Resist composition and resist pattern forming method

Abstract

An antireflective composition containing a resin component (A1) having a structural unit (a1) containing an acid decomposable group, a structural unit (a10) represented by formula (a10-1), and a plasticizer component (Z) having a structural unit (z1) represented by formula (z1-1) and containing no acid dissociation group, the content of the plasticizer component (Z) being 50 parts by mass or less relative to 100 parts by mass of the resin component (A1), and the solid content concentration being 25% by mass or more. In the formulae, Wa x1 is an aromatic hydrocarbon group. Vz 0 is a single bond or a 2-valent hydrocarbon group containing no acid dissociation group. Rz 0 is a hydrogen atom or a hydrocarbon group containing no acid dissociation group.[Chemical Formula 1]

Description

TECHNICAL FIELD

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

[0002] This application claims priority based on Japanese Patent Application No. 2019-223096 filed on December 10, 2019, and the contents thereof are incorporated herein. BACKGROUND

[0003] In a photolithography technique, for example, the following processes are performed: a resist film composed of a resist material is formed on a substrate, the resist film is selectively exposed, and a development treatment is performed, thereby forming a resist pattern of a prescribed shape on the resist film. A resist material in which the exposed portion of the resist film changes to a property of dissolving in a developer is called a positive type, and a resist material in which the exposed portion of the resist film changes to a property of not dissolving in a developer is called a negative type.

[0004] In recent years, in the production of semiconductor elements and liquid crystal display elements, due to the progress of photolithography techniques, the miniaturization of patterns has rapidly advanced. As a method of miniaturization, generally, the shortening of the wavelength (the increase of the energy) of an exposure light source is performed. Specifically, in the past, ultraviolet rays typified by g-rays and i-rays were used, and now, KrF excimer laser or ArF excimer laser is used for mass production of semiconductor elements. In addition, researches on EUV (extreme ultraviolet rays), EB (electron beams), X-rays, and the like, which have shorter wavelengths (higher energy) than these excimer lasers, are also being conducted.

[0005] For a resist material, sensitivity with respect to these exposure light sources, resolution of reproducibly forming a fine-sized pattern, and the like, are required as lithography characteristics.

[0006] As a resist material satisfying such requirements, a chemical amplification type resist composition containing a base material component whose solubility in a developer changes due to the action of an acid, and an acid generator component which generates an acid by exposure, has been used in the past.

[0007] For example, in the case where the above-mentioned developer is an alkali developer (alkali development process), as a chemical amplification type resist composition of a positive type, a composition containing a resin component (base resin) whose solubility in an alkali developer increases due to the action of an acid, and an acid generator component, is generally used. If a resist film formed using the resist composition is selectively exposed at the time of resist pattern formation, an acid is generated from the acid generator component at the exposed portion, the polarity of the base resin increases due to the action of the acid, and the exposed portion of the resist film becomes soluble with respect to the alkali developer. Therefore, by performing alkali development, a non-exposed portion of the resist film remains as a positive pattern.

[0008] On the other hand, in the case where such a chemically amplified resist composition is applied to a solvent developing process using a developing solution containing an organic solvent (organic developing solution), if the polarity of the base resin increases, the solubility to the organic developing solution relatively decreases, and thus the unexposed portions of the resist film are dissolved and removed by the organic developing solution, and a negative resist pattern in which the exposed portions of the resist film remain as a pattern is formed. The solvent developing process in which such a negative resist pattern is formed is sometimes referred to as a negative developing process.

[0009] Hitherto, as the base resin of a chemically amplified resist composition, for example, for a KrF excimer laser (248 nm), a polyhydroxystyrene (PHS) having high transparency or a resin in which the hydroxyl group of the PHS is protected by a dissolution inhibiting group having acid dissociability (PHS-based resin) is used. Or for example, for an ArF excimer laser (193 nm), a resin in which the hydroxyl group in the carboxyl group of (meth)acrylic acid is protected by a dissolution inhibiting group having acid dissociability ((meth)acrylic acid-based resin) is used (for example, refer to Patent Document 1).

[0010] As the dissolution inhibiting group having acid dissociability, a so-called acetal group such as a chain ether group represented by 1-ethoxyethyl or a cyclic ether group represented by tetrahydropyranyl, a tertiary alkyl group represented by a tert-butyl group, a tertiary alkoxycarbonyl group represented by a tert-butoxycarbonyl group, and the like are mainly used.

[0011] Further, as the acid generator component used in a chemically amplified resist composition, various acid generator components have been proposed hitherto, and onium salt-based acid generators such as iodonium salts or sulfonium salts, sulfonic acid oxime ester-based acid generators, diazomethane-based acid generators, nitrobenzyl sulfonic acid salt-based acid generators, imino sulfonic acid salt-based acid generators, disulfone-based acid generators, and the like are known.

[0012] Among them, onium salt-based acid generators are generally used, and onium salt-based acid generators having a triphenyl sulfonium or the like onium ion in the cation portion are mainly used. In the anion portion of the onium salt-based acid generators, an alkyl sulfonic acid ion or a fluoroalkyl sulfonic acid ion in which a part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the like are generally used.

[0013] However, currently, with the high integration of LSIs and the high speed of communication, an increase in memory capacity is required, and further miniaturization of patterns is rapidly progressing. However, in photolithography using electron rays or EUV, although the formation of a fine pattern of several tens of nanometers is targeted, there are still many technical problems in which productivity is low, and there are limitations in the technology of fine processing.

[0014] In response to this, in addition to miniaturization, development of three-dimensional structure devices in which memory is increased by stacking cells and laminating is being promoted.

[0015] Prior Art Documents

[0016] Patent Literature

[0017] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 2003-241385 SUMMARY

[0018] PROBLEMS TO BE SOLVED BY THE INVENTION

[0019] In the production of the three-dimensional structure device, there is a process of forming a thick resist film of, for example, 5 μm or more in thickness, which is thicker than conventional films, on the surface of a workpiece, forming a resist pattern, and performing etching or the like. In the case where a chemically amplified resist composition is used here, there is a problem that the thicker the resist film, the more difficult it is to maintain the sensitivity at the time of exposure, the resolution at the time of development decreases, and it is difficult to obtain a desired resist pattern shape. Further, there is a problem that the thicker the resist film, the more likely it is to cause cracks in the resist pattern. Further, there is a problem that surface roughness of the pattern at the time of etching is likely to occur.

[0020] The present invention has been achieved in view of the above-described circumstances, and a technical problem thereof is to provide a resist composition capable of forming a thick resist film and difficult to cause cracks and surface roughness at the time of etching, and a resist pattern forming method using the same.

[0021] SOLUTION TO THE PROBLEM

[0022] To solve the above-described technical problem, the present invention adopts the following configuration.

[0023] That is, the first aspect of the present invention is a resist composition which is a resist composition that generates acid by exposure and whose solubility to a developer changes due to the action of the acid, characterized by containing a resin component (Al) having a structural unit (al) containing an acid-decomposable group whose polarity increases due to the action of the acid, and a structural unit (a10) represented by the following general formula (a10-1), and a plasticizer component (Z) having a structural unit (zl) represented by the following general formula (zl-1) and not containing an acid-dissociable group, the content of the plasticizer component (Z) being 50 parts by mass or less relative to 100 parts by mass of the resin component (Al), and the solid content concentration being 25% by mass or more.

[0024] [Chemical Formula 1]

[0025]

[0026] (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. Ya x1 is a single bond or a divalent linking group. Wax1 is an aromatic hydrocarbon group which can have a substituent. n ax1 is an integer of 1 or more.

[0027] [Chem. 2]

[0028]

[0029] (In the formula, R is a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a halogenated alkyl group having a carbon number of 1 to 5. V 0 is a single bond or a 2-valent hydrocarbon group which can have a hetero atom. In the case where V 0 is a 2-valent hydrocarbon group which can have a hetero atom, V 0 does not have an acid dissociation group. Rz 0 is a hydrogen atom or a group represented by the following general formula (z1-r-1).

