of the resist film are dissolved and removed, forming a negative-working resist pattern.

[0067] The resist composition of this embodiment may be a positive-working resist composition or a negative-working resist composition. Furthermore, the resist composition of this embodiment may be used in an alkaline development process using an alkaline developer during the development process for resist pattern formation, or in a solvent development process using a developer containing an organic solvent (organic developer).

[0068] Hereinafter, details of a resist composition containing the component (A), the component (B), and the component (D0) as a resist composition according to one embodiment will be described.

[0069] <(A)Component>

[0070] In the resist composition of the present embodiment, the component (A) contains a resin component (A1) (hereinafter also referred to as “component (A1)”) whose solubility in a developer is changed by the action of an acid.

[0071] By using the component (A1), since the polarity of the base material components changes before and after exposure, good development contrast can be obtained not only in an alkaline development process but also in a solvent development process.

[0072] As the component (A), other high molecular weight compounds and / or low molecular weight compounds may be used in combination with the component (A1).

[0073] In the resist composition of the present embodiment, the component (A) may be used alone or in combination of two or more.

[0074] Regarding ingredient (A1)

[0075] The component (A1) is a resin component whose solubility in a developer solution changes due to the action of an acid.

[0076] The component (A1) has a structural unit (a01) represented by the following general formula (a0-1) and a structural unit (a10) represented by the following general formula (a10-1).

[0077] Structural Unit (a01)

[0078] The structural unit (a01) is a structural unit (a01) represented by the following general formula (a0-1).

[0079] [Chemistry 5]

[0080]

[0081] [Where R 0 Va is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 0 is a single bond or a divalent linking group. 0 It is an acid-dissociable group represented by the following general formula (a01-r-1).

[0082] [Chemistry 6]

[0083]

[0084] [Where, Ra 01 ~Ra 03 are each independently a hydrocarbon group which may have a substituent, Ra 02 and Ra 03 They can bond to each other to form a ring. * indicates the bonding position.]

[0085] In formula (a0-1), R 0The C1-5 alkyl group is preferably a linear or branched C1-5 alkyl group, and specifically includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. A C1-5 haloalkyl group is a group in which some or all of the hydrogen atoms of the C1-5 alkyl group are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms.

[0086] As R 0 , preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0087] In formula (a0-1), Va 0 It is a single bond or a divalent linking group.

[0088] As Va 0 The divalent linking group in is not particularly limited, and preferred examples include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom.

[0089] ·Divalent hydrocarbon group which may have a substituent:

[0090] In Va 0 In the case of a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0091] ··Va 0 Aliphatic hydrocarbon groups

[0092] The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0093] Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure.

[0094] ···Straight-chain or branched aliphatic hydrocarbon group

[0095] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0096] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples thereof include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0097] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

[0098] As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specific examples include -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2- and the like alkylmethylene groups; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2- and the like alkylethylene groups; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and the like alkylpropylene groups; and -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2- and the like alkylbutylene groups. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0099] The linear or branched aliphatic hydrocarbon group may or may not have a substituent, and examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

[0100] Aliphatic hydrocarbon groups containing rings in their structures

[0101] Examples of the aliphatic hydrocarbon group containing a ring in its structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may have a substituent including a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group include the same aliphatic hydrocarbon groups as described above.

[0102] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0103] The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a polycycloalkane having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0104] The cyclic aliphatic hydrocarbon group may or may not have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and a carbonyl group.

[0105] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0106] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and still more preferably a methoxy group and an ethoxy group.

[0107] The halogen atom as the substituent is preferably a fluorine atom.

[0108] Examples of the haloalkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0109] In a cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a heteroatom-containing substituent. Preferred heteroatom-containing substituents include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0110] ··Va 0 Aromatic hydrocarbon groups

[0111] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0112] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. This number of carbon atoms does not include the number of carbon atoms in the substituent.

[0113] Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting such aromatic hydrocarbon rings are replaced with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen, sulfur, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine and thiophene rings.

[0114] Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring or aromatic heterocyclic ring (an arylene group or a heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring or aromatic heterocyclic ring (an aryl group or a heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, or 2-naphthylethyl). The alkylene group bonded to the aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0115] In the aromatic hydrocarbon group, a hydrogen atom in the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of such substituents include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, and a hydroxyl group.

[0116] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0117] Examples of the alkoxy group, halogen atom, and haloalkyl group as the substituent include the groups exemplified as the substituents substituting for the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0118] Heteroatom-containing divalent linking group:

[0119] In Va 0 In the case of a divalent linking group containing a heteroatom, preferred linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and groups of the general formula -Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21-、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -represented by a group [wherein, Y 21 and Y 22 Each independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3] and the like.

[0120] When the heteroatom-containing bivalent linking group is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H group thereof may be substituted by a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

[0121] General formula-Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -Medium,Y 21 and Y 22 Each independently represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the following: 0 The same groups as those exemplified in the description of the divalent linking group (the divalent hydrocarbon group which may have a substituent).

[0122] As Y 21 , preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, further preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0123] As Y 22 , preferably a straight-chain or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0124] In the form of -[Y 21 -C(=O)-O] m” -Y 22 -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as a group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 -, particularly preferably a group represented by the formula -Y 21 -C(=O)-OY 22 - represented by a group. Among them, preferably a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ -. In this formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1.

[0125] Among the above, as Va 0 , preferably a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof, more preferably a single bond.

[0126] In formula (a0-1), Ra 0 It is an acid-dissociable group represented by the following general formula (a01-r-1).

[0127] [Chemistry 7]

[0128]

[0129] [Where, Ra 01 ~Ra 03 are each independently a hydrocarbon group which may have a substituent, Ra 02 and Ra 03 They can bond to each other to form a ring. * indicates the bonding position.]

[0130] In formula (a01-r-1), Ra 01 is a hydrocarbon group which may have a substituent, as Ra 01 The hydrocarbon group may be a linear or branched alkyl group, a linear or branched alkenyl group, or a cyclic hydrocarbon group.

[0131] The number of carbon atoms in the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl groups. Among them, methyl, ethyl, and n-butyl groups are preferred, and methyl or ethyl groups are more preferred.

[0132] The number of carbon atoms in the branched alkyl group is preferably 3 to 10, more preferably 3 to 5. Specific examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl, with isopropyl being preferred.

[0133] The linear or branched alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms.

[0134] In Ra 01 In the case of a cyclic hydrocarbon group, the hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0135] The alicyclic hydrocarbon group as the monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

[0136] The alicyclic hydrocarbon group as the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane. The polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0137] In Ra 01 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0138] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.

[0139] Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting such aromatic hydrocarbon rings are replaced with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen, sulfur, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine and thiophene rings.

[0140] As Ra 01Specifically, the aromatic hydrocarbon group in the formula (a) may be a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl or heteroaryl); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); or a group obtained by replacing one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocyclic ring with an alkylene group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0141] Ra 01 The hydrocarbon group in may have a substituent. As such a substituent, for example -R P1 、-R P2 -OR P1 、-R P2 -CO-R P1 、-R P2 -CO-OR P1 、-R P2 -O-CO-R P1 、-R P2 -OH, -R P2 -CN or -R P2 -COOH (hereinafter these substituents are collectively referred to as "Ra x5 ")wait.

[0142] Here, R P1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. P2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. P1 and R P2 A part or all of the hydrogen atoms in the chain saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group and aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the above substituents, or may have more than one of each of the above substituents.

[0143] Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group.

[0144] Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octyl, tricyclo[5.2.1.02,6]decyl, tricyclo[3.3.1.13,7]decyl, tetracyclo[6.2.1.13,6.02,7]dodecyl and adamantyl.

[0145] Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0146] As Ra 02 、Ra 03 The hydrocarbon group may be exemplified by the above Ra 03 Same hydrocarbon group.

[0147] In Ra 02 With Ra 03 When they are bonded to each other to form a ring, preferably, they are represented by the following general formula (a0-r1-01), the following general formula (a0-r1-02), or the following general formula (a0-r1-03).

[0148] On the other hand, in Ra 01 ~Ra 03 In the case of independent hydrocarbon groups that are not bonded to each other, preferably, a group represented by the following general formula (a0-r1-04) is mentioned.

[0149] [Chemistry 8]

[0150]

[0151] [In the formula (a0-r1-01), Ra 001 It is a linear or branched alkyl group which may have a substituent. 0 Is a carbon atom. 0 For Yaa 0 Groups that together form a cyclic hydrocarbon group. Some or all of the hydrogen atoms in the cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. * indicates a bonding position.

[0152] In the formula (a0-r1-02), Yab 0 Is a carbon atom. 0 For Yab 0A group that together forms a cyclic hydrocarbon group. Some or all of the hydrogen atoms in the cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. 002 ~Ra 004 Each of Ra is independently a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. 002 ~Ra 004 Two or more of them may be bonded to each other to form a ring structure. * indicates the bonding position.

[0153] In formula (a0-r1-03), Yac 0 Is a carbon atom. 0 For Yac 0 A group that together forms a cyclic hydrocarbon group. Some or all of the hydrogen atoms in the cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. 005 represents an aromatic hydrocarbon group. Some or all of the hydrogen atoms in the aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. * indicates a bonding position.

[0154] In the formula (a0-r1-04), Ra 006 and Ra 007 Each independently represents a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in the chain saturated hydrocarbon group may be substituted. 008 is a hydrocarbon group which may have a substituent. * indicates a bonding position.

[0155] In the formula (a0-r1-01), Ra 001 It is a linear or branched alkyl group which may have a substituent.

[0156] The number of carbon atoms in the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl groups. Among them, methyl, ethyl, and n-butyl groups are preferred, and methyl or ethyl groups are more preferred.

[0157] The number of carbon atoms in the branched alkyl group is preferably 3 to 10, more preferably 3 to 5. Specific examples thereof include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl.

[0158] As Ra 001 The substituents that the linear or branched alkyl group may have include the above-mentioned Ra x5 .

[0159] In the formula (a0-r1-01), as Ra 001 Among the above, a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms is preferred, and a linear alkyl group having 1 to 4 carbon atoms is more preferred.

[0160] In formula (a0-r1-01), Yaa 0 is a carbon atom, Xaa 0 For Yaa 0 A group that together forms a cyclic hydrocarbon group.

[0161] The cyclic hydrocarbon group may be an aliphatic hydrocarbon group or a condensed-ring hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0162] The aliphatic hydrocarbon group as the monocyclic group is preferably a group obtained by removing two or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, more preferably a monocycloalkane having 5 or 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

[0163] The aliphatic hydrocarbon group as the polycyclic group is preferably a group obtained by removing two or more hydrogen atoms from a polycycloalkane. The polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0164] The aromatic hydrocarbon group in the condensed-ring hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0165] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.

[0166] Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting such aromatic hydrocarbon rings are replaced with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen, sulfur, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine and thiophene rings.

[0167] Specific examples of the condensed-cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group are shown below.

[0168] [Chemistry 9]

[0169]

[0170] A part or all of the hydrogen atoms in the above-mentioned cyclic hydrocarbon group may be substituted, and a part of the carbon atoms constituting the ring may be substituted with a heteroatom.

[0171] Specific examples of the substituents that replace a part or all of the hydrogen atoms in the cyclic hydrocarbon group include the above-mentioned Ra x5 .

[0172] When a part of the carbon atoms constituting the ring is substituted with a hetero atom, examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.

[0173] As Xaa 0 with Yaa 0 Examples of the heterocyclic ring in the heterocyclic group formed together include aliphatic heterocyclic rings such as tetrahydrofuran, tetrahydropyran and tetrahydrothiophene.

[0174] In the formula (a0-r1-01), Xaa 0 with Yaa 0 The cyclic hydrocarbon group formed is preferably a monocyclic or polycyclic aliphatic hydrocarbon group or a monocyclic aliphatic heterocyclic group among the above, more preferably a monocyclic aliphatic hydrocarbon group, and still more preferably a monocyclic aliphatic hydrocarbon group having 5 or 6 carbon atoms.

[0175] In the formula (a0-r1-02), Yab 0 is a carbon atom, Xab 0 For Yab 0 As the cyclic hydrocarbon group, there can be exemplified the group consisting of Xaa and Xaa. 0 with Yaa 0 The cyclic hydrocarbon group formed is the same hydrocarbon group.

[0176] In the formula (a0-r1-02), Ra 002 ~Ra 004 Each independently represents a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms.

[0177] As Ra 002 ~Ra 004 The monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in the group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a decyl group.

[0178] As Ra 002 ~Ra 004The monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms may be exemplified by monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octyl, tricyclo[5.2.1.02,6]decyl, tricyclo[3.3.1.13,7]decyl, tetracyclo[6.2.1.13,6.02,7]dodecyl and adamantyl.

[0179] Ra 002 ~Ra 004 The chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group in the hydrogen atoms may be substituted. As a substituent for replacing a part or all of the hydrogen atoms of the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group, specifically, the above-mentioned Ra x5 When a part of the carbon atoms constituting the ring is substituted with a hetero atom, examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.

[0180] Ra 002 ~Ra 004 In the embodiment of the present invention, two or more of the carbon-carbon double bond are bonded to each other to form a cyclic structure, thereby generating a group containing a carbon-carbon double bond, as the group containing a carbon-carbon double bond, for example, cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, cyclopentylidene vinyl, cyclohexylidene vinyl, etc. Among them, cyclopentenyl, cyclohexenyl, and cyclopentylidene vinyl are preferred from the viewpoint of easy synthesis.

[0181] In the formula (a0-r1-02), as Ra 002 ~Ra 004 Among the above, each independently preferably is a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom.

[0182] In formula (a0-r1-03), Yac 0 is a carbon atom, Xac 0 For Yac 0 As the cyclic hydrocarbon group, there can be exemplified the group consisting of Xaa and Xaa. 0 with Yaa 0 The cyclic hydrocarbon group formed is the same hydrocarbon group.

[0183] In the formula (a0-r1-03), Ra 005The aromatic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, further preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene, and particularly preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0184] Some or all of the hydrogen atoms in the aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with hetero atoms.

[0185] Specific examples of the substituents that replace a part or all of the hydrogen atoms in the aromatic hydrocarbon group include the above-mentioned Ra x5 When a part of the carbon atoms constituting the ring is substituted with a hetero atom, examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.