[0030] [Chem. 3]

[0031]

[0032] (In the formula, Rz 01 is a hydrocarbon group which can have a substituent. Rz 02 is a hydrogen atom or a hydrocarbon group which can have a substituent. Rz 01 is a hydrogen atom or a hydrocarbon group which can have a substituent. Rz 02 can be bonded to each other to form a ring structure. In the case where Rz 01 and Rz 02 does not have an acid dissociation group. * is a bond.

[0033] The second aspect of the present application is a resist pattern forming method characterized by comprising: a step of forming a resist film on a support using the resist composition of the first aspect; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

[0034] Effects of the Invention

[0035] According to the present application, it is possible to provide a resist composition which can form a thick resist film and is difficult to generate cracks and difficult to generate surface roughness at the time of etching, and a resist pattern forming method using the same. DETAILED DESCRIPTION

[0036] In the present specification and claims, "aliphatic" is a relative concept with respect to aromatic, and is defined as a group, compound, etc. which does not have aromaticity.

[0037] Unless otherwise specified, "alkyl" includes a 1-valent saturated hydrocarbon group of a linear shape, a branched shape, and a cyclic shape. The same applies to the alkyl group in an alkoxy group.

[0038] "Alkylene" includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.

[0039] "Alkyl" is a monovalent saturated hydrocarbon group. As the number of carbon atoms, 1 to 20 can be mentioned. As the number of carbon atoms, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 can be mentioned.

[0040] "Fluoroalkyl" or "fluoroalkylene" means a group in which a part or all of the hydrogen atoms of alkyl or alkylene is replaced with a fluorine atom.

[0041] "Structural unit" means a monomeric unit (monomer unit) constituting a high molecular compound (resin, polymer, copolymer).

[0042] In the case where "may have a substituent" or "may have substituents" is described, both the case where a hydrogen atom (-H) is replaced with a monovalent group and the case where methylene (-CH2-) is replaced with a divalent group are included.

[0043] "Exposure" is a concept including irradiation of all kinds of radiation.

[0044] "Base component" means an organic compound having a film-forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. By making the molecular weight of the organic compound 500 or more, the film-forming ability is improved, and in addition, a nanoscale resist pattern is easily formed. The organic compound used as a base component is roughly classified into a non-polymer and a polymer. As the non-polymer, a non-polymer having a molecular weight of 500 or more and less than 4000 is generally used. Hereinafter, in the case where "low molecular compound" is mentioned, a non-polymer having a molecular weight of 500 or more and less than 4000 is meant. As the polymer, a polymer having a molecular weight of 1000 or more is generally used. Hereinafter, in the case where "resin", "high molecular compound", or "polymer" is mentioned, a polymer having a molecular weight of 1000 or more is meant. As the molecular weight of the polymer, weight average molecular weight based on polystyrene conversion by GPC (gel permeation chromatography) is used.

[0045] "Structural unit derived from an acrylate" means a structural unit constituted by cleavage of the olefinic double bond of an acrylate.

[0046] "Acrylate" is a compound in which the hydrogen atom at the carboxyl terminal of acrylic acid (CH2=CH-COOH) is replaced with an organic group.

[0047] The hydrogen atom bonded to the carbon atom at the α-position of the acrylate can be replaced with a substituent. The substituent (R α0) is an atom or a group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, and the like. In addition, a substituent (R α0 ) is a diester of itaconic acid substituted with a substituent containing an ester bond, a substituent (R α0 ) is an α-hydroxy acrylate substituted with a hydroxyalkyl group or a group modifying the hydroxy group thereof. In addition, unless otherwise specified, the carbon atom at the α-position of an acrylate refers to the carbon atom to which the carbonyl group of the acrylate is bonded.

[0048] Hereinafter, an acrylate in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent will be referred to as an α-substituted acrylate. In addition, an acrylate and an α-substituted acrylate will be collectively referred to as "(α-substituted) acrylate" unless otherwise specified.

[0049] The "structural unit derived from a hydroxystyrene" refers to a structural unit formed by cleavage of the olefinic double bond of a hydroxystyrene. The "structural unit derived from a hydroxystyrene derivative" refers to a structural unit formed by cleavage of the olefinic double bond of a hydroxystyrene derivative.

[0050] The "hydroxystyrene derivative" refers to a concept including a compound in which the hydrogen atom at the α-position of a hydroxystyrene is substituted with another substituent such as an alkyl group, a haloalkyl group, and the like, and derivatives thereof. As the derivatives thereof, there can be mentioned a compound in which the hydrogen atom of the hydroxy group of the hydroxystyrene, which can be substituted with a substituent, is substituted with an organic group; a compound in which the benzene ring of the hydroxystyrene, in which the hydrogen atom at the α-position can be substituted with a substituent, is bonded with a substituent other than a hydroxy group; and the like. In addition, the α-position (carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

[0051] As the substituent substituting the hydrogen atom at the α-position of the substituted hydroxystyrene, the same groups as those exemplified as the substituent at the α-position in the above-described α-substituted acrylate can be mentioned.

[0052] The "structural unit derived from a vinylbenzoic acid or a vinylbenzoic acid derivative" refers to a structural unit formed by cleavage of the olefinic double bond of a vinylbenzoic acid or a vinylbenzoic acid derivative.

[0053] The "vinylbenzoic acid derivative" refers to a concept including a compound in which the hydrogen atom at the α-position of a vinylbenzoic acid is substituted with another substituent such as an alkyl group, a haloalkyl group, and the like, and derivatives thereof. As the derivatives thereof, there can be mentioned a compound in which the hydrogen atom of the carboxyl group of the vinylbenzoic acid, which can be substituted with a substituent, is substituted with an organic group; a compound in which the benzene ring of the vinylbenzoic acid, in which the hydrogen atom at the α-position can be substituted with a substituent, is bonded with a substituent other than a hydroxy group and a carboxyl group; and the like. In addition, the α-position (carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

[0054] The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, examples include alkyl groups having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, isoamyl, neopentyl, and the like).

[0055] Further, the haloalkyl group as the substituent at the α-position specifically includes a group in which some or all of the hydrogen atoms of the "alkyl group as the substituent at the α-position" described above are replaced with a halogen atom. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be mentioned, and a fluorine atom is particularly preferred.

[0056] Further, the hydroxyalkyl group as the substituent at the α-position specifically includes a group in which some or all of the hydrogen atoms of the "alkyl group as the substituent at the α-position" described above are replaced with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

[0057] In the present specification and the present claims, depending on the structure represented by the chemical formula, there are asymmetric carbons, and structures of enantiomers or diastereomers can exist. In this case, these isomers are represented by one chemical formula. These isomers can be used individually or as a mixture.

[0058] (Resist composition)

[0059] The resist composition of the first aspect of the present application is a resist composition in which the solubility to a developer is changed by acid generated by exposure and by the action of acid, and contains a base material component (A) (hereinafter also referred to as "(A) component") in which the solubility to a developer is changed by the action of acid, and a plasticizer component (Z) (hereinafter also referred to as "(Z) component"). In the resist composition of the present embodiment, the content of the (Z) component is 50 parts by mass or less relative to 100 parts by mass of the (A) component. Further,

[0060] If the above-described resist composition is used to form a resist film, a thick resist film (for example, a film thickness of 5 μm or more) can be formed.

[0061] If the above-described resist composition is used to form a resist film, and the resist film is subjected to selective exposure, an acid is generated in the exposed portion of the resist film, the solubility of the (A) component to a developer is changed by the action of the acid, on the other hand, in the unexposed portion of the resist film, the solubility of the (A) component to a developer does not change, and thus a difference in the solubility to a developer is generated between the exposed portion and the unexposed portion of the resist film. Therefore, if the resist film is developed, in the case where the resist composition is a positive type, the exposed portion of the resist film is dissolved and removed, and thus a positive resist pattern is formed, in the case where the resist composition is a negative type, the unexposed portion of the resist film is dissolved and removed, and thus a negative resist pattern is formed.