[0186] In the formula (a0-r1-04), Ra 006 and Ra 007 Each independently represents a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms.

[0187] As Ra 006 and Ra 007 The monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms may be exemplified by the above Ra 002 ~Ra 004 The same groups as the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms are included.

[0188] In formula (a0-r1-04), as Ra 006 and Ra 007 Among the above, an alkyl group having 1 to 5 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is further preferred.

[0189] In Ra 006 and Ra 007 When the chain saturated hydrocarbon group represented by is substituted, the substituent group may be, for example, the same as the above Ra x5 Same group.

[0190] In the formula (a0-r1-04), Ra 008 is a hydrocarbon group which may have a substituent. 008 The hydrocarbon group in may be a linear or branched alkyl group, a linear or branched alkenyl group, or a cyclic hydrocarbon group.

[0191] Ra 008The number of carbon atoms in the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, methyl, ethyl, n-propyl, n-butyl, and n-pentyl groups may be mentioned. Among them, methyl, ethyl, and n-butyl groups are preferred, and methyl or ethyl groups are more preferred.

[0192] Ra 008 The number of carbon atoms in the branched alkyl group is preferably 3 to 10, more preferably 3 to 5. Specific examples thereof include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl, with isopropyl being preferred.

[0193] As Ra 008 Specific examples of the straight-chain or branched alkenyl group in include straight-chain alkenyl groups such as vinyl, propenyl (allyl), and 2-butenyl; and branched alkenyl groups such as 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0194] In Ra 008 In the case of a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0195] The aliphatic hydrocarbon group as the monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

[0196] The aliphatic hydrocarbon group as the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane. The polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0197] As Ra 008 The aromatic hydrocarbon group in Ra 005 The same group as the aromatic hydrocarbon group in 008 Preferably, it is a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, further preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene, and most preferably a group obtained by removing one or more hydrogen atoms from naphthalene.

[0198] As Ra 008 The substituents that may be present include Ra 005 The substituents that may be possessed are the same as those mentioned above.

[0199] Ra in the formula (a0-r1-04) 008 In the case of a naphthyl group, the position of bonding to the tertiary carbon atom in the above formula (a1-r2-4) may be either the 1-position or the 2-position of the naphthyl group.

[0200] Ra in the formula (a0-r1-04) 008 In the case of an anthracene group, the position of bonding to the tertiary carbon atom in the formula (a0-r1-04) may be any of the 1-position, 2-position, and 9-position of the anthracene group.

[0201] As Ra in the formula (a0-r1-04) 008 Among the above, a linear or branched alkyl group or a linear or branched alkenyl group is preferred, a linear or branched alkyl group is more preferred, and a linear alkyl group is further preferred.

[0202] Specific examples of the group represented by the formula (a0-r1-01) are listed below.

[0203] [Chemistry 10]

[0204]

[0205] [Chemistry 11]

[0206]

[0207] [Chemistry 12]

[0208]

[0209] Specific examples of the group represented by the formula (a0-r1-02) are listed below.

[0210] [Chemistry 13]

[0211]

[0212] [Chemistry 14]

[0213]

[0214] [Chemistry 15]

[0215]

[0216] Specific examples of the group represented by the formula (a0-r1-03) are listed below.

[0217] [Chemistry 16]

[0218]

[0219] Specific examples of the group represented by the formula (a0-r1-04) are listed below.

[0220] [Chemistry 17]

[0221]

[0222] In the above formula (a0-1), as Ra 0 Among the above, the acid-dissociable group is preferably a group represented by the above formula (a0-r1-01) or a group represented by the above formula (a0-r1-04), and more preferably a group represented by the above formula (a0-r1-04).

[0223] The ratio of the structural unit (a01) in the component (A1) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the component (A1).

[0224] When the ratio of the structural unit (a01) is equal to or greater than the lower limit of the preferred range, lithographic characteristics such as sensitivity, CD stability, adhesion, and pattern shape are further improved.

[0225] On the other hand, when it is below the upper limit of the preferred range, a balance with other structural units can be achieved, and various lithographic characteristics become good.

[0226] Structural Unit (a10)

[0227] The structural unit (a10) is a structural unit represented by the following general formula (a10-1) (excluding the structural unit belonging to the structural unit (a01)).

[0228] [Chemistry 18]

[0229]

[0230] [wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. x1 Is a single bond or a divalent connecting group. x1 It is an aromatic hydrocarbon group which may have a substituent. ax1 is an integer greater than 1.]

[0231] In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.

[0232] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is particularly preferred.

[0233] In the formula (a10-1), Ya x1 It is a single bond or a divalent linking group.

[0234] In the chemical formula, as Ya x1 The divalent linking group in is not particularly limited, and preferred linking groups include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom.

[0235] As Ya x1 , preferably a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, more preferably a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], further preferably a single bond.

[0236] In the formula (a10-1), Wa x1 It is an aromatic hydrocarbon group which may have a substituent.

[0237] As Wa x1 The aromatic hydrocarbon group in the embodiment may be a hydrocarbon group which is removed from an aromatic ring which may have a substituent (n ax1 +1) hydrogen atoms. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. As the aromatic ring, specifically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted by heteroatoms, etc. As heteroatoms in the aromatic heterocycle, oxygen atoms, sulfur atoms, nitrogen atoms, etc. can be mentioned. As the aromatic heterocycle, specifically, pyridine rings, thiophene rings, etc. can be mentioned.

[0238] In addition, as Wa x1 The aromatic hydrocarbon group in the present invention may be removed from an aromatic compound containing two or more aromatic rings which may have substituents (e.g., biphenyl, fluorene, etc.) (n ax1 +1) hydrogen atoms.

[0239] Among the above, as Wa x1 , preferably from benzene, naphthalene, anthracene or biphenyl (n ax1 +1) hydrogen atoms, more preferably a group obtained by removing (n ax1+1) hydrogen atoms, preferably (n ax1 +1) hydrogen atoms.

[0240] Wa x1 The aromatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include the same as Ya x1 The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group.

[0241] Wa x1 The aromatic hydrocarbon group in preferably has no substituent.

[0242] In the formula (a10-1), n ax1 It is an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1 or 2, and particularly preferably 1.

[0243] Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below.

[0244] In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0245] [Chemistry 19]

[0246]

[0247] [Chemistry 20]

[0248]

[0249] [Chemistry 21]

[0250]

[0251] The structural unit (a10) contained in the component (A1) may be one type or two or more types.

[0252] When the component (A1) has a structural unit (a10), the ratio of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 80 mol%, relative to the total (100 mol%) of all structural units constituting the component (A1).

[0253] By setting the ratio of the structural unit (a10) to be equal to or greater than the lower limit, lithography characteristics such as sensitivity, CD stability, adhesion, and pattern shape are further improved.

[0254] On the other hand, by setting it to be below the upper limit of the above-mentioned preferred range, it becomes easy to achieve a balance with other structural units.

[0255] Other structural units

[0256] The component (A1) may have other structural units as needed in addition to the structural units (a01) and (a10).

[0257] As other structural units, for example, there can be mentioned: a structural unit (a1) containing an acid-decomposable group whose polarity increases due to the action of an acid; a structural unit (a2) containing a lactone cyclic group, a -SO2- cyclic group or a carbonate cyclic group; a structural unit (a3) ​​containing an aliphatic hydrocarbon group containing a polar group; a structural unit (a4) containing an acid-non-dissociable aliphatic cyclic group; a structural unit (st) derived from styrene or a styrene derivative, etc.

[0258] Regarding structural unit (a1):

[0259] The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid, but does not include the structural units (a01) or (a10) described above.

[0260] Examples of the acid-dissociable group include groups that have been proposed as acid-dissociable groups for base resins for chemically amplified resist compositions.

[0261] Specifically, groups proposed as acid-dissociating groups of the base resin for chemically amplified resist compositions include the "tertiary alkyl ester type acid-dissociating group" represented by the above-mentioned general formula (a01-r-1), the "acetal type acid-dissociating group" and the "tertiary alkoxycarbonyl acid-dissociating group" described below.

[0262] Acetal acid-dissociative group:

[0263] Examples of the acid-dissociable group that protects the carboxyl group or hydroxyl group in the polar group include an acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group").

[0264] [Chemistry 22]

[0265]

[0266] [where Ra' 1 、Ra'2 is a hydrogen atom or an alkyl group. 3 is a hydrocarbon group, and Ra' 3 Can be with Ra' 1 、Ra' 2 Any one of them is bonded to form a ring.]

[0267] In formula (a1-r-1), Ra' is preferred 1 and Ra' 2 At least one of them is a hydrogen atom, and more preferably both of them are hydrogen atoms.

[0268] In Ra' 1 or Ra' 2 In the case of an alkyl group, examples of the alkyl group include the same alkyl groups as those exemplified as substituents that may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylate above, and preferably an alkyl group having 1 to 5 carbon atoms. Specifically, preferred examples include linear or branched alkyl groups. More specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. Methyl or ethyl groups are more preferred, and methyl groups are particularly preferred.

[0269] In formula (a1-r-1), as Ra' 3 The hydrocarbon group may be a linear or branched alkyl group or a cyclic hydrocarbon group.

[0270] Ra' 3 The linear or branched alkyl group, cyclic hydrocarbon group (aliphatic hydrocarbon group as a monocyclic group, aliphatic hydrocarbon group as a polycyclic group, aromatic hydrocarbon group) in the formula (R) can be exemplified by the above-mentioned 01 Same group.

[0271] In Ra' 3 With Ra' 1 、Ra' 2 When any one of them is bonded to form a ring, the cyclic group is preferably a four- to seven-membered ring, and more preferably a four- to six-membered ring. Specific examples of the cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0272] Tertiary alkoxycarbonyl acid dissociative group:

[0273] Examples of the acid-dissociable group that protects the hydroxyl group in the polar group include an acid-dissociable group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as a "tertiary alkoxycarbonyl acid-dissociable group" for convenience of explanation).

[0274] [Chemistry 23]

[0275]

[0276] [where Ra' 7 ~Ra' 9 are alkyl groups, respectively.]

[0277] In formula (a1-r-3), Ra' 7 ~Ra' 9 An alkyl group having 1 to 5 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred.

[0278] Furthermore, the total number of carbon atoms of the alkyl groups is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0279] As the structural unit (a1), a structural unit represented by the following general formula (a1-1-1) may be mentioned.

[0280] [Chemistry 24]

[0281]

[0282] [Wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va 1 It is a divalent hydrocarbon group which may have an ether bond. a1 is an integer from 0 to 2. 1 " is an acid-dissociable group.

[0283] *Indicates bonding position.]

[0284] The ratio of the structural unit (a1) in the component (A1) is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and even more preferably 0 to 5 mol%, based on the total (100 mol%) of all structural units constituting the component (A1).

[0285] By setting the ratio of the structural unit (a1) within the above-mentioned preferred range, lithography characteristics such as sensitivity, resolution, and roughness improvement are further improved.

[0286] Regarding structural unit (a2):

[0287] The component (A1) may further have a structural unit (a2) containing a lactone cyclic group, a -SO2- cyclic group, or a carbonate cyclic group (excluding structural units belonging to the structural unit (a01) or the structural unit (a1)).

[0288] When component (A1) is used to form a resist film, the lactone cyclic group, -SO2- cyclic group, or carbonate cyclic group in the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate. Furthermore, the presence of the structural unit (a2) improves photolithographic properties, for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0289] A "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -OC(=O)- in its ring backbone. A lactone ring is counted as the first ring. A group consisting solely of the lactone ring is referred to as a monocyclic group. A group containing other ring structures is referred to as a polycyclic group regardless of their structure. A lactone-containing cyclic group may be either a monocyclic group or a polycyclic group.

[0290] The lactone-containing ring group in the structural unit (a2) is not particularly limited, and any lactone-containing ring group can be used. Specifically, groups represented by the following general formulae (a2-r-1) to (a2-r-7) can be mentioned.

[0291] [Chemistry 25]

[0292]

[0293] [where Ra' 21 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2-containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom which may contain an oxygen atom (-O-) or a sulfur atom (-S-); n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bonding position.]

[0294] In the general formulas (a2-r-1) to (a2-r-7), Ra' 21 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. Among these, methyl or ethyl is preferred, and methyl is particularly preferred.

[0295] As Ra' 21 The alkoxy group in the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra' 21 The alkyl group in the alkyl group is a group formed by connecting an oxygen atom (-O-) to the alkyl group exemplified.

[0296] As Ra' 21 The halogen atom in , is preferably a fluorine atom.

[0297] As Ra' 21 The haloalkyl group in the above-mentioned Ra' 21 A group in which a part or all of the hydrogen atoms of the alkyl group are substituted by the halogen atoms. The halogenated alkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0298] In Ra' 21 In -COOR" and -OC(=O)R", R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group or a -SO2-containing cyclic group.

[0299] The alkyl group in R" may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms.

[0300] When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0301] When R" is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10. Specifically, examples include groups obtained by removing one or more hydrogen atoms from a monocycloalkane which may be substituted or unsubstituted with a fluorine atom or a fluoroalkyl group; groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes; and more specifically, groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0302] Examples of the lactone ring-containing group in R" include the same groups as those represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7).

[0303] Examples of the carbonate-containing cyclic group in R″ include the carbonate-containing cyclic group described below, and specifically, groups represented by the general formulae (ax3-r-1) to (ax3-r-3) may be mentioned.

[0304] The -SO2-containing cyclic group in R" is the same as the -SO2-containing cyclic group described later, and specifically, groups represented by general formulae (a5-r-1) to (a5-r-4) can be mentioned.

[0305] As Ra' 21The hydroxyalkyl group in the hydroxyalkyl group is preferably a hydroxyalkyl group having 1 to 6 carbon atoms. Specifically, the Ra' 21 A group in which at least one hydrogen atom of an alkyl group is substituted with a hydroxy group.

[0306] As Ra' 21 , among the above, preferably each independently represents a hydrogen atom or a cyano group.