[0062] In the present specification, a resist composition in which the exposed portion of a resist film is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition in which the unexposed portion of a resist film is dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. The resist composition of the present embodiment can be either a positive resist composition or a negative resist composition. In addition, the resist composition of the present embodiment can be used in an alkali development process in which an alkali developer is used in a development treatment at the time of resist pattern formation, or can be used in a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.

[0063] The resist composition of the present embodiment has an acid-generating ability by which an acid is generated by exposure, and can be either a (A) component that generates an acid by exposure or an additive component that generates an acid by exposure, which is mixed separately from the (A) component.

[0064] Specifically, the resist composition of the present embodiment (1) can further contain an acid-generating agent component (B) that generates an acid by exposure (hereinafter referred to as a "(B) component"); (2) can be a (A) component that is a component that generates an acid by exposure; (3) can be a (A) component that is a component that generates an acid by exposure and further contains a (B) component. That is, in the cases of the above-described (2) and (3), the (A) component is a "base material component that generates an acid by exposure and in which the solubility to a developer is changed by the action of the acid". In the case where the (A) component is a base material component that generates an acid by exposure and in which the solubility to a developer is changed by the action of the acid, the (Al) component described later is preferably a high molecular compound that generates an acid by exposure and in which the solubility to a developer is changed by the action of the acid. As such a high molecular compound, a resin having a structural unit that generates an acid by exposure can be used. As the structural unit that generates an acid by exposure, a publicly known structural unit can be used. Among them, the resist composition of the present embodiment is preferably the resist composition of the above-described (1).

[0065] <(A) component>

[0066] In the resist composition of the present embodiment, it is preferable that the (A) component contain a resin component (Al) whose solubility in a developer changes due to the action of an acid (hereinafter also referred to as "(Al) component"). By using the (Al) component, since the polarity of the base material component changes before and after exposure, a good developing contrast can be obtained not only in an alkaline developing process but also in a solvent developing process.

[0067] As the (A) component, at least the (Al) component is used, and other high molecular compounds and / or low molecular compounds can be used together with the (Al) component.

[0068] In the case of applying an alkaline developing process, the base material component containing the (Al) component is insoluble in an alkaline developer before exposure, and for example, if an acid is generated from the (B) component by exposure, the polarity thereof increases due to the action of the acid, and thus the solubility in the alkaline developer increases. Therefore, in the formation of a resist pattern, if the resist film obtained by applying the resist composition on a support is selectively exposed, the solubility of the exposed part of the resist film in the alkaline developer changes from insolubility to solubility, and on the other hand, since the unexposed part of the resist film remains insoluble in the alkaline developer and does not change, a positive resist pattern can be formed by performing an alkaline development.

[0069] On the other hand, in the case of applying a solvent developing process, the base material component containing the (Al) component has a high solubility in an organic developer before exposure, and for example, if an acid is generated from the (B) component by exposure, the polarity thereof increases due to the action of the acid, and thus the solubility in the organic developer decreases. Therefore, in the formation of a resist pattern, if the resist film obtained by applying the resist composition on a support is selectively exposed, the solubility of the exposed part of the resist film in the organic developer changes from solubility to insolubility, and on the other hand, since the unexposed part of the resist film remains soluble and does not change, by performing development with an organic developer, a contrast can be generated between the exposed part and the unexposed part, and thus a negative resist pattern can be formed.

[0070] In the resist composition of the present embodiment, one kind of the (A) component can be used alone, or two or more kinds thereof can be used in combination.

[0071] • Regarding the (Al) component

[0072] The (Al) component is a resin component whose solubility in a developer changes due to the action of an acid. The (Al) component has a structural unit (al) containing an acid-decomposable group whose polarity increases due to the action of an acid, and a structural unit (a10) represented by general formula (a10-1).

[0073] The (Al) component can have other structural units in addition to the structural unit (al) and the structural unit (a10) as necessary.

[0074]

[0075] The structural unit (al) is a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid.

[0076] The "acid-decomposable group" is a group having acid-decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.

[0077] As the acid-decomposable group whose polarity increases due to the action of an acid, for example, a group that generates a polar group by the action of an acid can be exemplified.

[0078] As the polar group, for example, a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group (-SO3H), and the like can be exemplified. Among these, a polar group containing -OH in the structure (hereinafter also referred to as "polar group containing OH") is preferred, a carboxyl group or a hydroxyl group is more preferred, and a carboxyl group is particularly preferred.

[0079] As the acid-decomposable group, more specifically, a group in which the above-described polar group is protected by an acid dissociation group (for example, a group in which the hydrogen atom of the polar group containing OH is protected by an acid dissociation group) can be exemplified.

[0080] Here, the "acid dissociation group" means either (i) a group having acid dissociation in which the bond between the acid dissociation group and the atom adjacent to the acid dissociation group can be cleaved by the action of an acid; or (ii) a group in which a part of the bond is cleaved by the action of an acid, and further, a decarboxylation reaction occurs, whereby the bond between the acid dissociation group and the atom adjacent to the acid dissociation group can be cleaved.

[0081] The acid dissociation group constituting the acid-decomposable group must be a group having lower polarity than the polar group generated by the dissociation of the acid dissociation group, and thus, when the acid dissociation group is dissociated by the action of an acid, a polar group having higher polarity than the acid dissociation group is generated, and thus the polarity increases. As a result, the polarity of the (Al) component as a whole increases. By the increase in the polarity, the solubility to the developer changes relatively, and in the case where the developer is an alkali developer, the solubility increases, and in the case where the developer is an organic developer, the solubility decreases.

[0082] As the acid dissociation group, a group that has been proposed so far as an acid dissociation group of a base resin for a chemical amplification-type resist composition can be exemplified.

[0083] ​As the acid-dissociable group for the base resin for the chemically amplified resist composition, specifically, the "acetal type acid-dissociable group", the "tertiary alkyl ester type acid-dissociable group", and the "tertiary alkoxycarbonyl type acid-dissociable group" described below can be exemplified.

[0084] Acetal type acid-dissociable group:

[0085] As the acid-dissociable group for protecting the carboxyl group or the hydroxyl group in the polar group, for example, the acid-dissociable group represented by the following general formula (al-r-l) (hereinafter also referred to as "acetal type acid-dissociable group") can be exemplified.

[0086] [Chemical 4]

[0087]

[0088] [In the formula, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. Ra' 3 is a hydrocarbon group, Ra' 3 may be bonded to any one of Ra' 1 , Ra' 2 to form a ring.]

[0089] In the formula (al-r-l), preferably, at least one of Ra' 1 and Ra' 2 is a hydrogen atom, more preferably both are hydrogen atoms.

[0090] In the case where Ra' 1 or Ra' 2 is an alkyl group, as the alkyl group, the same alkyl group as exemplified above in the description about the α-substituted acrylic ester as the substituent which can be bonded to the carbon atom at the α-position can be exemplified, and preferably an alkyl group having a carbon number of 1 to 5. Specifically, a linear or branched alkyl group can be exemplified. More specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like can be exemplified, and more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0091] In the formula (al-r-l), as the hydrocarbon group of Ra' 3 , a linear or branched alkyl group, or a cyclic hydrocarbon group can be exemplified.

[0092] The linear alkyl group preferably has a carbon number of 1 to 5, more preferably a carbon number of 1 to 4, and further preferably a carbon number of 1 or 2. Specifically, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, and the like can be exemplified. Among them, a methyl group, an ethyl group, or a n-butyl group is preferred, and more preferably a methyl group or an ethyl group.

[0093] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specifically, examples include isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, and the like, with isopropyl being preferred.