[0307] In the general formulas (a2-r-2), (a2-r-3) and (a2-r-5), as the alkylene group with 1 to 5 carbon atoms in A", a linear or branched alkylene group is preferred, and examples include methylene, ethylene, n-propylene, isopropylene and the like. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups with -O- or -S- at the end of the alkylene group or between carbon atoms, such as O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2- and the like. As A", an alkylene group with 1 to 5 carbon atoms or -O- is preferred, an alkylene group with 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0308] Specific examples of the groups represented by general formulae (a2-r-1) to (a2-r-7) are listed below.

[0309] [Chemistry 26]

[0310]

[0311] [Chemistry 27]

[0312]

[0313] A "-SO2-containing cyclic group" refers to a cyclic group containing a ring containing -SO2- in its ring backbone. Specifically, it refers to a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring backbone of the cyclic group. The ring containing -SO2- is counted as the first ring in the ring backbone. A group consisting of only this ring is referred to as a monocyclic group. A group containing other ring structures is referred to as a polycyclic group regardless of the structure. A -SO2-containing cyclic group may be either a monocyclic group or a polycyclic group.

[0314] The -SO2-containing cyclic group is particularly preferably a cyclic group containing -O-SO2- in its ring skeleton, that is, a cyclic group containing a sultone ring in which -OS- in -O-SO2- forms a part of the ring skeleton.

[0315] More specifically, the -SO2-containing cyclic group includes groups represented by the following general formulae (a5-r-1) to (a5-r-4).

[0316] [Chemistry 28]

[0317]

[0318] [where Ra' 51 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2-containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, which may contain an oxygen atom or a sulfur atom; and n' is an integer from 0 to 2. * indicates a bonding position.]

[0319] In the general formulas (a5-r-1) to (a5-r-2), A" is the same as A" in the general formulas (a2-r-2), (a2-r-3), and (a2-r-5).

[0320] As Ra' 51 The alkyl, alkoxy, halogen atom, haloalkyl, -COOR", -OC(=O)R", hydroxyalkyl, can be exemplified by the same as Ra' in the above general formula (a2-r-1) to (a2-r-7). 21 The same groups as exemplified in the description of .

[0321] Specific examples of the groups represented by the general formulae (a5-r-1) to (a5-r-4) are listed below: "Ac" in the formulae represents an acetyl group.

[0322] [Chemistry 29]

[0323]

[0324] [Chemistry 30]

[0325]

[0326] [Chemistry 31]

[0327]

[0328] A "carbonate-containing cyclic group" refers to a cyclic group containing a ring (carbonate ring) containing -OC(=O)-O- in its ring skeleton. A carbonate ring is counted as the first ring. A group consisting solely of a carbonate ring is referred to as a monocyclic group. A group containing other ring structures is referred to as a polycyclic group regardless of the structure. A carbonate-containing cyclic group may be either a monocyclic group or a polycyclic group.

[0329] The carbonate-containing cyclic group is not particularly limited, and any carbonate-containing cyclic group can be used. Specifically, groups represented by the following general formulae (ax3-r-1) to (ax3-r-3) can be mentioned.

[0330] [Chemistry 32]

[0331]

[0332] [where Ra' x31 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2-containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom which may contain an oxygen atom or a sulfur atom; p' is an integer from 0 to 3, and q' is 0 or 1. * indicates a bonding position.]

[0333] In the general formulas (ax3-r-2) to (ax3-r-3), A” is the same as A” in the general formulas (a2-r-2), (a2-r-3), and (a2-r-5).

[0334] As Ra' 31 The alkyl, alkoxy, halogen atom, haloalkyl, -COOR", -OC(=O)R", hydroxyalkyl, can be exemplified by the same as Ra' in the above general formula (a2-r-1) to (a2-r-7). 21 The same groups as exemplified in the description of .

[0335] Specific examples of the groups represented by the general formulae (ax3-r-1) to (ax3-r-3) are listed below.

[0336] [Chemistry 33]

[0337]

[0338] Among these, the structural unit (a2) is preferably a structural unit derived from an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.

[0339] The structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

[0340] [Chemistry 34]

[0341]

[0342] [wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 21is a single bond or a divalent linking group. 21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, R' represents a hydrogen atom or a methyl group. 21 In the case of -O-, Ya 21 It won't be -CO-. 21 It is a lactone cyclic group, a carbonate cyclic group or a -SO2- cyclic group.]

[0343] In the formula (a2-1), R is the same as described above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms, and is particularly preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0344] In the formula (a2-1), as Ya 21 The divalent linking group in is not particularly limited, and preferred examples include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom.

[0345] ·Divalent hydrocarbon group which may have a substituent:

[0346] In Ya 21 In the case of a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0347] ··Ya 21 Aliphatic hydrocarbon groups

[0348] The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0349] Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure.

[0350] ···Straight-chain or branched aliphatic hydrocarbon group

[0351] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0352] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples thereof include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0353] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

[0354] As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specific examples include -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2- and the like alkylmethylene groups; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2- and the like alkylethylene groups; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and the like alkylpropylene groups; and -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2- and the like alkylbutylene groups. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0355] The linear or branched aliphatic hydrocarbon group may or may not have a substituent, and examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

[0356] Aliphatic hydrocarbon groups containing rings in their structures

[0357] Examples of the aliphatic hydrocarbon group containing a ring in its structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may have a substituent including a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group include the same aliphatic hydrocarbon groups as described above.

[0358] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0359] The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a polycycloalkane having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0360] The cyclic aliphatic hydrocarbon group may or may not have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and a carbonyl group.

[0361] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0362] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and still more preferably a methoxy group and an ethoxy group.

[0363] The halogen atom as the substituent is preferably a fluorine atom.

[0364] Examples of the haloalkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0365] In a cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a heteroatom-containing substituent. Preferred heteroatom-containing substituents include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0366] ··Ya 21 Aromatic hydrocarbon groups

[0367] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0368] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. This number of carbon atoms does not include the number of carbon atoms in the substituent.

[0369] Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting such aromatic hydrocarbon rings are replaced with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen, sulfur, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine and thiophene rings.

[0370] Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring or aromatic heterocyclic ring (an arylene group or a heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring or aromatic heterocyclic ring (an aryl group or a heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, or 2-naphthylethyl). The alkylene group bonded to the aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0371] In the aromatic hydrocarbon group, a hydrogen atom in the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of such substituents include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, and a hydroxyl group.

[0372] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0373] Examples of the alkoxy group, halogen atom, and haloalkyl group as the substituent include the groups exemplified as the substituents substituting for the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0374] Heteroatom-containing divalent linking group:

[0375] In Ya 21 In the case of a divalent linking group containing a heteroatom, preferred linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and groups of the general formula -Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21-、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -represented by a group [wherein, Y 21 and Y 22 Each independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3] and the like.

[0376] When the heteroatom-containing bivalent linking group is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H group thereof may be substituted by a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

[0377] General formula-Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -Medium,Y 21 and Y 22 Each independently represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the following: 21 The same groups as those exemplified in the description of the divalent linking group (the divalent hydrocarbon group which may have a substituent).

[0378] As Y 21 , preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, further preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0379] As Y 22 , preferably a straight-chain or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0380] In the form of -[Y 21 -C(=O)-O] m” -Y 22 -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as a group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 -, particularly preferably a group represented by the formula -Y 21 -C(=O)-OY 22 - represented by a group. Among them, preferably a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ -. In this formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1.

[0381] Among them, as Ya 21 , preferably a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof.

[0382] In the formula (a2-1), Ra 21 It contains a lactone cyclic group, a -SO2- cyclic group or a carbonate cyclic group.

[0383] As Ra 21 The lactone-containing cyclic group, -SO2--containing cyclic group, and carbonate-containing cyclic group can be preferably exemplified by the above-mentioned groups represented by the general formulae (a2-r-1) to (a2-r-7), the groups represented by the general formulae (a5-r-1) to (a5-r-4), and the groups represented by the general formulae (ax3-r-1) to (ax3-r-3).

[0384] Among them, preferred are lactone cyclic groups or -SO2- cyclic groups, more preferred are groups represented by the general formula (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r-1), and further preferred are groups represented by the general formula (a2-r-2) or (a5-r-1). Specifically, any group represented by the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r-lc-6-1), (r-sl-1-1), and (r-sl-1-18) is preferred, any group represented by the chemical formulas (r-lc-2-1) to (r-lc-2-18), and (r-sl-1-1) is more preferred, and any group represented by the chemical formulas (r-lc-2-1), (r-lc-2-12), and (r-sl-1-1) is further preferred.

[0385] The structural unit (a2) contained in the component (A1) may be one type or two or more types.

[0386] The ratio of the structural unit (a2) in the component (A1) is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and even more preferably 0 to 5 mol%, based on the total (100 mol%) of all structural units constituting the component (A1).

[0387] When the ratio of the structural unit (a2) is within the above-mentioned preferred range, a balance with other structural units can be achieved, and various lithographic characteristics become favorable.

[0388] Regarding structural unit (a3):

[0389] In addition to the structural unit (a1), the component (A1) may further include a structural unit (a3) ​​containing a polar group-containing aliphatic hydrocarbon group (excluding structural units belonging to the structural unit (a01), structural unit (a1), or structural unit (a2)). The inclusion of the structural unit (a3) ​​in the component (A1) improves the hydrophilicity of the component (A), contributing to improved resolution. Furthermore, the acid diffusion length can be appropriately adjusted.

[0390] The polar group may, for example, be a hydroxyl group, a cyano group, a carboxyl group, or a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with fluorine atoms. A hydroxyl group is particularly preferred.

[0391] Examples of the aliphatic hydrocarbon group include linear or branched hydrocarbon groups (preferably alkylene groups) and cyclic aliphatic hydrocarbon groups (cyclic groups) having 1 to 10 carbon atoms. The cyclic group may be a monocyclic group or a polycyclic group, and for example, the cyclic groups mentioned many times for the resin for the ArF excimer laser resist composition can be appropriately selected and used.

[0392] When the cyclic group is a monocyclic group, the number of carbon atoms is more preferably 3 to 10. Among them, a structural unit derived from an acrylic acid ester containing an aliphatic monocyclic group is more preferred, wherein the aliphatic monocyclic group contains a hydroxyl group, a cyano group, a carboxyl group, or a hydroxyalkyl group in which a portion of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. As the monocyclic group, a group obtained by removing two or more hydrogen atoms from a monocycloalkane can be exemplified. Specifically, a group obtained by removing two or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, or cyclooctane can be exemplified. Among these monocyclic groups, a group obtained by removing two or more hydrogen atoms from cyclopentane and a group obtained by removing two or more hydrogen atoms from cyclohexane are industrially preferred.

[0393] When the cyclic group is a polycyclic group, the number of carbon atoms of the polycyclic group is more preferably 7 to 30. Among them, a structural unit derived from an acrylate containing an aliphatic polycyclic group is more preferred, wherein the aliphatic polycyclic group contains a hydroxyl group, a cyano group, a carboxyl group, or a hydroxyalkyl group in which a portion of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Examples of the polycyclic group include groups obtained by removing two or more hydrogen atoms from bicycloalkanes, tricycloalkanes, tetracycloalkanes, and the like. Specifically, groups obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be mentioned. Among these polycyclic groups, groups obtained by removing two or more hydrogen atoms from adamantane, groups obtained by removing two or more hydrogen atoms from norbornane, and groups obtained by removing two or more hydrogen atoms from tetracyclododecane are industrially preferred.

[0394] The structural unit (a3) ​​is not particularly limited as long as it contains an aliphatic hydrocarbon group containing a polar group, and any structural unit can be used.

[0395] The structural unit (a3) ​​is preferably a structural unit derived from an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and a structural unit containing an aliphatic hydrocarbon group containing a polar group.

[0396] As the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a structural unit derived from hydroxyethyl acrylic acid is preferred.

[0397] In addition, when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a polycyclic group, the preferred structural unit as the structural unit (a3) ​​may include the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-3); when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a monocyclic group, the preferred structural unit as the structural unit (a3) ​​may include the structural unit represented by the formula (a3-4).

[0398] [Chemistry 35]

[0399]

[0400] [In the formula, R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t' is an integer of 1 to 3, l is an integer of 0 to 5, and s is an integer of 1 to 3.]

[0401] In formula (a3-1), j is preferably 1 or 2, more preferably 1. When j is 2, the hydroxyl group preferably bonds to the 3- and 5-positions of the adamantyl group. When j is 1, the hydroxyl group preferably bonds to the 3-position of the adamantyl group.

[0402] j is preferably 1, and it is particularly preferred that the hydroxyl group is bonded to the 3-position of the adamantyl group.

[0403] In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5-position or 6-position of the norbornyl group.

[0404] In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. A 2-norbornyl group or a 3-norbornyl group is preferably bonded to the terminal of the carboxyl group of the acrylic acid. The fluoroalkyl alcohol is preferably bonded to the 5- or 6-position of the norbornyl group.

[0405] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluoroalkyl alcohol is preferably bonded to the 3- or 5-position of the cyclohexyl group.

[0406] The structural unit (a3) ​​contained in the component (A1) may be one type or two or more types.

[0407] When the component (A1) has a structural unit (a3), the proportion of the structural unit (a3) ​​is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and even more preferably 5 to 20 mol%, relative to the total of all structural units constituting the component (A1) (100 mol%).

[0408] By making the proportion of structural unit (a3) ​​above the preferred lower limit, the effect brought about by containing structural unit (a3) ​​can be fully obtained through the above-mentioned effect. If it is below the preferred upper limit, a balance with other structural units can be achieved, and various lithography characteristics become good.

[0409] Regarding structural unit (a4):

[0410] The component (A1) may further have a structural unit (a4) containing an acid-non-dissociable aliphatic cyclic group in addition to the structural unit (a1).

[0411] By including the structural unit (a4) in the component (A1), the dry etching resistance of the resulting resist pattern is improved. Furthermore, the hydrophobicity of the component (A) is improved. The improved hydrophobicity contributes to improvements in resolution, resist pattern shape, and the like, particularly in solvent development processes.

[0412] The "acid-non-dissociable cyclic group" in the structural unit (a4) is a cyclic group that does not dissociate even under the action of an acid when an acid is generated in the resist composition by exposure (for example, when an acid is generated by the structural unit that generates an acid by exposure or the component (B)). The cyclic group remains in the structural unit as it is.