[0094] Ra' in the case where Ra 3 The cyclic hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and can be a polycyclic group or a monocyclic group.

[0095] The aliphatic hydrocarbon group that is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, and the like.

[0096] The aliphatic hydrocarbon group that is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 12 carbon atoms. Specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0097] Ra' in the case where Ra 3 The cyclic hydrocarbon group is an aromatic hydrocarbon group having at least one aromatic ring.

[0098] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and can be monocyclic or polycyclic. 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.

[0099] Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings obtained by substituting a part of the carbon atoms of the aromatic hydrocarbon ring with a heteroatom. Examples of the heteroatom in the aromatic heterocyclic ring include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocyclic ring include pyridine rings and thiophene rings.

[0100] Ra' in the case where Ra 3 Specific examples of the aromatic hydrocarbon group in Ra' include groups obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocyclic ring (aryl or heteroaryl); groups obtained by removing one hydrogen atom from an aromatic compound having two or more aromatic rings (e.g., biphenyl, fluorene, and the like); and groups obtained by substituting one hydrogen atom of the aromatic hydrocarbon ring or the aromatic heterocyclic ring with an alkylene group (e.g., benzyl, phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, arylalkyl groups, and the like). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0101] Ra' 3 The cyclic hydrocarbon group in the formula (1) can have a substituent. As the substituent, for example, -R P1 , -R P2 -O-R 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 05 " and the like) can be exemplified.

[0102] Here, R P1 is a monovalent chain saturated hydrocarbon group having a carbon number of 1 to 10, a monovalent aliphatic cyclic saturated hydrocarbon group having a carbon number of 3 to 20, or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 30. In addition, R P2 is a single bond, a divalent chain saturated hydrocarbon group having a carbon number of 1 to 10, a divalent aliphatic cyclic saturated hydrocarbon group having a carbon number of 3 to 20, or a divalent aromatic hydrocarbon group having a carbon number of 6 to 30. Among them, a part or all of the hydrogen atoms of the chain saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group, and the aromatic hydrocarbon group of R P1 and R P2 may be substituted with a fluorine atom. The above aliphatic cyclic hydrocarbon group can have one or more of the above substituents each individually.

[0103] As the monovalent chain saturated hydrocarbon group having a carbon number of 1 to 10, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and the like can be exemplified.

[0104] As the monovalent aliphatic cyclic saturated hydrocarbon group having a carbon number of 3 to 20, for example, monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, and the like; polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octyl group, a tricyclo[5.2.1.02,6]decyl group, a tricyclo[3.3.1.13,7]decyl group, a tetracyclo[6.2.1.13,6.02,7]dodecyl group, an adamantyl group, and the like can be exemplified.

[0105] As the monovalent aromatic hydrocarbon group having a carbon number of 6 to 30, for example, a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, and the like can be exemplified.

[0106] Ra' 3With Ra' 1 Ra' 2 When a ring is formed by bonding any one of the elements, the cyclic group is preferably a four- to seven-membered ring, more preferably a four- to six-membered ring. Specific examples of this cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0107] Tertiary alkyl ester type acid dissociable groups:

[0108] As an acid-dissociating group that protects the carboxyl group in the above-mentioned polar groups, examples of acid-dissociating groups represented by the following general formula (a1-r-2) can be cited.

[0109] In addition, for ease of explanation, the alkyl group in the acid dissociation group represented by the following formula (a1-r-2) will be referred to as the "tertiary alkyl ester type acid dissociation group".

[0110]

Transformation 5

[0111]

[0112] [In the formula, Ra'] 4 ~Ra' 6 They are hydrocarbon groups, Ra' 5 Ra' 6 They can bond together to form a ring.

[0113] As Ra' 4 The hydrocarbon group can be exemplified by straight-chain or branched alkyl groups, chain or cyclic alkenyl groups, or cyclic hydrocarbon groups.

[0114] Ra' 4 The linear or branched alkyl groups and cyclic hydrocarbon groups (aliphatic hydrocarbon groups as monocyclic groups, aliphatic hydrocarbon groups as polycyclic groups, and aromatic hydrocarbon groups) in Ra' can be exemplified by those described above. 3 The same group.

[0115] Ra' 4 The chain or cyclic alkenyl group is preferably an alkenyl group with 2 to 10 carbon atoms.

[0116] As Ra' 5 Ra' 6 Hydrocarbon groups, for example, can be related to the above Ra' 3 The same hydrocarbon group.

[0117] In Ra' 5 With Ra' 6 When the groups are bonded together to form a ring, examples of groups represented by the following general formula (a1-r2-1), the following general formula (a1-r2-2), and the following general formula (a1-r2-3) can be preferably cited.

[0118] On the other hand, in Ra' 4 ~Ra' 6 In the case where the hydrocarbon groups are independent and not bonded to each other, groups represented by the following general formula (a1-r2-4) are preferred examples.

[0119]

Transformation 6

[0120]

[0121] In the formula (a1-r2-1), Ra' 10 This refers to an alkyl group having 1 to 10 carbon atoms, or a group represented by the following general formula (a1-r2-r1). Ra' 11 Indicates Ra' 10 The bonded carbon atoms together form an aliphatic cyclic group. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group can be substituted. Ra 01 ~Ra 03 Each 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 this chain saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may be substituted. Ra 01 ~Ra 03 Two or more atoms in the formula can bond together to form a ring structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group with Yaa. Ra 04 It is an aromatic hydrocarbon group that can have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each is independently a monovalent chain-like saturated hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group can be substituted. Ra' 14 This refers to a hydrocarbon group that can have substituents. * indicates a bond.

[0122]

Transformation 7

[0123]

[0124] [In the formula, Ya 0 It is a quaternary carbon atom. Ra 031 Ra 032 and Ra 033 Each is an independent hydrocarbon group that can have substituents. Among them, Ra 031 Ra 032 and Ra 033 One or more of them are hydrocarbon groups having at least one polar group.

[0125] In the formula (al-r2-1) above, Ra 10 The alkyl group having 1 to 10 carbons is preferably a group exemplified as the Ra 3 linear or branched alkyl group in the formula (al-r-1) above. Ra 10 The alkyl group having 1 to 5 carbons is preferred.

[0126] In the formula (al-r2-r1) above, Ya 0 is a quaternary carbon atom. That is, the number of adjacent carbon atoms bonded to Ya 0 (carbon atom) is four.

[0127] In the formula (al-r2-r1) above, Ra 031 , Ra 032 and Ra 033 are each independently a hydrocarbon group which can have a substituent. As the hydrocarbon group in Ra 031 , Ra 032 and Ra 033 , a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group can be each independently exemplified.

[0128] In Ra 031 , Ra 032 and Ra 033 , the linear alkyl group preferably has 1 to 5, more preferably 1 to 4, and further preferably 1 or 2 carbons. Specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and the like can be exemplified. Among them, a methyl group, an ethyl group or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0129] In Ra 031 , Ra 032 and Ra 033 , the branched alkyl group preferably has 3 to 10, and more preferably 3 to 5 carbons. Specifically, an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group, and the like can be exemplified, and an isopropyl group is preferred.

[0130] In Ra 031 , Ra 032 and Ra 033 , the chain or cyclic alkenyl group is preferably an alkenyl group having 2 to 10 carbons.

[0131] In Ra 031 , Ra 032 and Ra 033 , the cyclic hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and in addition, can be a polycyclic group or a monocyclic group.

[0132] As the aliphatic hydrocarbon group of the monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. As the monocycloalkane, a monocycloalkane having a carbon number of 3 to 6 is preferable, and specifically, cyclopentane, cyclohexane and the like can be exemplified.

[0133] As the aliphatic hydrocarbon group of the polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable, and as the polycycloalkane, a polycycloalkane having a carbon number of 7 to 12 is preferable, and specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like can be exemplified.

[0134] Ra 031 , Ra 032 and Ra 033 The aromatic hydrocarbon group in the above is a hydrocarbon group having at least one aromatic ring. The aromatic ring, if it is a cyclic conjugated system having 4n+2 π electrons, is not particularly limited, and can be monocyclic or polycyclic. The carbon number of 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, phenanthrene and the like; aromatic heterocyclic rings obtained by substituting a part of carbon atoms constituting the aromatic hydrocarbon ring with a hetero atom; and the like can be exemplified. As the hetero atom in the aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom and the like can be exemplified. As the aromatic heterocyclic ring, specifically, pyridine ring, thiophene ring and the like can be exemplified. As the aromatic hydrocarbon group, specifically, a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocyclic ring (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound having two or more aromatic rings (for example, biphenyl, fluorene and the like); a group obtained by substituting one hydrogen atom of the aromatic hydrocarbon ring or the aromatic heterocyclic ring with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, arylalkyl groups and the like); and the like can be exemplified. The carbon number of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0135] In the case where the hydrocarbon group represented by Ra 031 , Ra 032 and Ra 033 is substituted, as the substituent, for example, a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom and the like), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group and the like), an alkoxycarbonyl group and the like can be exemplified.

[0136] Among the above, the hydrocarbon group in Ra 031 , Ra 032 and Ra 033 which can have a substituent is preferably a straight-chain or branched-chain alkyl group which can have a substituent, and more preferably a straight-chain alkyl group.

[0137] wherein one or more of Ra 031 , Ra 032 , and Ra 033 is a hydrocarbon group having at least a polar group.

[0138] The "hydrocarbon group having a polar group" means a hydrocarbon group in which a methylene group (-CH2-) constituting the hydrocarbon group is substituted with a polar group or a hydrocarbon group in which at least one hydrogen atom constituting the hydrocarbon group is substituted with a polar group.

[0139] As the above "hydrocarbon group having a polar group", a functional group represented by the following general formula (al-pl) is preferable.

[0140] [Chem. 8]

[0141]

[0142] [In the formula, Ra 07 represents a divalent hydrocarbon group having a carbon number of 2 to 12. Ra 08 represents a divalent linking group containing a hetero atom. Ra 06 represents a monovalent hydrocarbon group having a carbon number of 1 to 12. n p0 is an integer of 1 to 6.]

[0143] In the formula (al-pl), Ra 07 represents a divalent hydrocarbon group having a carbon number of 2 to 12. Ra 07 has a carbon number of 2 to 12, preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2.

[0144] Ra 07 is a hydrocarbon group, preferably a chain or cyclic aliphatic hydrocarbon group, more preferably a chain hydrocarbon group.

[0145] As Ra 07 , for example, there can be mentioned a linear alkane diyl group such as ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, and the like; a branched alkane diyl group such as propane-1, 2-diyl, 1-methylbutane-1, 3-diyl, 2-methylpropane-1, 3-diyl, pentane-1, 4-diyl, 2-methylbutane-1, 4-diyl, and the like; a cyclic alkane diyl group such as cyclobutane-1, 3-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 4-diyl, cyclooctane-1, 5-diyl, and the like; a polycyclic aliphatic divalent hydrocarbon group such as norbornane-1, 4-diyl, norbornane-2, 5-diyl, adamantane-1, 5-diyl, adamantane-2, 6-diyl, and the like.

[0146] Among the above, an alkandiyl group is preferable, and a straight-chain alkandiyl group is more preferable.

[0147] In the formula (al-pl), Ra 08 represents a 2-valent linking group containing a hetero atom.

[0148] As Ra 08 For example, -0-, -C(=0)-0-, -C(=0)-, -0-C(=0)-0-, -C(=0)-NH-, -NH-, -NH-C(=NH)- (H can be substituted with an alkyl group, an acyl group, or the like), -S-, -S(=0)2-, -S(=0)2-0-, and the like can be exemplified.

[0149] Among these, from the aspect of solubility to a developing solution, -0-, -C(=0)-0-, -C(=0)-, -0-C(=0)-0- are preferable, and -0-, -C(=0)- are particularly preferable.

[0150] In the formula (al-pl), Ra 06 represents a 1-valent hydrocarbon group having a carbon number of 1 to 12. Ra 06 The carbon number of Ra

[0151] Ra 06 The hydrocarbon group in Ra

[0152] As a chain hydrocarbon group, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and the like can be exemplified.

[0153] The cyclic hydrocarbon group can be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

[0154] As an alicyclic hydrocarbon group, either a monocyclic or a polycyclic one can be used, and as a monocyclic alicyclic hydrocarbon group, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and the like can be exemplified. As a polycyclic alicyclic hydrocarbon group, for example, a decalinyl group, an adamantyl group, a 2-alkyladamant-2-yl group, a l-(adamant-l-yl)alkane-l-yl group, a norbornyl group, a methyl norbornyl group, an isobornyl group, and the like can be exemplified.

[0155] As the aromatic hydrocarbon group, for example, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, and the like can be exemplified.

[0156] As Ra 06 From the viewpoint of solubility to a developing solution, a chain hydrocarbon group is preferred, an alkyl group is more preferred, and a straight-chain alkyl group is further preferred.

[0157] In the formula (al-p1), n p0 is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1.

[0158] Specific examples of the hydrocarbon group having at least a polar group are shown below.

[0159] In the following formula, * is a bond to a quaternary carbon atom (Ya 0 ).

[0160] [Chemical 9]

[0161]

[0162] In the formula (al-r2-r1), Ra 031 , Ra 032 , and Ra 033 , the number of the hydrocarbon group having at least a polar group is one or more, and is appropriately determined in consideration of solubility to a developing solution at the time of resist pattern formation, for example, it is preferred that one or two of Ra 031 , Ra 032 , and Ra 033 have at least a polar group, and it is particularly preferred that one hydrocarbon group have at least a polar group.

[0163] The hydrocarbon group having at least a polar group can have a substituent other than the polar group. As the substituent, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, and the like), a halogenated alkyl group having a carbon number of 1 to 5 can be exemplified.

[0164] In the formula (al-r2-1), Ra 11 (the aliphatic cyclic group formed together with the carbon atom to which Ra 10 is bonded) is preferably a group exemplified as the aliphatic hydrocarbon group of the monocyclic group or the polycyclic group of Ra3in the formula (al-r-1).

[0165] In the formula (al-r2-2), as the cyclic hydrocarbon group formed together with Ya, a group exemplified as Ra 3a group obtained by further removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in the above Ra

[0166] The cyclic hydrocarbon group formed together with Ya can have a substituent. As the substituent, the same group as the above Ra 3 The cyclic hydrocarbon group in the above Ra

[0167] In the formula (al-r2-2), as the Ra 01 ~Ra 03 The monovalent chain saturated hydrocarbon group having a carbon number of 1 to 10 in the above Ra

[0168] As the Ra 01 ~Ra 03 The monovalent aliphatic cyclic saturated hydrocarbon group having a carbon number of 3 to 20 in the above Ra

[0169] Among them, from the viewpoint of easy synthesis of the monomer compound derived from the structural unit (al), the Ra 01 ~Ra 03 is preferably a hydrogen atom, a monovalent chain saturated hydrocarbon group having a carbon number of 1 to 10, and more preferably a hydrogen atom, a methyl group, and an ethyl group, and particularly preferably a hydrogen atom.

[0170] As the chain saturated hydrocarbon group represented by the above Ra 01 ~Ra 03 As the substituent possessed by the chain saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by the above Ra 05 , the same group as the above Ra

[0171] The Ra 01 ~Ra 03 two or more of the above Ra

[0172] In formula (a1-r2-3), Xaa and Yaa together form an aliphatic cyclic group, which is preferably a monocyclic or polycyclic aliphatic hydrocarbon group as Ra 3 in formula (a1-r-1).