[0413] As the structural unit (a4), for example, a structural unit derived from an acrylate containing an acid-non-dissociable aliphatic cyclic group is preferred. As the cyclic group, a large number of groups conventionally known as groups used as resin components of resist compositions for ArF excimer lasers, KrF excimer lasers (preferably ArF excimer lasers) and the like can be used.

[0414] From the viewpoint of industrial availability, the cyclic group is particularly preferably at least one selected from tricyclodecanyl, adamantyl, tetracyclododecyl, isobornyl, and norbornyl. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

[0415] Specific examples of the structural unit (a4) include structural units represented by the following general formulae (a4-1) to (a4-7).

[0416] [Chemistry 36]

[0417]

[0418] [Where R α Same as above.]

[0419] The structural unit (a4) contained in the component (A1) may be one type or two or more types.

[0420] The ratio of the structural unit (a4) in the component (A1) is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and even more preferably 0 to 5 mol%, based on the total (100 mol%) of all structural units constituting the component (A1).

[0421] When the ratio of the structural unit (a4) is within the above-mentioned preferred range, a balance with other structural units can be achieved, and various lithographic properties become favorable.

[0422] About structural unit (st):

[0423] The structural unit (st) is a structural unit derived from styrene or a styrene derivative. A "structural unit derived from styrene" is a structural unit formed by cleaving the olefinic double bonds of styrene. A "structural unit derived from a styrene derivative" is a structural unit formed by cleaving the olefinic double bonds of a styrene derivative.

[0424] "Styrene derivatives" refer to compounds in which at least some of the hydrogen atoms of styrene are replaced by substituents. Examples of styrene derivatives include compounds in which the hydrogen atom at the α-position of styrene is replaced by a substituent, compounds in which one or more hydrogen atoms on the benzene ring of styrene are replaced by substituents, and compounds in which the hydrogen atom at the α-position of styrene and one or more hydrogen atoms on the benzene ring are replaced by substituents.

[0425] As the substituent substituting the hydrogen atom at the α-position of styrene, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms may be mentioned.

[0426] The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl.

[0427] The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. The halogen atom is particularly preferably a fluorine atom.

[0428] As the substituent replacing the hydrogen atom at the α-position of styrene, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is further preferred from the perspective of industrial availability.

[0429] Examples of the substituent for substituting the hydrogen atom of the benzene ring of styrene include an alkyl group, an alkoxy group, a halogen atom, and a haloalkyl group.

[0430] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0431] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and still more preferably a methoxy group and an ethoxy group.

[0432] The halogen atom as the substituent is preferably a fluorine atom.

[0433] Examples of the haloalkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0434] As the substituent for the hydrogen atom of the benzene ring of styrene, an alkyl group having 1 to 5 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is further preferred.

[0435] As the structural unit (st), a structural unit derived from styrene, or a structural unit derived from a styrene derivative obtained by replacing the hydrogen atom at the α-position of styrene with an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms is preferred, a structural unit derived from styrene, or a structural unit derived from a styrene derivative obtained by replacing the hydrogen atom at the α-position of styrene with a methyl group is more preferred, and a structural unit derived from styrene is still more preferred.

[0436] The structural unit (st) contained in the component (A1) may be one type or two or more types.

[0437] When the component (A1) has a structural unit (st), the ratio of the structural unit (st) is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 30 mol%, relative to the total (100 mol%) of all structural units constituting the component (A1).

[0438] The component (A1) contained in the resist composition may be used alone or in combination of two or more.

[0439] In the resist composition of this embodiment, as the component (A1), a polymer compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10) can be cited, preferably a polymer compound consisting only of a repeating structure of the structural unit (a01) and the structural unit (a10), or a polymer compound consisting only of a repeating structure of the structural unit (a01), the structural unit (a10), and the structural unit (st).

[0440] In particular, from the viewpoint of improving pattern shape and CD stability, a polymer compound consisting only of a repeating structure of the structural unit (a01), the structural unit (a10), and the structural unit (st) is preferred.

[0441] In the polymer compound having a repeating structure of the structural unit (a01) and the structural unit (a10), the proportion of the structural unit (a01) relative to the total of all the structural units constituting the polymer compound (100 mol%) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0442] The proportion of the structural unit (a10) in the polymer compound is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol%, relative to the total of all structural units constituting the polymer compound (100 mol%).

[0443] In the polymer compound having a repeating structure of structural unit (a01), structural unit (a10) and structural unit (st), the proportion of structural unit (a01) relative to the total of all structural units constituting the polymer compound (100 mol%) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 40 mol%.

[0444] The proportion of the structural unit (a10) in the polymer compound is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total of all structural units constituting the polymer compound (100 mol%).

[0445] The ratio of the structural unit (st) in the polymer compound is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, and even more preferably 5 to 30 mol%, relative to the total of all structural units constituting the polymer compound (100 mol%).

[0446] The molar ratio of the structural unit (a01) to the structural unit (a10) in the polymer compound (structural unit (a01):structural unit (a10)) is preferably 1:9 to 6:4, more preferably 1:9 to 5:5, and even more preferably 2:8 to 4:6.

[0447] The component (A1) can be produced by dissolving monomers from which the structural units are derived in a polymerization solvent, and adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (eg, V-601) to carry out polymerization.

[0448] Alternatively, the component (A1) can be produced by dissolving a monomer from which the structural unit (a01) is derived, a monomer from which the structural unit (a10) is derived, and, if necessary, a monomer from which a structural unit other than the structural units (a01) and (a10) (e.g., the structural unit (st)) is derived in a polymerization solvent, adding the above-described free radical polymerization initiator thereto to carry out polymerization, and then carrying out a deprotection reaction.

[0449] Furthermore, during polymerization, a -C(CF3)2-OH group can be introduced at the terminal by using a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH. Such copolymers containing a hydroxyalkyl group in which some of the alkyl group's hydrogen atoms are replaced with fluorine atoms are effective in reducing development defects and LER (line edge roughness: uneven surface roughness of line sidewalls).

[0450] The weight average molecular weight (Mw) of the component (A1) (polystyrene conversion basis based on gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.

[0451] When the Mw of the component (A1) is below the preferred upper limit of the range, the solubility in the resist solvent is sufficient for use as a resist, while when it is above the preferred lower limit of the range, the dry etching resistance and the cross-sectional shape of the resist pattern are good.

[0452] The molecular weight distribution coefficient (Mw / Mn) of the component (A1) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. In addition, Mn represents the number average molecular weight.

[0453] Regarding ingredient (A2)

[0454] The resist composition of the present embodiment may contain, as the component (A), a base component (hereinafter referred to as "component (A2)") which is not included in the component (A1) and whose solubility in a developer is changed by the action of an acid.

[0455] The component (A2) is not particularly limited, and may be arbitrarily selected from a large number of components conventionally known as base components for chemically amplified resist compositions and used.

[0456] As the component (A2), a high molecular compound or a low molecular compound may be used alone or in combination of two or more.

[0457] The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more, and may be 100% by mass, relative to the total mass of component (A). When this proportion is 25% by mass or more, a resist pattern having excellent lithographic properties such as increased sensitivity, improved resolution, and improved roughness can be easily formed.

[0458] In the resist composition of the present embodiment, the content of the component (A) may be adjusted according to the thickness of the resist film to be formed, etc.

[0459] <Acid Generator Component (B)>

[0460] The resist composition of this embodiment further contains an acid generator component (B) that generates an acid by exposure.

[0461] The component (B) is not particularly limited, and any acid generator that has been proposed as an acid generator for a chemically amplified resist composition can be used.

[0462] Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, sulfonic acid oxime ester acid generators; diazomethane acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes; nitrobenzylsulfonate acid generators, iminosulfonate acid generators, imidosulfonate acid generators, disulfone acid generators, and the like.

[0463] As the component (B), among the above, an onium salt-based acid generator or an imide sulfonate-based acid generator is preferred.

[0464] Onium Salt Acid Generators

[0465] Examples of onium salt acid generators include compounds represented by the general formula (b-1) (hereinafter also referred to as “component (b-1)”), compounds represented by the general formula (b-2) (hereinafter also referred to as “component (b-2)”), and compounds represented by the general formula (b-3) (hereinafter also referred to as “component (b-3)”).

[0466] [Chemistry 37]

[0467]

[0468] [Where R 101 and R 104 ~R 108 Each of R is independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. 104 With R 105 They can bond with each other to form a ring structure. 102 Y is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom.101 It is a divalent linking group or a single bond containing an oxygen atom. 101 ~V 103 are independently a single bond, an alkylene group or a fluoroalkylene group. 101 ~L 102 are independently a single bond or an oxygen atom. 103 ~L 105 Each independently represents a single bond, -CO- or -SO2-. m is an integer greater than 1, and M m+ is an m-valent onium cation.]

[0469] {Anion Section}

[0470] Anions in component (b-1)

[0471] In formula (b-1), R 101 It is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0472] The cyclic group which may have a substituent:

[0473] The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group is preferably saturated.

[0474] R 101 The aromatic hydrocarbon group in is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.

[0475] As R 101 Specifically, the aromatic ring possessed by the aromatic hydrocarbon group in the group may be benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocycle in which a portion of the carbon atoms constituting these aromatic rings are substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0476] As R 101 Specifically, the aromatic hydrocarbon group in the alkyl group may be a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl, naphthyl, etc.), or a group obtained by replacing one hydrogen atom of the aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, etc.). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0477] R 101The cyclic aliphatic hydrocarbon group in the cyclic aliphatic hydrocarbon group may include an aliphatic hydrocarbon group containing a ring in the structure.

[0478] Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed between straight-chain or branched aliphatic hydrocarbon groups.

[0479] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0480] The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferred. Among them, as the polycycloalkane, polycycloalkane having a cross-linked ring type polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; polycycloalkane having a condensed ring type polycycloalkane such as a cyclic group having a steroid skeleton is more preferred.

[0481] Among them, as R 101 The cyclic aliphatic hydrocarbon group in is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, further preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0482] The number of carbon atoms in the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include methylene [—CH 2 —], ethylene [—(CH 2 ) 2 —], propylene [—(CH 2 ) 3 —], butylene [—(CH 2 ) 4 —], and pentylene [—(CH 2 ) 5 —].

[0483] The number of carbon atoms in the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 2 to 10, more preferably 3 to 6, further preferably 3 or 4, and most preferably 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specific examples include -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2- and the like alkylmethylene groups; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2- and the like alkylethylene groups; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and the like alkylpropylene groups; and -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2- and the like alkylbutylene groups. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0484] In addition, R 101 The cyclic hydrocarbon group in the formula (a2-r-1) to (a2-r-7) may contain heteroatoms, such as heterocyclic groups. Specifically, lactone-containing cyclic groups represented by the general formulas (a5-r-1) to (a5-r-4) and -SO2-containing cyclic groups represented by the general formulas (r-hr-1) to (r-hr-16) are exemplified. In the formula, * represents the same as Y in formula (b-1). 101 The bonding position of the bond.

[0485] [Chemistry 38]

[0486]

[0487] As R 101 The substituent in the cyclic group may, for example, be an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group or the like.

[0488] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms.

[0489] The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and most preferably a methoxy group and an ethoxy group.

[0490] The halogen atom as a substituent is preferably a fluorine atom, a bromine atom or an iodine atom.

[0491] Examples of the haloalkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are substituted with the above-mentioned halogen atoms.

[0492] The carbonyl group as a substituent is a group that replaces the methylene group (—CH 2 —) constituting the cyclic hydrocarbon group.

[0493] R 101 The cyclic hydrocarbon group in can be a condensed ring group comprising a condensed ring formed by condensing an aliphatic hydrocarbon ring and an aromatic ring. As the condensed ring, for example, a condensed ring formed by condensing more than one aromatic ring and a polycycloalkane having a cross-linked ring polycyclic skeleton can be cited. As a specific example of the cross-linked ring polycycloalkane, bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane and other bicycloalkanes can be cited. As the condensed ring group, it is preferably a group comprising a condensed ring formed by condensing 2 or 3 aromatic rings and a bicycloalkane, and more preferably a group comprising a condensed ring formed by condensing 2 or 3 aromatic rings and a bicyclo[2.2.2]octane. As R 101 Specific examples of the fused ring group in the formula (r-br-1) to (r-br-2) can be cited as the following groups. In the formula, * represents the same as Y in the formula (b-1). 101 The bonding position of the bond.

[0494] [Chemistry 39]

[0495]

[0496] As R 101 Examples of the substituent that the fused cyclic group in may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.

[0497] As the alkyl group, alkoxy group, halogen atom, or halogenated alkyl group as a substituent of the condensed ring group, the following examples are mentioned: 101 The same groups as those exemplified as the substituents of the cyclic group in .

[0498] As the aromatic hydrocarbon group as a substituent of the fused cyclic group, there may be mentioned a group obtained by removing one hydrogen atom from an aromatic ring (aryl group: for example, phenyl, naphthyl, etc.), a group obtained by replacing one hydrogen atom of the aromatic ring with an alkylene group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and a heterocyclic group represented by the above formulae (R-HR-1) to (R-HR-6).

[0499] The alicyclic hydrocarbon group as a substituent of the condensed ring group may be a group obtained by removing one hydrogen atom from a monocyclic alkane such as cyclopentane, cyclohexane, etc.; a group obtained by removing one hydrogen atom from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; a lactone-containing cyclic group represented by the general formula (a2-r-1) to (a2-r-7), respectively; a -SO2-containing cyclic group represented by the general formula (a5-r-1) to (a5-r-4), respectively; a heterocyclic group represented by the formula (r-hr-7) to (r-hr-16), respectively, etc.

[0500] A chain alkyl group which may have a substituent:

[0501] As R 101 The chain alkyl group may be straight chain or branched chain.

[0502] The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.

[0503] The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples thereof include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0504] Chain alkenyl groups which may have substituents:

[0505] As R 101 The chain alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl, propenyl (allyl), and butenyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0506] As the chain alkenyl group, among the above, a straight-chain alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0507] As R 101 The substituents in the chain alkyl or chain alkenyl groups include, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, the above-mentioned R 101 In the cyclic group, etc.