[0173] In formula (a1-r2-3), Ra 04 is an aromatic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms can be exemplified. Among them, Ra 04 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, naphthalene, or anthracene, particularly preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene, and most preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0174] In formula (a1-r2-3), Ra 04 may have a substituent, for example, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkoxycarbonyl group, etc. can be exemplified.

[0175] In formula (a1-r2-4), Ra 12 and Ra 13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. As the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 12 and Ra 13 , the same groups as the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 01 to Ra 03 above can be exemplified. Part or all of the hydrogen atoms possessed by this chain saturated hydrocarbon group can be substituted.

[0176] In formula (a1-r2-4), Ra 12 and Ra 13 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group, an ethyl group, and particularly preferably a methyl group.

[0177] In the case where the chain saturated hydrocarbon group represented by Ra 12 and Ra 13 is substituted, as the substituent, for example, the same groups as Ra 05 above can be exemplified.

[0178] In formula (a1-r2-4), Ra 14 is a hydrocarbon group which can have a substituent. As Ra14 The hydrocarbon group in the text can be exemplified by straight-chain or branched alkyl groups, or cyclic hydrocarbon groups.

[0179] Ra' 14 The linear alkyl group in the form preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0180] Ra' 14 The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being preferred.

[0181] In Ra' 14 In the case of a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0182] The aliphatic hydrocarbon group that is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane.

[0183] The aliphatic hydrocarbon group that is the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms. Examples of such polycyclic alkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0184] As Ra' 14 Aromatic hydrocarbon groups in [the text] can be exemplified by those related to Ra. 04 The same group as the aromatic hydrocarbon group in it. Among them, Ra' 14 Preferably, the group is obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; more preferably, the group is obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene; even more preferably, the group is obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene; particularly preferably, the group is obtained by removing one or more hydrogen atoms from naphthalene or anthracene; and most preferably, the group is obtained by removing one or more hydrogen atoms from naphthalene.

[0185] As Ra' 14 Possible substituents include those related to Ra. 04 It can have the same substituents as the substituents.

[0186] In equation (a1-r2-4), Ra' 14In the case of a naphthyl group, the position bonded to the tertiary carbon atom in the formula (al-r2-4) can be any of the 1 -position or the 2-position of the naphthyl group.

[0187] Ra' in the formula (al-r2-4) 14 In the case of an anthryl group, the position bonded to the tertiary carbon atom in the formula (al-r2-4) can be any of the 1 -position, the 2-position, or the 9-position of the anthryl group.

[0188] The following exemplifies specific examples of the group represented by the formula (al-r2-1).

[0189] [Chem. 10]

[0190]

[0191] [Chem. 11]

[0192]

[0193] [Chem. 12]

[0194]

[0195] The following exemplifies specific examples of the group represented by the formula (al-r2-2).

[0196] [Chem. 13]

[0197]

[0198] [Chem. 14]

[0199]

[0200] [Chem. 15]

[0201]

[0202] The following exemplifies specific examples of the group represented by the formula (al-r2-3).

[0203] [Chem. 16]

[0204]

[0205] The following exemplifies specific examples of the group represented by the formula (al-r2-4).

[0206] [Chem. 17]

[0207]

[0208] Tertiary alkoxy carbonyl acid dissociation group:

[0209] As the acid dissociable group for protecting the hydroxyl group in the polar group, for example, an acid dissociable group represented by the following general formula (al-r-3) (hereinafter also referred to as "tertiary alkoxycarbonyl acid dissociable group" for convenience of explanation) can be exemplified.

[0210] [Chem. 18]

[0211]

[0212] [In the formula, Ra 7 ~Ra 9 are each an alkyl group.]

[0213] In the formula (al-r-3), Ra 7 ~Ra 9 are each preferably an alkyl group having a carbon number of 1 to 5, more preferably an alkyl group having a carbon number of 1 to 3.

[0214] Further, the total carbon number of each alkyl group is preferably 3 to 7, more preferably a carbon number of 3 to 5, and most preferably a carbon number of 3 to 4.

[0215] As the structural unit (al), from the viewpoint of inhibiting the decrease in light transmittance in a thick film resist film, it is preferable to contain an acid dissociable group represented by the general formula (al-r-2), and more preferable to contain an acid dissociable group represented by the general formula (al-r2-4). In the general formula (al-r2-4), Ra 12 and Ra 13 are each preferably independently an alkyl group having a carbon number of 1 to 5, more preferably an alkyl group having a carbon number of 1 to 3, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. In the general formula (al-r2-4), Ra 14 is preferably an alkyl group having a carbon number of 1 to 5, more preferably an alkyl group having a carbon number of 1 to 3, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0216] As the structural unit (al), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at an α position can be substituted with a substituent, a structural unit derived from an acrylamide, a structural unit in which at least a part of hydrogen atoms in a hydroxyl group of a structural unit derived from a hydroxyl styrene or a hydroxyl styrene derivative is protected with a substituent containing the acid dissociable group, a structural unit in which at least a part of hydrogen atoms in -C(=O)-OH of a structural unit derived from a vinylbenzoic acid or a vinylbenzoic acid derivative is protected with a substituent containing the acid dissociable group, and the like can be exemplified.

[0217] As the structural unit (a1), among the above-mentioned structural units, a propenoate-derived structural unit in which a hydrogen atom bonded to a carbon atom at the α-position can be substituted with a substituent is preferable. As a preferable specific example of the structural unit (a1), a structural unit represented by the following general formula (a1-1) or (a1-2) can be exemplified.

[0218] [Chem. 19]

[0219]

[0220] (In the formula, R is a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a halogenated alkyl group having a carbon number of 1 to 5. Va 1 is a divalent hydrocarbon group which can have an ether bond. n a1 is an integer of 0 to 2. Ra 1 is an acid dissociable group represented by the above-mentioned general formula (a1-r-1) or (a1-r-2). Wa 1 is an integer of 1 to 3. n a2 is a monovalent hydrocarbon group, n a2 is an integer of 1 to 3. Ra 2 is an acid dissociable group represented by the above-mentioned general formula (a1-r-1) or (a1-r-3).]

[0221] In the formula (a1-1), the alkyl group having a carbon number of 1 to 5 for R is preferably a linear or branched alkyl group having a carbon number of 1 to 5, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like can be exemplified. The halogenated alkyl group having a carbon number of 1 to 5 is a group in which a part or all of the hydrogen atoms of the above-mentioned alkyl group having a carbon number of 1 to 5 are substituted with halogen atoms. As the halogen atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified, and a fluorine atom is particularly preferable.

[0222] As R, a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a fluoroalkyl group having a carbon number of 1 to 5 is preferable, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

[0223] In the formula (a1-1), the divalent hydrocarbon group in Va 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0224] As the divalent hydrocarbon group in Va 1 may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and a saturated aliphatic hydrocarbon group is generally preferable.

[0225] More specifically, as the aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having a ring in the structure, and the like can be exemplified.

[0226] The straight-chain aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, further preferably a carbon number of 1 to 4, and most preferably a carbon number of 1 to 3. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specifically, methylene [-CH2-], ethylene [- (CH2)2-], propylene [- (CH2)3-], butylene [- (CH2)4-], pentylene [- (CH2)5-], and the like can be exemplified.

[0227] The branched aliphatic hydrocarbon group preferably has a carbon number of 2 to 10, more preferably a carbon number of 3 to 6, further preferably a carbon number of 3 or 4, and most preferably a carbon number of 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, alkylmethylene groups such as -CH (CH3) -, -CH (CH2CH3) -, -C (CH3)2-, -C (CH3) (CH2CH3) -, -C (CH3) (CH2CH2CH3) -, -C (CH2CH3)2-, and the like; alkylethylene groups such as -CH (CH3) CH2-, -CH (CH3) CH (CH3) -, -C (CH3)2CH2-, -CH (CH2CH3) CH2-, -C (CH2CH3)2CH2-, and the like; alkylpropylene groups such as -CH (CH3) CH2CH2-, -CH2CH (CH3) CH2-, and the like; alkylbutylene groups such as -CH (CH3) CH2CH2CH2-, -CH2CH (CH3) CH2CH2-, and the like; and the like can be exemplified. As the alkyl group in the alkylalkylene group, a straight-chain alkyl group having a carbon number of 1 to 5 is preferable.