[0508] Among the above, R 101Preferably, the cyclic group may be substituted, and more preferably, the cyclic hydrocarbon group may be substituted. More specifically, the cyclic hydrocarbon group is preferably a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7); or an -SO2-containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4). More preferably, the group is obtained by removing one or more hydrogen atoms from a polycycloalkane or an -SO2-containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4). Further preferably, the group is an adamantyl group or an -SO2-containing cyclic group represented by the general formula (a5-r-1).

[0509] When the cyclic hydrocarbon group has a substituent, the substituent is preferably a hydroxyl group.

[0510] In formula (b-1), Y 101 It is a single bond or a divalent linking group containing an oxygen atom.

[0511] In Y 101 In the case of a divalent linking group containing an oxygen atom, the Y 101 Atoms other than oxygen atoms may be contained. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.

[0512] Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following general formulae (y-a1-1) to (y-a1-7). 101 The bond is V' in the following general formula (y-al-1) to (y-al-7) 101 .

[0513] [Chemistry 40]

[0514]

[0515] [Where, V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, V' 102 It is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0516] V' 102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 5 carbon atoms.

[0517] As V' 101 and V' 102The alkylene group in may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group.

[0518] As V' 101 and V' 102 Specifically, the alkylene group in the group includes methylene [—CH2-]; alkylmethylene groups such as —CH(CH3)-, —CH(CH2CH3)-, —C(CH3)2-, —C(CH3)(CH2CH3)-, —C(CH3)(CH2CH2CH3)-, and —C(CH2CH3)2-; ethylene [—CH2CH2-]; —CH(CH3)CH2-, —CH(CH3)CH(CH3)-, —C(CH3)2CH2-, -CH(CH2CH3)CH2- and other alkylethylene groups; propylene (n-propylene) [-CH2CH2CH2-]; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and other alkylpropylene groups; butylene [-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylbutylene groups; pentylene [-CH2CH2CH2CH2CH2CH2-] and the like.

[0519] In addition, V' 101 or V' 102 A portion of the methylene groups in the alkylene group may be substituted by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably selected from Ra' in the formula (a1-r-1). 3 A divalent group obtained by removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group), more preferably a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group.

[0520] As Y 101 , preferably a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond, more preferably a linking group represented by the above formulae (y-a1-1) to (y-a1-5), respectively.

[0521] In formula (b-1), V 101 is a single bond, an alkylene group or a fluoroalkylene group. 101 The alkylene and fluoroalkylene groups in the group preferably have 1 to 4 carbon atoms. 101 It is preferably a single bond or a linear fluoroalkylene group having 1 to 4 carbon atoms.

[0522] In formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102A fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is preferred, and a fluorine atom is more preferred.

[0523] As a specific example of the anion part represented by the formula (b-1), for example, in Y 101 In the case of a single bond, fluoroalkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion can be mentioned; 101 In the case of a divalent linking group containing an oxygen atom, an anion represented by any one of the following formulae (an-1) to (an-3) may be mentioned.

[0524] [Chemistry 41]

[0525]

[0526] [Where, R” 101 R" is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above chemical formulas (R-HR-1) to (R-HR-6), a condensed cyclic group represented by the above formula (R-Br-1) or (R-Br-2), an acyclic alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent. 102 An aliphatic cyclic group which may have a substituent, a condensed cyclic group represented by the formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formula (a2-r-1), (a2-r-3) to (a2-r-7), or a -SO2-containing cyclic group represented by the general formula (a5-r-1) to (a5-r-4). R" 103 V" is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluoroalkylene group having 1 to 4 carbon atoms. 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v" is each independently an integer of 0 to 3, q" is each independently an integer of 0 to 20, and n" is 0 or 1.]

[0527] R” 101 , R” 102 and R” 103 An aliphatic cyclic group which may have a substituent is preferably used as R in the formula (b-1). 101 As the substituent, there can be exemplified the group corresponding to R in the formula (b-1). 101 The substituents of the substitutable cyclic aliphatic hydrocarbon group are the same as those of the substituents of the substitutable cyclic aliphatic hydrocarbon group.

[0528] R” 101 and R” 103The aromatic cyclic group which may have a substituent is preferably used as R in the formula (b-1). 101 The substituents are exemplified by the aromatic hydrocarbon groups in the cyclic hydrocarbon groups. 101 The substituents which may substitute the aromatic hydrocarbon group are the same groups.

[0529] R” 101 The chain alkyl group which may have a substituent is preferably used as R in the formula (b-1). 101 The group exemplified by the chain alkyl group in .

[0530] R” 103 The chain alkenyl group which may have a substituent is preferably used as R in the formula (b-1). 101 The group exemplified by the chain alkenyl group in .

[0531] Anions in component (b-2)

[0532] In formula (b-2), R 104 、R 105 Each of them is independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the following: 101 The same group. 104 、R 105 They may be bonded to each other to form a ring.

[0533] R 104 、R 105 It is preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluoroalkyl group.

[0534] The number of carbon atoms in the chain alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. 104 、R 105 The carbon number of the chain alkyl group is preferably as small as possible within the above range of carbon atoms. 104 、R 105 In the chain alkyl group, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength and the higher the transparency to high-energy light or electron beams of 250 nm or less, which is preferred. The ratio of fluorine atoms in the chain alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0535] In formula (b-2), V 102 、V103 are independently a single bond, an alkylene group or a fluoroalkylene group, and examples thereof include V 101 Same group.

[0536] In formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0537] As the anion in the component (b-2), an anion represented by the following general formula (b-2-1) is preferred.

[0538] [Chemistry 42]

[0539]

[0540] [In formula (b-2-1), X" represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.]

[0541] X" represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom. The alkylene group here may be linear or branched and has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and more preferably 3 carbon atoms.

[0542] For reasons such as increasing the strength of the acid, the alkylene group of X" preferably has a larger number of hydrogen atoms substituted by fluorine atoms. The fluorination rate of the alkylene group or alkyl group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted by fluorine atoms.

[0543] Anions in component (b-3)

[0544] In formula (b-3), R 106 ~R 108 Each of them is independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the following: 101 Same group.

[0545] In formula (b-3), L 103 ~L 105 are each independently a single bond, -CO- or -SO2-.

[0546] In the above, the anion portion of component (B) is preferably an anion in component (b-1). Among them, an anion represented by any of the general formulas (an-1) to (an-3) is more preferred, an anion represented by any of the general formulas (an-1) and (an-2) is further preferred, and an anion represented by the general formula (an-2) is particularly preferred.

[0547] {Cation Department}

[0548] In the formula (b-1), formula (b-2), and formula (b-3), M m+ represents an m-valent onium cation, among which sulfonium cation and iodonium cation are preferred.

[0549] m is an integer greater than or equal to 1.

[0550] As a preferred cationic moiety ((M m+ ) 1 / m ), and examples thereof include organic cations represented by the following general formulas (ca-1) to (ca-3).

[0551] [Chemistry 43]

[0552]

[0553] [Where R 201 ~R 207 R each independently represents an aryl group, an alkyl group or an alkenyl group which may have a substituent. 201 ~R 203 、R 206 ~R 207 They may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 It is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO2-containing cyclic group which may have a substituent. 201 represents -C(=O)- or -C(=O)-O-.]

[0554] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 The aryl group in may be an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.

[0555] As R 201 ~R 207 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0556] As R 201 ~R 207 The alkenyl group in preferably has 2 to 10 carbon atoms.

[0557] As R 201 ~R 207 and R 210Examples of the substituent that may be possessed include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulae (ca-r-1) to (ca-r-7).

[0558] [Chemistry 44]

[0559]

[0560] [Wherein, R' 201 Each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.]

[0561] The cyclic group which may have a substituent:

[0562] The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. In addition, an aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferably saturated.

[0563] R' 201 The aromatic hydrocarbon group in is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituent.

[0564] As R' 201 Specifically, the aromatic ring possessed by the aromatic hydrocarbon group in the group may be benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocycle in which a portion of the carbon atoms constituting these aromatic rings are substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0565] As R' 201 Specifically, the aromatic hydrocarbon group in the group may be a group obtained by removing one hydrogen atom from the aromatic ring (aryl groups such as phenyl and naphthyl), or a group obtained by replacing one hydrogen atom of the aromatic ring with an alkylene group (arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0566] R' 201 The cyclic aliphatic hydrocarbon group in the cyclic aliphatic hydrocarbon group may include an aliphatic hydrocarbon group containing a ring in the structure.

[0567] Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed between straight-chain or branched aliphatic hydrocarbon groups.

[0568] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0569] The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferred. Among them, as the polycycloalkane, polycycloalkane having a cross-linked ring type polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; polycycloalkane having a condensed ring type polycycloalkane such as a cyclic group having a steroid skeleton is more preferred.

[0570] Among them, as R' 201 The cyclic aliphatic hydrocarbon group in the group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0571] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0572] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples thereof include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0573] As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specific examples include -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2- and the like alkylmethylene groups; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2- and the like alkylethylene groups; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and the like alkylpropylene groups; and -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2- and the like alkylbutylene groups. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0574] In addition, R' 201 The cyclic hydrocarbon group in the formula (a2-r-1) to (a2-r-7) may contain a heteroatom. Specifically, the cyclic groups containing lactones, the cyclic groups containing -SO2-, and the heterocyclic groups represented by the above-mentioned formulas (r-hr-1) to (r-hr-16) may be mentioned.

[0575] As R' 201 The substituent in the cyclic group may, for example, be an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group or the like.

[0576] The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0577] The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and most preferably a methoxy group and an ethoxy group.

[0578] The halogen atom as a substituent is preferably a fluorine atom.

[0579] Examples of the haloalkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are substituted with the above-mentioned halogen atoms.

[0580] The carbonyl group as a substituent is a group that replaces the methylene group (—CH 2 —) constituting the cyclic hydrocarbon group.

[0581] A chain alkyl group which may have a substituent:

[0582] As R' 201 The chain alkyl group may be straight chain or branched chain.

[0583] The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.

[0584] The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0585] Chain alkenyl groups which may have substituents:

[0586] As R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl, propenyl (allyl), and butenyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0587] As the chain alkenyl group, among the above, a straight-chain alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0588] As R' 201 The substituents in the chain alkyl or chain alkenyl groups include, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, the above-mentioned R' 201 In the cyclic group, etc.

[0589] R' 201 In addition to the above-mentioned groups, the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent may include, as the cyclic group which may have a substituent or the chain alkyl group which may have a substituent, the same groups as the acid-dissociable groups represented by the above-mentioned formula (a1-r-2) may also be mentioned.

[0590] Among them, R' 201Preferably, the group is a cyclic group which may have a substituent, and more preferably, a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7), or an -SO2-containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4).

[0591] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 、R 206 ~R 207 When they are bonded to each other to form a ring together with the sulfur atom in the formula, the ring may be mediated by a sulfur atom, an oxygen atom, a nitrogen atom or other heteroatom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH- or -N(R N )-(The R N is an alkyl group having 1 to 5 carbon atoms) and is bonded to a functional group. The ring formed is preferably a three- to ten-membered ring including the sulfur atom in the ring skeleton, and particularly preferably a five- to seven-membered ring. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0592] R 208 ~R 209 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 208 ~R 209 In the case of an alkyl group, they may be bonded to each other to form a ring.

[0593] R 210 It is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an -SO2-containing cyclic group which may have a substituent.

[0594] As R 210 The aryl group in may be an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.

[0595] As R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0596] As R 210 The alkenyl group in preferably has 2 to 10 carbon atoms.

[0597] As R 210The optionally substituted -SO2-containing cyclic group is preferably a "-SO2-containing polycyclic group", and more preferably a group represented by the above-mentioned general formula (a5-r-1).

[0598] Specific examples of the cation represented by the above formula (ca-1) are shown below.

[0599] [Chemistry 45]

[0600]

[0601] [Chemistry 46]

[0602]

[0603] [Chemistry 47]

[0604]

[0605] [In the formula, g1, g2, and g3 represent the number of repetitions, g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0606] [Chemistry 48]

[0607]

[0608] [Chemistry 49]

[0609]

[0610] [Chemistry 50]

[0611]

[0612] [Where, R” 201 is a hydrogen atom or a substituent, and as the substituent, 201 ~R 207 and R 210 ~R 212 The substituents that may be possessed are the same as those exemplified above.]

[0613] Specific examples of preferred cations represented by the formula (ca-2) include diphenyliodonium cations and bis(4-tert-butylphenyl)iodonium cations.

[0614] Specific examples of preferred cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0615] [Chemistry 51]

[0616]

[0617] Among the above, the cation part ((M m+ ) 1 / m ) is preferably a cation represented by the general formula (ca-1).

[0618] As the onium salt-based acid generator, among the above, a compound represented by the following general formula (b01) is preferred.

[0619] [Chemistry 52]

[0620]

[0621] [Where, X - As the counter anion. 01 Lb is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 01 Rb is a single bond or a divalent linking group. 02 and Rb 03 Each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 02 and Rb 03 They may bond to each other to form an aliphatic ring together with the sulfur atom in the formula.]

[0622] {Cation Department}

[0623] In the general formula (b01), Rb 01 ~Rb 03 The aryl group in is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group.

[0624] As Rb 01 ~Rb 03 The alkyl group in the group may be a chain or cyclic alkyl group, and is preferably an alkyl group having 1 to 30 carbon atoms.

[0625] As Rb 01 ~Rb 03 The alkenyl group in is preferably an alkenyl group having 2 to 10 carbon atoms.

[0626] As Rb 01 ~Rb 03 The substituents that the aryl, alkyl and alkenyl groups in the group may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, and an aryl group.

[0627] In Rb 02 and Rb 03 When they are bonded to each other to form a ring together with the sulfur atom in the formula, the ring may be mediated by a sulfur atom, an oxygen atom, a nitrogen atom or other heteroatom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH- or -N(R N )-(The RN is an alkyl group having 1 to 5 carbon atoms) and is bonded to a functional group. The ring formed is preferably a three- to ten-membered ring including the sulfur atom in the ring skeleton, and particularly preferably a five- to seven-membered ring. Specific examples of the ring formed include a tetrahydrothiophene ring, a cyclopentane sulfide ring, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, and a tetrahydrothiopyranium ring.

[0628] In the general formula (b01), Rb 01 , among the above, unsubstituted aryl is preferred.

[0629] In the general formula (b01), Rb 02 and Rb 03 , preferably bonded to each other and form a ring together with the sulfur atom in the formula, more preferably Rb 02 and Rb 03 They bond to each other to form an aliphatic ring together with the sulfur atom in the formula, and more preferably form a tetrahydrothiophene ring or a cyclopentane sulfide ring.

[0630] In the general formula (b01), Lb 01 It is a single bond or a divalent linking group.

[0631] As Lb 01 The divalent linking group in the is preferably an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, and more preferably a group consisting of a combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear or branched alkylene group.

[0632] As Lb 01 , among the above, a single bond is preferred.

[0633] Among the above, the cation portion of the compound represented by the general formula (b01) is preferably a cation represented by the following general formula (ca-b0-1).

[0634] [Chemistry 53]

[0635]

[0636] [Wherein, Rb 01 Lb is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 01 Yb is a single bond or a divalent linking group. 01 It is a group that forms an aliphatic ring together with the sulfur atom in the formula. 01The formed aliphatic ring may have a substituent.]

[0637] Rb in the general formula (ca-b0-1) 01 and Rb in the general formula (b01) 01 same.

[0638] Lb in the general formula (ca-b0-1) 01 and Lb in the general formula (b01) 01 same.

[0639] Yb in the general formula (ca-b0-1) 01 is a group that forms an aliphatic ring together with the sulfur atom in the formula. The aliphatic ring may have a substituent, and examples of the substituent include Rb in the general formula (b01). 01 The substituents that may be possessed are the same as those of the group.

[0640] Yb in the general formula (ca-b0-1) 01 It is preferably a group that forms a tetrahydrothiophene ring or a cyclopentane sulfide ring together with the sulfur atom in the formula, and more preferably a group that forms a cyclopentane sulfide ring.

[0641] {Anion Section}

[0642] In the general formula (b01), X - is the counter anion. - There are no particular limitations, and any anion that has been proposed as the anion portion of an acid generator used in a resist composition can be used.

[0643] As X - Specifically, the anions of the above-mentioned component (b-1), component (b-2), and component (b-3) may be mentioned.

[0644] Imidosulfonate acid generators

[0645] Examples of the imide sulfonate acid generator include compounds represented by the following general formula (B3-1).

[0646] [Chemistry 54]

[0647]

[0648] [Where, Rx 1 Is a fluoroalkyl group. 2 ~Rx 7 are each independently a hydrogen atom or an alkyl group which may have a substituent.]

[0649] In the general formula (B3-1), Rx 1It is a fluoroalkyl group, preferably a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a fluoroalkyl group having 1 to 5 carbon atoms, and further preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

[0650] In the general formula (B3-1), Rx 2 ~Rx 7 Each independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0651] Examples of the alkyl group which may have a substituent include the following: 01 The substituents that may be possessed by the alkyl group are the same as those of the alkyl group.

[0652] In the general formula (B3-1), Rx 2 ~Rx 7 Among the above, Rx is preferred 2 ~Rx 7 At least one of them is an alkyl group having 1 to 10 carbon atoms, and the rest are alkyl groups having 1 to 10 carbon atoms.

[0653] Specific examples of preferred component (B) in the resist composition of this embodiment are shown below.

[0654] [Chemistry 55]

[0655]

[0656] [Chemistry 56]

[0657]

[0658] [Chemistry 57]

[0659]

[0660] In the resist composition of the present embodiment, the component (B) may be used alone or in combination of two or more.

[0661] In the resist composition of the present embodiment, the content of the component (B) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the component (A1).

[0662] By setting the content of component (B) within the above-mentioned preferred range, sufficient pattern formation can be achieved. In addition, when the components of the resist composition are dissolved in an organic solvent, a uniform solution is easily obtained, which improves the storage stability of the resist composition and is therefore preferred.

[0663] <Compound (D0)>

[0664] The resist composition of the present embodiment further contains a compound (D0) having a group represented by the following general formula (d0-r).

[0665] The component (D0) functions as a quencher (acid diffusion controller) for capturing acid generated by exposure in the resist composition.

[0666] [Chemistry 58]

[0667]

[0668] [Where, Rx 01 is a hydrogen atom, an alkyl group or an alkoxy group. 021 ~Rx 028 are independently a hydrogen atom or an alkyl group. nd is 0 or 1. * indicates a bonding position.]

[0669] In the general formula (d0-r), Rx 01 is a hydrogen atom, an alkyl group or an alkoxy group.

[0670] As Rx 01 The alkyl group in is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms.

[0671] As Rx 01 The alkoxy group in is preferably an alkoxy group having 1 to 25 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, further preferably an alkoxy group having 1 to 15 carbon atoms, and particularly preferably an alkoxy group having 8 to 15 carbon atoms.

[0672] From the viewpoint of further improving pattern shape, adhesion and CD stability, in the general formula (d0-r), Rx 01 An alkoxy group is preferred.

[0673] In the general formula (d0-r), Rx 021 ~Rx 028 are each independently a hydrogen atom or an alkyl group.

[0674] As Rx 021 ~Rx 028 The alkyl group in Rx 01 The alkyl groups in are the same as the alkyl groups.

[0675] In the general formula (d0-r), Rx 021 、Rx 022 、Rx 027 , and Rx 028 Among the above, an alkyl group is preferred.

[0676] In the general formula (d0-r), Rx023 、Rx 024 、Rx 025 , and Rx 026 Among the above, a hydrogen atom is preferred.

[0677] In the general formula (d0-r), nd is 0 or 1, preferably 1.

[0678] In addition, when nd is 0, the group represented by the general formula (d0-r) is a five-membered ring structure and does not have Rx 023 and Rx 024 .

[0679] Specific examples of the group represented by the general formula (d0-r) include groups represented by the following formulae (d0-r-01) to (d0-r-04).

[0680] [Chemistry 59]

[0681]

[0682] As the group represented by the general formula (d0-r), among the above, the group represented by the formula (d0-r-01) or (d0-r-02) is preferred, and the group represented by the formula (d0-r-01) is more preferred.

[0683] As the component (D0), among the above, a compound represented by the following general formula (d0) is preferred.

[0684] [Chemistry 60]

[0685]

[0686] [In formula (d0), Rd 01 is a group represented by the general formula (d0-r), wherein * in the general formula (d0-r) represents the bonding position to the oxygen atom (-O-) in the formula (d0). p is 0 or 1. q is an integer greater than 1, and Rdx is a hydrogen atom, a hydroxyl group, or a q-valent organic group. When q is greater than 2, multiple [Rd 01 -O-(C=O)p-] may be the same or different.]

[0687] In the general formula (d0), the organic group in Rdx may be a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0688] The aliphatic hydrocarbon group preferably has 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 1 to 25 carbon atoms, and particularly preferably 1 to 20 carbon atoms.

[0689] The aliphatic hydrocarbon group may be an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group.

[0690] The aliphatic hydrocarbon group may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group.

[0691] The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 25, and even more preferably 6 to 20.

[0692] An aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons and may be monocyclic or polycyclic. Specifically, examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and pyrene.

[0693] The aromatic ring contained in the aromatic hydrocarbon group may be an aromatic heterocycle in which a portion of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyrrolidine ring, a pyridine ring, a thiophene ring, and a triazine ring.

[0694] In the hydrocarbon group, a hydrogen atom contained in the hydrocarbon group may be substituted with a monovalent substituent, and a methylene group contained in the hydrocarbon group may be substituted with a divalent substituent.

[0695] Examples of the monovalent substituent include a group represented by the general formula (d0-r), an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, and an amino group.

[0696] Examples of the divalent substituent include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -represented by a group [wherein, Y 21 and Y22 Each independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3] and the like.

[0697] Specific examples of the organic group in Rdx include an alkylene group, an alkenyl group, -O-Rd 01 wait.

[0698] In the general formula (d0), q is an integer of 1 or greater, and preferably an integer of 1-10.

[0699] When q is 2 or more, multiple [Rd 01 -O-(C=O)p-] may be the same or different, but are preferably the same.

[0700] As the component (D0), among the above, a compound represented by the following general formula (d0-1) or (d0-2) is more preferable.

[0701] [Chemistry 61]

[0702]

[0703] [Where, Rd 011 、Rd 012 and Rd 021 ~Rd 024 are groups represented by the general formula (d0-r), which may be the same group or different groups. * in the general formula (d0-r) represents the bonding position to the oxygen atom (-O-) in formula (d0-1) or (d0-2). Ld is a single bond or a divalent organic group. p1 is 0 or 1.

[0704] In the general formula (d0-1), Rd 011 and Rd 012 The groups represented by the general formula (d0-r) may be the same group or different groups, but are preferably the same group.

[0705] In the general formula (d0-1), Ld is a single bond or a divalent organic group.

[0706] Examples of the organic group include an alkylene group which may have a substituent. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, further preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

[0707] In the alkylene group, a hydrogen atom contained in the alkylene group may be substituted with a monovalent substituent, and a methylene group contained in the alkylene group may be substituted with a divalent substituent.

[0708] Examples of the monovalent substituent include an alkoxy group, a halogen atom, a haloalkyl group, a hydroxy group, a carbonyl group, a nitro group, and an amino group.

[0709] Examples of the divalent substituent include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -represented by a group [wherein, Y 21 and Y 22 Each independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3] and the like.

[0710] In the general formula (d0-1), among the above, Ld is preferably a single bond or an alkylene group, and more preferably a single bond.

[0711] In the general formula (d0-1), p1 is 0 or 1, preferably 0.

[0712] In the general formula (d0-2), Rd 021 ~Rd 024 The groups represented by the general formula (d0-r) may be the same group or different groups, but are preferably the same group.

[0713] The boiling point of the component (D0) is preferably 250 to 800°C, more preferably 400 to 750°C, and even more preferably 600 to 750°C.

[0714] When the boiling point of the component (D0) is equal to or higher than the preferred lower limit, decomposition or volatilization due to heat can be further suppressed, and the function as the acid diffusion controller can be more fully exhibited.

[0715] When the boiling point of the component (D0) is equal to or higher than the above-described preferred lower limit, lithography characteristics such as CD stability, adhesion, and pattern shape are further improved.

[0716] Specific examples of preferred component (D0) in the resist composition of this embodiment are shown below.

[0717] The boiling point (BP) is also listed below the chemical formula name.

[0718] [Chemistry 62]

[0719]

[0720] [Chemistry 63]

[0721]

[0722] As the component (D0), among the above, compounds represented by the above formulae (D0-1) to (D0-4) are preferred, and compounds represented by the above formulae (D0-1) or (D0-2) are more preferred.

[0723] Furthermore, the component (D0) in the resist composition of the present embodiment may be a compound represented by the following general formula (D0-7).

[0724] [Chemistry 64]

[0725]

[0726] [Wherein, Rn 1 ~Rn 6 are each independently a hydrogen atom or an alkyl group.]

[0727] In the resist composition of this embodiment, the component (D0) may be used alone or in combination of two or more.

[0728] In the resist composition of the present embodiment, the content of the component (D0) is preferably 0.005 to 1 part by mass, more preferably 0.005 to 0.1 part by mass, and even more preferably 0.005 to 0.05 part by mass, based on 100 parts by mass of the component (A1).

[0729] By setting the content of the component (D0) to be equal to or greater than the above-described preferred lower limit, lithography properties such as CD stability, adhesion, and pattern shape are further improved.

[0730] Furthermore, by setting the content of the component (D0) to be below the preferred upper limit, good sensitivity can be maintained and throughput can be further improved.

[0731] <Other ingredients>

[0732] The resist composition of this embodiment may further contain other components in addition to the above-mentioned components (A), (B) and (D0). Examples of other components include the following components (D), (E), (F) and (S).

[0733] 《Alkali component (D)》

[0734] The resist composition of this embodiment may further contain an alkaline component (component (D)) that traps the acid generated by exposure (i.e., controls the diffusion of the acid). Component (D) functions as a quencher (acid diffusion controller) in the resist composition that traps the acid generated by exposure.

[0735] Examples of the component (D) include a photodegradable base (D1) that loses its acid diffusion control property by decomposition due to exposure (hereinafter referred to as "component (D1)"), a nitrogen-containing organic compound (D2) that does not belong to the component (D1) and does not belong to the above-mentioned component (D0) (hereinafter referred to as "component (D2)"), and the like.

[0736] About the (D1) ingredient

[0737] By using a resist composition containing the component (D1), the contrast between the exposed portion and the unexposed portion of the resist film can be further improved when forming a resist pattern.

[0738] The (D1) component is not particularly limited as long as it is a component that loses its acid diffusion control property by decomposition due to exposure, but is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component").

[0739] Components (d1-1) to (d1-3) decompose in the exposed portion of the resist film and lose their acid diffusion control property (basicity), and thus cannot function as a quencher. Instead, they function as a quencher in the unexposed portion of the resist film.

[0740] [Chemistry 65]

[0741]

[0742] [Where, Rd 1 ~Rd 4 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. 2There is no fluorine atom bonded to the carbon atom adjacent to the S atom in Yd. 1 is a single bond or a divalent linking group. m is an integer greater than 1, M m+ are each independently an m-valent organic cation.]

[0743] {(d1-1)Component}

[0744] ··Anion part

[0745] In formula (d1-1), Rd 1 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the above-mentioned R' 201 Same group.

[0746] Among these, as Rd 1 , preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkyl group which may have a substituent. As substituents which these groups may have, there may be mentioned hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluoroalkyl groups, lactone-containing cyclic groups represented by the above-mentioned general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. In the case where an ether bond or an ester bond is included as a substituent, an alkylene group may be used, and as a substituent in this case, a connecting group represented by the above-mentioned formulas (y-al-1) to (y-al-5) is preferred. In addition, in Rd 1 In the case where the aromatic hydrocarbon group, aliphatic cyclic group or chain alkyl group has a connecting group represented by the above general formulas (y-al-1) to (y-al-7) as a substituent, in the above general formulas (y-al-1) to (y-al-7), Rd in formula (d3-1) 1 The carbon atom that constitutes the aromatic hydrocarbon group, aliphatic cyclic group or chain alkyl group is bonded to V' in the above general formulas (y-al-1) to (y-al-7). 101 .