[0228] As the ring-containing aliphatic hydrocarbon group in the structure, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded at the terminal of a straight-chain or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed between straight-chain or branched aliphatic hydrocarbon groups, and the like can be exemplified. As the straight-chain or branched aliphatic hydrocarbon group, the same groups as the straight-chain aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group can be exemplified.

[0229] The alicyclic hydrocarbon group preferably has a carbon number of 3 to 20, and more preferably a carbon number of 3 to 12.

[0230] The alicyclic hydrocarbon group can be either a polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocyclic alkane is preferable. As the monocyclic alkane, a monocyclic alkane having a carbon number of 3 to 6 is preferable, and specifically, cyclopentane, cyclohexane, and the like can be exemplified. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycyclic alkane is preferable, and as the polycyclic alkane, a polycyclic alkane having a carbon number of 7 to 12 is preferable, and specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like can be exemplified.

[0231] as Va 1 The aromatic hydrocarbon group as the divalent hydrocarbon group in the formula (a1-1) is a hydrocarbon group having an aromatic ring.

[0232] The carbon number of the above-mentioned aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, most preferably 6 to 12. Among the carbon number, the carbon number in the substituent is not included. As the aromatic ring which the aromatic hydrocarbon group has, specifically, there can be mentioned an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, and the like; an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting the aromatic hydrocarbon ring with a hetero atom; and the like. As the hetero atom in the aromatic heterocyclic ring, there can be mentioned an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0233] As the aromatic hydrocarbon group, specifically, there can be mentioned a group obtained by removing 2 hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by substituting 1 hydrogen atom of a group obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring (aryl group) with an alkylene group (for example, a group obtained by removing 1 hydrogen atom from an aryl group in arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, and the like); and the like. The carbon number of the alkylene group (alkyl chain in arylalkyl groups) is preferably 1 to 4, more preferably 1 to 2, particularly preferably 1.

[0234] In the formula (a1-1), Ra 1 is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-2).

[0235] In the formula (a1-1), n a1 is an integer of 0 to 2. n a1 is preferably 0 or 1, more preferably 0.

[0236] In the formula (a1-2), Wa 1 is n a2 The valence of the hydrocarbon group is preferably 2 to 4, more preferably 2 or 3. The valence of the hydrocarbon group is preferably 2 to 4, more preferably 2 or 3. a2 The valence of the hydrocarbon group is preferably 2 to 4, more preferably 2 or 3.

[0237] In the formula (a1-2), Ra 2 is an acid dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).

[0238] Specific examples of the structural unit represented by the formula (a1-1) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0239] [Chem. 20]

[0240]

[0241] [Chem. 21]

[0242]

[0243] [Chem. 22]

[0244]

[0245] [Chem. 23]

[0246]

[0247] [Chem. 24]

[0248]

[0249] [Chem. 25]

[0250]

[0251] [Chem. 26]

[0252]

[0253] [Chem. 27]

[0254]

[0255] [Chem. 28]

[0256]

[0257] [Chem. 29]

[0258]

[0259] [Chem. 30]

[0260]

[0261] Specific examples of the structural unit represented by the formula (a1-2) are shown below.

[0262] [Chem. 31]

[0263]

[0264] The structural unit (a1) possessed by the (Al) component can be one or two or more.

[0265] As the structural unit (a1), more preferably, a structural unit represented by the formula (a1-1) is used from the viewpoint of further improving the characteristics (sensitivity, shape, etc.) in lithography using electron beams or EUV.

[0266] Among them, as the structural unit (a1), particularly preferably, a structural unit represented by the following general formula (a1-1-1) is contained.

[0267]

Chemical Formula 32

[0268]

[0269] [In the formula, Ra 1 is an acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4).

[0270] In the formula (a1-1-1), R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the formula (a1-1).

[0271] The acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4) is as described above. From the viewpoint of maintaining transparency in a thick resist film, Ra 1 is preferably an acid dissociable group represented by the general formula (a1-r2-4). Ra 12 , Ra 13 and Ra 14 in the general formula (a1-r2-4) are preferably as described above.

[0272] The proportion of the structural unit (a1) in the (Al) component is preferably 5 to 80 mol%, more preferably 5 to 75 mol%, further preferably 10 to 70 mol%, still further preferably 10 to 60 mol%, particularly preferably 10 to 30 mol%, relative to the total (100 mol%) of all the structural units constituting the (Al) component.

[0273] By setting the proportion of the structural unit (a1) to be the lower limit value or more of the preferred range, the lithography characteristics such as sensitivity, resolution, roughness improvement are improved. On the other hand, if it is the upper limit value or less of the preferred range, a balance with other structural units can be achieved and various lithography characteristics are good.

[0274] Regarding the structural unit (a10):

[0275] The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0276]

Transformation 33

[0277]

[0278] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ya] x1 It is a single bond or a divalent linker. Wa x1 It is (n ax1 +1) valence aromatic hydrocarbon group. ax1 Integers greater than or equal to 1.

[0279] In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.

[0280] The alkyl group having 1 to 5 carbon atoms in R is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0281] The alkyl halogroup having 1 to 5 carbon atoms in R is a group obtained by substituting some or all of the hydrogen atoms of the alkyl halogroup having 1 to 5 carbon atoms with halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0282] 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, it is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. It is even more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

[0283] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linker.

[0284] In the chemical formula, Ya is used as... x1 The divalent linking group is not particularly limited, and examples such as divalent hydrocarbon groups with substituents and divalent linking groups containing heteroatoms can be used as preferred linking groups.

[0285] • Divalent hydrocarbon groups that may have substituents:

[0286] In Ya x1 In the case of a divalent hydrocarbon group that may have substituents, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0287] ··Ya x1 aliphatic hydrocarbon groups

[0288] The aliphatic hydrocarbon group represents a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group can be saturated or unsaturated, and is usually preferably a saturated aliphatic hydrocarbon group. As the aliphatic hydrocarbon group, a straight-chain or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having a ring in the structure, etc. can be exemplified.

[0289] • Straight-chain or branched aliphatic hydrocarbon group

[0290] The straight-chain aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, further preferably a carbon number of 1 to 4, and most preferably a carbon number of 1 to 3.

[0291] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specifically, methylene [-CH2-], ethylene [- (CH2)2-], propylene [- (CH2)3-], butylene [- (CH2)4-], pentylene [- (CH2)5-], etc. can be exemplified.

[0292] The branched aliphatic hydrocarbon group preferably has a carbon number of 2 to 10, more preferably a carbon number of 3 to 6, further preferably a carbon number of 3 or 4, and most preferably a carbon number of 3.

[0293] As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, alkylmethylene such as -CH (CH3) -, -CH (CH2CH3) -, -C (CH3) 2-, -C (CH3) (CH2CH3) -, -C (CH3) (CH2CH2CH3) -, -C (CH2CH3) 2-, etc.; alkylethylene such as -CH (CH3) CH2-, -CH (CH3) CH (CH3) -, -C (CH3) 2CH2-, -CH (CH2CH3) CH2-, -C (CH2CH3) 2CH2-, etc.; alkylpropylene such as -CH (CH3) CH2CH2-, -CH2CH (CH3) CH2-, etc.; alkylbutylene such as -CH (CH3) CH2CH2CH2-, -CH2CH (CH3) CH2CH2-, etc.; and alkylalkylene groups, etc. can be exemplified. As the alkyl group in the alkylalkylene group, a straight-chain alkyl group having a carbon number of 1 to 5 is preferable.