[0747] Preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and other ring structures).

[0748] The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

[0749] The chain alkyl group preferably has 1 to 10 carbon atoms. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0750] When the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0751] Preferred specific examples of the anion portion of the component (d1-1) are shown below.

[0752] [Chemistry 66]

[0753]

[0754] ··Cationic part

[0755] In formula (d1-1), M m+ It is an m-valent organic cation.

[0756] As M m+ The organic cations may preferably be cations that are the same as the cations represented by the general formulas (ca-1) to (ca-5), more preferably cations represented by the general formula (ca-1), and further preferably cations represented by the formulas (ca-1-1) to (ca-1-70).

[0757] The component (d1-1) may be used alone or in combination of two or more.

[0758] {(d1-2)Component}

[0759] ··Anion part

[0760] In formula (d1-2), Rd 2 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the same group as R' 201 Same group.

[0761] Among them, Rd 2There is no fluorine atom bonded to the carbon atom adjacent to the S atom (no fluorine substitution). As a result, the anion of the component (d1-2) becomes an appropriate weak acid anion, and the quenching ability as the component (D) is improved.

[0762] As Rd 2 , preferably a chain alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent. The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like (which may have a substituent); or a group obtained by removing one or more hydrogen atoms from camphor, or the like.

[0763] Rd 2 The hydrocarbon group may have a substituent, and examples of the substituent include Rd 1 The substituents that the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) may have are the same as those in the preceding text.

[0764] Preferred specific examples of the anion portion of the component (d1-2) are shown below.

[0765] [Chemistry 67]

[0766]

[0767] ··Cationic part

[0768] In formula (d1-2), M m+ is an organic cation with a valence of m, and M in the formula (d1-1) m+ same.

[0769] The component (d1-2) may be used alone or in combination of two or more.

[0770] {(d1-3)Component}

[0771] ··Anion part

[0772] In formula (d1-3), Rd 3 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the same group as R' 201 The same group is preferably a cyclic group containing fluorine atoms, a chain alkyl group or a chain alkenyl group. Among them, a fluoroalkyl group is preferred, and more preferably the same as the above Rd 1 The fluoroalkyl group is the same as the fluoroalkyl group.

[0773] In formula (d1-3), Rd 4is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the same group as R' 201 Same group.

[0774] Among them, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group which may have a substituent are preferred.

[0775] Rd 4 The alkyl group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. 4 Some of the hydrogen atoms in the alkyl group may be substituted by a hydroxyl group, a cyano group, or the like.

[0776] Rd 4 The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy. Among them, methoxy and ethoxy are preferred.

[0777] For Rd 4 The alkenyl group in the above R' 201 The alkenyl group in the same group as the alkenyl group is preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may further have an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms as a substituent.

[0778] As Rd 4 The cyclic group in the above R' 201 The same group as the cyclic group in Rd is preferably an alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or an aromatic group such as phenyl or naphthyl. 4 When Rd is an alicyclic group, the resist composition dissolves well in an organic solvent, thereby improving the photolithographic properties. 4 When the group is an aromatic group, the resist composition has excellent light absorption efficiency in photolithography using EUV or the like as an exposure light source, and has good sensitivity and photolithographic characteristics.

[0779] In formula (d1-3), Yd 1 It is a single bond or a divalent linking group.

[0780] As Yd 1The divalent linking group in is not particularly limited, and examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, a divalent linking group containing a heteroatom, and the like. These can be exemplified by the same group as Ya in the above formula (a2-1). 21 The same connecting groups as those exemplified in the description of the divalent connecting group in the above, the divalent hydrocarbon group which may have a substituent and the divalent connecting group containing a heteroatom.

[0781] As Yd 1 , preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. As the alkylene group, a linear or branched alkylene group is more preferred, and a methylene group or an ethylene group is further preferred.

[0782] Preferred specific examples of the anion portion of the component (d1-3) are shown below.

[0783] [Chemistry 68]

[0784]

[0785] [Chemistry 69]

[0786]

[0787] ··Cationic part

[0788] In formula (d1-3), M m+ is an organic cation with a valence of m, and M in the formula (d1-1) m+ same.

[0789] The component (d1-3) may be used alone or in combination of two or more.

[0790] As the component (D1), only one of the components (d1-1) to (d1-3) may be used, or two or more of them may be used in combination.

[0791] When the resist composition contains the component (D1), the content of the component (D1) in the resist composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 8 parts by mass, based on 100 parts by mass of the component (A1).

[0792] When the content of the component (D1) is at least the lower limit, particularly good lithographic properties and resist pattern shapes are easily obtained. On the other hand, when it is at most the upper limit, good sensitivity can be maintained and throughput is excellent.

[0793] (D1) Method for producing component:

[0794] The production method of the above-mentioned component (d1-1) and component (d1-2) is not particularly limited, and they can be produced by a known method.

[0795] The method for producing the component (d1-3) is not particularly limited, and the component can be produced in the same manner as described in, for example, US 2012-0149916 .

[0796] Although the compound of component (D1) is shown as an example of the alkaline component (component (D)) that captures acid generated by exposure, the compound of component (D1) can also be used as component (B).

[0797] For example, in the resist composition of this embodiment, component (D1) may be used as component (B), and a compound that generates an acid with a relatively low acidity due to the acid generated by the compound of component (D1) upon exposure may be used as component (D). Furthermore, in the resist composition of this embodiment, component (D1) may be used as component (B), and component (D2) described later may be used as component (D).

[0798] About the (D2) ingredient

[0799] The component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not belong to the component (D1) and the component (D0).

[0800] As the component (D2), any one of known nitrogen-containing organic compound components may be used. Among them, aliphatic amines are preferred, and secondary aliphatic amines or tertiary aliphatic amines are particularly preferred.

[0801] The aliphatic amine refers to an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.

[0802] Examples of the aliphatic amine include amines obtained by replacing at least one hydrogen atom of ammonia NH 3 with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkylolamines), and cyclic amines.

[0803] Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, with tri-n-pentylamine and tri-n-octylamine being particularly preferred.

[0804] Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).

[0805] Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.

[0806] The aliphatic polycyclic amine is preferably an aliphatic polycyclic amine having 6 to 10 carbon atoms, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0807] Examples of other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, and triethanolamine triacetate, with triethanolamine triacetate being preferred.

[0808] Furthermore, as the component (D2), an aromatic amine can also be used.

[0809] Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, n-tert-butoxycarbonylpyrrolidine and 2,6-di-tert-butylpyridine.

[0810] The component (D2) may be used alone or in combination of two or more.

[0811] When the resist composition contains the component (D2), the content of the component (D2) in the resist composition is usually in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the component (A1). By setting it within the above range, the resist pattern shape, stability over time, etc. are improved.

[0812] At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxyacids, and derivatives thereof

[0813] For the purpose of preventing sensitivity degradation or improving the resist pattern shape and stability over time, the resist composition of the present embodiment can contain at least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxyacids, and derivatives thereof (hereinafter referred to as "component (E)") as an optional component.

[0814] Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid and salicylic acid. Among them, salicylic acid is preferred.

[0815] Examples of the phosphorus oxyacid include phosphoric acid, phosphonic acid and phosphinic acid. Among these, phosphonic acid is particularly preferred.

[0816] In the resist composition of the present embodiment, the component (E) may be used alone or in combination of two or more.

[0817] When the resist composition contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of component (A). By setting the content within the above range, sensitivity and lithographic characteristics are improved.

[0818] 《Fluorine additive ingredients (F)》

[0819] The resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. Component (F) is used to impart water repellency to the resist film and, by using it as a different resin from component (A), can improve lithographic properties.

[0820] As the component (F), for example, fluorine-containing polymer compounds described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226 can be used.

[0821] More specifically, component (F) includes a polymer having a structural unit (f1) represented by the following general formula (f1-1). Preferred examples of such a polymer include a polymer (homopolymer) consisting solely of the structural unit (f1) represented by the following general formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1); a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1); and more preferably a copolymer of the structural unit (f1) and the structural unit (a1). The structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate or a structural unit derived from 1-methyl-1-adamantyl (meth)acrylate, and more preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate.

[0822] [Chemistry 70]

[0823]

[0824] [wherein, R is the same as above, Rf 102 and Rf 103 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 Can be the same or different. 1 is an integer from 0 to 5, Rf 101 is an organic group containing a fluorine atom.]

[0825] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. R is preferably a hydrogen atom or a methyl group.

[0826] In formula (f1-1), as Rf 102 and Rf 103 The halogen atom of Rf is preferably a fluorine atom. 102 and Rf 103 The alkyl group having 1 to 5 carbon atoms in Rf may be the same as the alkyl group having 1 to 5 carbon atoms in Rf, and preferably methyl or ethyl. 102 and Rf 103 The halogenated alkyl group having 1 to 5 carbon atoms is specifically a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are replaced by halogen atoms. As the halogen atom, a fluorine atom is preferred. 102 and Rf 103 , preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, further preferably a hydrogen atom.

[0827] In formula (f1-1), nf 1 It is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

[0828] In formula (f1-1), Rf 101 It is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom.

[0829] The hydrocarbon group containing a fluorine atom may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

[0830] In addition, the hydrocarbon group containing fluorine atoms preferably has 25% or more of the hydrogen atoms therein fluorinated, more preferably 50% or more, and particularly preferably 60% or more of the hydrogen atoms fluorinated from the viewpoint of improving the hydrophobicity of the resist film during immersion exposure.

[0831] Among them, as Rf101 , more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, particularly preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF3.

[0832] The weight average molecular weight (Mw) of component (F) (polystyrene conversion based on gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, the solubility in the resist solvent is sufficient for use as a resist, while if it is above the lower limit of this range, the water repellency of the resist film is good.

[0833] The molecular weight distribution coefficient (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0834] In the resist composition of the present embodiment, the component (F) may be used alone or in combination of two or more.

[0835] When the resist composition contains the component (F), the content of the component (F) is preferably 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (A).

[0836] 《Organic solvent component (S)》

[0837] The resist composition of the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component").

[0838] The component (S) may be any component that can dissolve the components used to form a uniform solution, and any component can be appropriately selected from conventionally known solvents for chemically amplified resist compositions.

[0839] In the resist composition of this embodiment, the component (S) may be used alone or as a mixed solvent of two or more. Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0840] Furthermore, as the component (S), a mixed solvent obtained by mixing PGMEA with a polar solvent is also preferred. The blending ratio (mass ratio) thereof may be appropriately determined in consideration of the compatibility of PGMEA with the polar solvent.

[0841] In addition, component (S) is preferably a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5.

[0842] The amount of component (S) used is not particularly limited and is appropriately set according to the coating film thickness at a concentration that allows application to a substrate, etc. For example, component (S) is used so that the solid content concentration of the resist composition is 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more.

[0843] The resist composition of this embodiment can also be prepared by dissolving the resist material in the (S) component and then removing impurities using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition can be filtered using a filter composed of a polyimide porous membrane, a filter composed of a polyamide-imide porous membrane, or a filter composed of a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include the porous membranes described in Japanese Patent Application Laid-Open No. 2016-155121.

[0844] The resist composition of the present embodiment described above contains the resin component (A1) having the structural unit (a01) and the structural unit (a10), and the compound (D0).

[0845] The resist composition of this embodiment uses a compound (D0) having relatively low nucleophilicity, for example, capable of moderately increasing the diffusion of the acid generated from component (B) by exposure, in the resin component (A1) having structural units (a01) and structural units (a10) with good adhesion to the substrate, thereby achieving high adhesion to the substrate and being able to form a pattern of a good shape.

[0846] Furthermore, since the resin component (A1) and the compound (D0) have good heat resistance, the variation in CD is small.

[0847] As described above, according to the resist composition of the present embodiment, a pattern can be formed that achieves both a good shape and improved adhesion and CD stability.

[0848] Furthermore, since the resist composition of the present embodiment has the above-mentioned effects, it is a resist material particularly useful for forming a thick film resist in which light hardly reaches the bottom during exposure.

[0849] (Resist Pattern Formation Method)

[0850] The resist pattern forming method according to the second embodiment of the present invention is a method comprising: a step (i) of forming a resist film on a support using the resist composition of the above-mentioned embodiment; a step (ii) of exposing the resist film; and a step (iii) of developing the exposed resist film to form a resist pattern.

[0851] As one embodiment of the resist pattern forming method, for example, a resist pattern forming method performed as follows can be mentioned.

[0852] Step (i):

[0853] First, the resist composition of the above embodiment is applied to a support using a spin coater or the like, and then baked (pre-baked (PAB)) at, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.

[0854] Step (ii):

[0855] Next, the resist film is selectively exposed by exposing through a mask having a predetermined pattern (mask pattern) using an exposure device such as a KrF exposure device, and then baked (post-exposure bake (PEB)) at a temperature of 80 to 150°C for 40 to 120 seconds, preferably for 60 to 90 seconds.

[0856] Step (iii):

[0857] Next, the exposed resist film is developed using an alkaline developer in an alkaline development process or an organic solvent-containing developer (organic developer) in a solvent development process.

[0858] After the development process, a rinsing process is preferably performed. In the case of an alkaline development process, the rinsing process is preferably performed using pure water, and in the case of a solvent development process, the rinsing process is preferably performed using a rinsing liquid containing an organic solvent.

[0859] In the case of a solvent development process, after the development process or the rinsing process, a process of removing the developing solution or the rinsing solution attached to the pattern by a supercritical fluid may be performed.

[0860] Drying is performed after the development process or after the rinsing process. In addition, a baking process (post-baking) may be performed after the above-mentioned development process, depending on the situation.

[0861] In this manner, a resist pattern can be formed.

[0862] The resist pattern forming method according to this embodiment will be described below in detail.

[0863] The support is not particularly limited, and conventionally known supports can be used. Examples include substrates for electronic components and supports on which a predetermined wiring pattern is formed. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Materials for the wiring pattern include copper, aluminum, nickel, and gold.

[0864] The resist pattern forming method of the present embodiment forms a resist film using the resist composition of the above-described embodiment, and is therefore useful when the resist film formed in step (i) is relatively thick.

[0865] The thickness of the resist film formed in step (i) is preferably in the range of 5 to 30 μm, more preferably 7 to 20 μm, and even more preferably 10 to 20 μm, for example.

[0866] The thickness of the resist film can be adjusted by the content of the component (A) in the resist composition used in step (i). That is, the higher the content of the component (A) in the resist composition, the easier it is to form a thick resist film.

[0867] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, and soft X-ray can be used.

[0868] The resist composition is highly useful for KrF excimer lasers. That is, the resist pattern forming method of the present embodiment is particularly useful when the resist film is exposed to KrF excimer laser light in the step of exposing the resist film.

[0869] The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion lithography.

[0870] Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index greater than that of air, and exposure is performed in this state (immersion exposure).

[0871] The immersion medium is preferably a solvent having a refractive index larger than that of air and smaller than that of the resist film to be exposed, and examples thereof include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.

[0872] As the immersion medium, water is preferably used.

[0873] As an alkaline developer used for the development treatment in the alkaline development process, a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution may be mentioned, for example.

[0874] The organic solvent contained in the organic developer used for the development treatment in the solvent development process can be any organic solvent that can dissolve component (A) (component (A) before exposure) and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents can be mentioned.

[0875] Ketone solvents are organic solvents containing C-C(=O)-C in their structure. Ester solvents are organic solvents containing C-C(=O)-O-C in their structure. Alcohol solvents are organic solvents containing an alcoholic hydroxyl group in their structure. "Alcoholic hydroxyl" refers to a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents containing a nitrile group in their structure. Amide solvents are organic solvents containing an amide group in their structure. Ether solvents are organic solvents containing a C-O-C in their structure.

[0876] Some organic solvents contain multiple functional groups that are characteristic of the above-mentioned solvents in their structures. In such cases, the organic solvent is simultaneously classified as any solvent type containing the functional groups. For example, diethylene glycol monomethyl ether is classified as both an alcohol solvent and an ether solvent in the above-mentioned classifications.

[0877] The hydrocarbon solvent is composed of a halogenated hydrocarbon and has no substituents other than halogen atoms. The halogen atom is preferably a fluorine atom.

[0878] As the organic solvent contained in the organic developer, polar solvents are preferred among those mentioned above, and ketone solvents, ester solvents, nitrile solvents and the like are preferred.

[0879] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0880] Examples of the nitrile solvent include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0881] The organic developer may be mixed with known additives as needed. Examples of such additives include surfactants. Surfactants are not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants may be used.

[0882] The development process can be carried out by a known development method, for example, a method of immersing the support in a developer for a certain period of time (immersion method), a method of carrying the developer on the surface of the support by surface tension and allowing it to remain at rest for a certain period of time (static method), a method of spraying the developer onto the surface of the support (spraying method), a method of continuously discharging the developer onto the support rotating at a certain speed while scanning a developer discharge nozzle at a certain speed (dynamic distribution method), etc.

[0883] As the organic solvent contained in the rinse solution used for the rinse treatment after the development process in the solvent development process, for example, an organic solvent that is difficult to dissolve the resist pattern among the organic solvents listed as the organic solvents used in the organic developer can be appropriately selected and used. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used.

[0884] These organic solvents may be used alone or in combination of two or more, or may be mixed with organic solvents other than those listed above or water.

[0885] The rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of such rinsing methods include a method of continuously discharging the rinsing liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinsing liquid for a predetermined period of time (immersion method), and a method of spraying the rinsing liquid onto the surface of the support (spray coating method).

[0886] According to the resist pattern forming method of the present embodiment described above, since the above-mentioned resist composition is used, a resist pattern having small CD variation, high adhesion to the substrate, and a good shape can be formed.

[0887] The various materials used in the resist composition of the above embodiment and the resist pattern forming method of the above embodiment (for example, a resist solvent, a developer, a rinse solution, an anti-reflective film forming composition, an outer coating forming composition, etc.) are preferably free of impurities such as metals, metal salts containing halogens, acids, bases, components containing sulfur atoms or phosphorus atoms, etc.

[0888] Here, examples of impurities including metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially no impurities (below the detection limit of the measuring device).

[0889] Example

[0890] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.

[0891] <Preparation of Resist Composition>

[0892] (Examples 1 to 16, Comparative Examples 1 to 4)

[0893] The components shown in Tables 1 to 4 were mixed and dissolved to prepare resist compositions of respective examples.

[0894] [Table 1]

[0895]

[0896] [Table 2]

[0897]

[0898] [Table 3]

[0899]

[0900] [Table 4]

[0901]

[0902] In Tables 1 to 4, each abbreviation has the following meanings: The numerical value in [ ] is the blending amount (parts by mass).

[0903] The following are the meanings of the abbreviations of the component (A), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement, the molecular weight distribution coefficient (Mw / Mn), and the 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was determined by C-NMR.

[0904] (A1)-1: A polymer compound represented by the following chemical formula (A1-1). The polymer compound (A1-1) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0905] (A1)-2: A polymer compound represented by the following chemical formula (A1-2). The polymer compound (A1-2) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0906] (A1)-3: A polymer compound represented by the following chemical formula (A1-3). The polymer compound (A1-3) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0907] (A1)-4: A polymer compound represented by the following chemical formula (A1-4). The polymer compound (A1-4) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0908] (A1)-5: A polymer compound represented by the following chemical formula (A1-5). The polymer compound (A1-5) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0909] (A1)-6: A polymer compound represented by the following chemical formula (A1-6). The polymer compound (A1-6) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m / n = 50 / 20 / 30.

[0910] [Chemistry 71]

[0911]

[0912] (A2)-1: A polymer compound represented by the following chemical formula (A2-1). The polymer compound (A2-1) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0913] (A2)-2: A polymer compound represented by the following chemical formula (A2-2). The polymer compound (A2-2) has a weight average molecular weight (Mw) of 10,000, a molecular weight distribution coefficient (Mw / Mn) of 2.0, and a copolymerization composition ratio (the ratio (molar ratio) of the structural units in the structural formula) of l / m = 70 / 30.

[0914] [Chemistry 72]

[0915]

[0916] (B)-1 to (B)-8: Acid generators composed of the following compounds (B-1) to (B-8), respectively.

[0917] [Chemistry 73]

[0918]

[0919] [Chemistry 74]

[0920]

[0921] [Chemistry 75]

[0922]

[0923] (D0)-1 to (D0)-4: Acid diffusion controllers composed of the following compounds (D0-1) to (D0-4), respectively.

[0924] (D2)-1, (D2)-2: Acid diffusion controllers composed of the following compounds (D2-1) and (D2-2).

[0925] In addition, the boiling point (BP) is also described below the chemical formula name.

[0926] (S)-1: a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 50 / 50 (mass ratio).

[0927] [Chemistry 76]

[0928]

[0929] [Chemistry 77]

[0930]

[0931] <Resist Pattern Formation Method 1>

[0932] Step (i):

[0933] The resist composition of each example was applied onto an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a coater, and pre-baked (PAB) on a hot plate at 140° C. for 90 seconds and dried to form a 15 μm thick resist film.

[0934] Step (ii):

[0935] Next, the resist film was selectively irradiated with KrF excimer laser light (248 nm) via a mask pattern (6% halftone) using a KrF exposure apparatus NSR-S203B (manufactured by Nikon Corporation; NA (numerical aperture) = 0.60, σ = 0.68).

[0936] Next, a post-exposure bake (PEB) treatment was performed at 120° C. for 90 seconds.

[0937] Step (iii):

[0938] Next, alkaline development was performed at 23° C. for 60 seconds using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developer.

[0939] Then, post-baking was performed at 100° C. for 60 seconds.

[0940] As a result, an isolated space pattern (hereinafter referred to as "IS pattern") having a space width of 3 μm and a pitch of 18 μm was formed.

[0941] [Evaluation of pattern shape]

[0942] The cross-sectional shape of the IS pattern formed with the optimal exposure amount in the above-mentioned <Formation of Resist Pattern 1> was observed using a length measurement SEM (scanning electron microscope, accelerating voltage 15 kV, trade name: SU-5000, manufactured by Hitachi High-Technologies Corporation) to measure Figure 1 The gap width A at the portion of the resist pattern in contact with the substrate and the gap width B at a position 30% above the portion in the height direction of the resist pattern in contact with the substrate are shown. The difference (B [nm]) between the gap width B and the gap width A is calculated and used as an indicator for evaluating the pattern shape. The closer the difference between B and A is to 0, the more rectangular the shape.

[0943] The results are shown in Tables 5 to 7 as "Pattern Shapes B to A [nm]".

[0944] [Shot dimensional uniformity (CDU)]

[0945] The IS pattern formed with the optimal exposure dose in the above-mentioned "Resist Pattern Formation 1" was observed from above (7×15 shots) using a length-measuring SEM (scanning electron microscope, accelerating voltage 300V, trade name: S-9220, manufactured by Hitachi High-Technologies Corporation). The width of the spaces within the IS pattern (38 points within the above-mentioned shot) was measured. The value (3σ) tripled the standard deviation (σ) calculated from the measurement results. A smaller value (3σ) thus determined indicates a higher uniformity in the dimensional (CD) of the space widths formed in the resist film.

[0946] The results are shown in Tables 5 to 7 as "CDU (nm)".

[0947] <Resist Pattern Formation Method 2>

[0948] A 1:1 SL pattern with a line width of 4 μm was formed by the same method as in the above-mentioned <Formation of Resist Pattern 1> except that the photomask was changed.

[0949] [Evaluation of pattern collapse]

[0950] In the step (ii) of the above-mentioned <Formation of Resist Pattern 1>, the exposure dose [mJ / cm 2 At this time, a length measurement SEM (scanning electron microscope, accelerating voltage 300V, trade name: S-9220, manufactured by Hitachi High-Technologies Corporation) was used to measure the maximum size of the spaced portion of the SL pattern imaged without pattern collapse.

[0951] The results are shown in Tables 5 to 7 as "Pattern collapse (maximum size) (μm)".

[0952] [Table 5]

[0953]

[0954] [Table 6]

[0955]

[0956] [Table 7]

[0957]

[0958] As shown in Tables 5 to 7, it was confirmed that the resist compositions of Examples were better in pattern shape, CDU, and pattern collapse (maximum dimension) than the resist compositions of Comparative Examples.

[0959] Therefore, it was confirmed that the resist composition of the example can form a pattern having small CD variation, high adhesion to the substrate, and a good shape.

[0960] On the other hand, since the resist compositions of Comparative Examples 1 and 2 contained an acid diffusion controller having a relatively low boiling point, the acid diffusion controller was decomposed or volatilized by heating during resist pattern formation, and thus could not fully exhibit its function as an acid diffusion controller.

[0961] Therefore, the resist patterns formed from the resist compositions of Comparative Examples 1 and 2 had large values ​​of pattern shape BA [nm] and large variations in CD.

[0962] The resist compositions of Comparative Examples 3 and 4 contain a resin having a structural unit having relatively poor adhesion to the substrate and heat resistance. Therefore, the resist patterns formed from the resist compositions of Comparative Examples 3 and 4 have low adhesion to the substrate and large CD variations.

[0963] While preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications may be made to the configuration without departing from the spirit of the present invention. The present invention is not limited by the foregoing description but is limited only by the scope of the appended claims.

Claims

1. A resist composition which generates acid by exposure and whose solubility in a developer changes due to the action of the acid, characterized in that: contain: The solubility of the resin component (A1) in the developer solution changes due to the action of the acid; The compound (D0) has a group represented by the following general formula (d0-r), The resin component (A1) has a structural unit (a01) represented by the following general formula (a0-1) and a structural unit (a10) represented by the following general formula (a10-1), [Chemistry 1] In the formula, Rx 01 is a hydrogen atom, an alkyl group or an alkoxy group, Rx 021 ~Rx 028 are independently a hydrogen atom or an alkyl group, nd is 0 or 1, and * represents a bonding position. [Chemistry 2] In the formula, R 0 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, Va 0 is a single bond or a divalent linking group, Ra 0 is an acid dissociable group represented by the following general formula (a01-r-1), [Chemistry 3] Where Ra 01 ~Ra 03 are each independently a hydrocarbon group which may have a substituent, Ra 02 and Ra 03 Can bond to each other to form a ring, * indicates the bonding position, [Chemistry 4] In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, x1 is a single bond or a divalent linking group, Wa x1 is an aromatic hydrocarbon group which may have a substituent, n ax1 An integer greater than 1.

2. The resist composition according to claim 1, wherein The compound (D0) is a compound represented by the following general formula (d0), [Chemistry 5] In formula (d0), Rd 01 is a group represented by the general formula (d0-r), wherein the general formula (d0-r) The * in the formula (d0) represents the bonding position with the oxygen atom (-O-), p is 0 or 1, q is an integer greater than 1, Rdx is a hydrogen atom, a hydroxyl group or a q-valent organic group, and when q is greater than 2, multiple [Rd 01 -O-(C=O)p-] may be the same as or different from each other.

3. The resist composition according to claim 1 or 2, characterized in that The Rx 01 It is an alkoxy group.

4. The resist composition according to claim 1, wherein The compound (D0) is a compound represented by the following general formula (d0-1) or (d0-2), [Chemistry 6] Where Rd 011 , Rd 012 and Rd 021 ~Rd 024 The groups are represented by the general formula (d0-r), which may be the same groups or different groups. The * in the general formula (d0-r) represents the bonding position with the oxygen atom (-O-) in the formula (d0-1) or (d0-2), Ld is a single bond or a divalent organic group, and p1 is 0 or 1.

5. The resist composition according to claim 1, wherein The compound (D0) has a boiling point of 250 to 800°C.

6. The resist composition according to claim 1, wherein It further contains an acid generator component (B) that generates acid upon exposure, The acid generator component (B) includes a compound represented by the following general formula (b01), [Chemistry 7] Where, X - As the counter anion, Rb 01 is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent, Lb 01 is a single bond or a divalent linking group, Rb 02 and Rb 03 are each independently an alkyl group which may have a substituent, or an alkenyl group which may have a substituent, Rb 02 and Rb 03 They may bond to each other to form an aliphatic ring together with the sulfur atom in the formula.

7. A method for forming a resist pattern, characterized in that: The method comprises: forming a resist film on a support using the resist composition according to claim 1; exposing the resist film to light; and developing the exposed resist film to form a resist pattern.

Images