[0294] The straight-chain or branched aliphatic hydrocarbon group can have a substituent or can not have a substituent. As the substituent, a fluorine atom, a fluoroalkyl group having a carbon number of 1 to 5 substituted with a fluorine atom, a carbonyl group, etc. can be exemplified.

[0295] • Aliphatic hydrocarbon group having a ring in the structure

[0296] As the cyclic aliphatic hydrocarbon group having a ring structure, mention can be made of a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which can have a substituent, a group obtained by bonding a terminal of the cyclic aliphatic hydrocarbon group to a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups, and the like. As the linear or branched aliphatic hydrocarbon group, the same aliphatic hydrocarbon group as described above can be mentioned.

[0297] The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably from 3 to 20, more preferably from 3 to 12.

[0298] The cyclic aliphatic hydrocarbon group can be a polycyclic group or a monocyclic group. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having a number of carbon atoms of from 3 to 6 is preferred, and specifically mention can be made of cyclopentane, cyclohexane, and the like. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a polycycloalkane having a number of carbon atoms of from 7 to 12 is preferred, and specifically mention can be made of adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0299] The cyclic aliphatic hydrocarbon group can have a substituent or can not have a substituent. As the substituent, mention can be made of an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and the like.

[0300] As the substituent, an alkyl group having a number of carbon atoms of from 1 to 5 is preferred, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group.

[0301] As the substituent, an alkoxy group having a number of carbon atoms of from 1 to 5 is preferred, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a t-butoxy group, and further preferably a methoxy group, an ethoxy group.

[0302] As the substituent, a halogen atom can be mentioned, and mention can be made of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and preferably a fluorine atom.

[0303] As the substituent, a halogenated alkyl group can be mentioned, and mention can be made of a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

[0304] A part of the carbon atoms constituting the ring structure of the cyclic aliphatic hydrocarbon group can also be substituted with a substituent containing a hetero atom. As the substituent containing a hetero atom, -0-, -C(=0)-0-, -S-, -S(=0)2-, -S(=0)2-0- are preferred.

[0305] ••• Ya x1 aromatic hydrocarbon group

[0306] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0307] The aromatic ring is not particularly limited if it is a cyclic conjugated system having 4n+2 π electrons, and can be monocyclic or polycyclic. The number of carbons of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. The number of carbons in this context does not include the number of carbons in a substituent.

[0308] As the aromatic ring, specifically, there can be mentioned an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting the aromatic hydrocarbon ring with a hetero atom. As the hetero atom in the aromatic heterocyclic ring, there can be mentioned an oxygen atom, a sulfur atom, a nitrogen atom, and the like. As the aromatic heterocyclic ring, specifically, there can be mentioned a pyridine ring, a thiophene ring, and the like.

[0309] As the aromatic hydrocarbon group, specifically, there can be mentioned a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or the 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 (for example, biphenyl, fluorene, and the like); a group obtained by substituting one hydrogen atom of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocyclic ring (an aryl group or a heteroaryl group) with an alkylene group (for example, a group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, and the like); and the like. The number of carbons of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0310] In the aromatic hydrocarbon group, a hydrogen atom possessed by the aromatic hydrocarbon group can be substituted with a substituent. For example, a hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group can be substituted with a substituent. As the substituent, for example, there can be mentioned an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and the like.

[0311] As the alkyl group of the substituent, an alkyl group having a number of carbons of 1 to 5 is preferred, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group are more preferred.

[0312] As the alkoxy group, the halogen atom, and the haloalkyl group of the substituent, there can be mentioned the groups exemplified as substituents for substituting a hydrogen atom possessed by the cyclic aliphatic hydrocarbon group.

[0313] • a divalent linking group containing a hetero atom:

[0314] In Ya x1In the case of a divalent linking group containing a heteroatom, examples of such linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and those with 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 - represents a group [where Y is a group that represents ... 21 and Y 22 Preferred groups include divalent hydrocarbon groups that can be independently substituted, where O is an oxygen atom and m" is an integer from 0 to 3.

[0315] When the divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, its H can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in the substituent (alkyl, acyl, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0316] 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 is independently a divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include those related to Ya. x1 The same groups (which may be divalent hydrocarbon groups with substituents) are listed in the description of the divalent linking groups.

[0317] 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 carbons, particularly preferably a methylene group or an ethylene group.

[0318] as Y 22 , preferably a linear 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 linear alkyl group having 1 to 5 carbons, more preferably a linear alkyl group having 1 to 3 carbons, most preferably a methyl group.

[0319] as the group represented by the formula -Y 21 -C(=O)-O] m” -Y 22 In the group represented by the formula -Y 21 -C(=O)-O] m” -Y 22 , particularly preferably the group represented by the formula -Y 21 -C(=O)-O-Y 22 . Among them, preferably the group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ . In the 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, 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, most preferably 1.

[0320] Among the above, as Ya x1 , preferably a single bond, an ester bond [-C(=O)-O-, -O-C(=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-, -O-C(=O)-], further preferably a single bond.

[0321] In the formula (a10-1), Wa x1 is an aromatic hydrocarbon group having (n ax1 +1) valences.

[0322] As the aromatic hydrocarbon group in Wa x1 , examples include aromatic rings from which (n ax1A group obtained by adding (+1) hydrogen atoms. The aromatic ring here is not particularly limited to a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of such aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained by replacing a portion of the carbon atoms constituting the aromatic hydrocarbon ring with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0323] In addition, as Wa x1 The aromatic hydrocarbon groups in the text can also be exemplified by removing them from aromatic compounds containing two or more aromatic rings (such as biphenyl, fluorene, etc.). ax1 A group obtained by adding 1+ hydrogen atoms.

[0324] Of the above, as Wa x1 Preferably, it is removed from benzene, naphthalene, anthracene, or biphenyl (n ax1 A group obtained by removing (n) hydrogen atoms is more preferably derived from benzene or naphthalene. ax1 The group obtained by removing (n) hydrogen atoms is further preferably derived from benzene. ax1 A group obtained by adding 1+ hydrogen atoms.

[0325] Wa x1 The aromatic hydrocarbon group in the form may or may not have substituents, preferably without substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and haloalkyl groups. Examples of alkyl, alkoxy, halogen atoms, and haloalkyl groups that can be used as substituents include those used as Ya. x1 The cyclic aliphatic hydrocarbon group substituents in the example are the same groups as those listed. In Wa x1 To remove (n) from the aromatic ring ax1 In the case of a group obtained by adding (+1) hydrogen atoms, the substituent is a substitution that removes (n) hydrogen atoms from the aromatic ring. ax1 The substituent is a group containing hydrogen atoms in a group obtained by adding (+1) hydrogen atoms. The substituent is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms, further preferably methyl or ethyl, and particularly preferably methyl.

[0326] In the formula (a10-1), n ax1 The integer is 1 or higher, preferably an integer from 1 to 10, more preferably an integer from 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2. Wherein, n ax1 The preferred value is 1.

[0327] The following shows specific examples of the structural unit (a10) represented by the formula (a10-1).

[0328] In the following formulae, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0329] [Chem. 34]

[0330]

[0331] [Chem. 35]

[0332]

[0333] [Chem. 36]

[0334]

[0335] [Chem. 37]

[0336]

[0337] The structural unit (a10) possessed by the (A1) component can be one or two or more.

[0338] In the case where the (A1) component has the structural unit (a10), the proportion of the structural unit (a10) in the (A1) component is preferably 5 to 80 mol%, more preferably 5 to 75 mol%, and further preferably 10 to 70 mol%, relative to the total (100 mol%) of all the structural units constituting the (A1) component.

[0339] By setting the proportion of the structural unit (a10) to be equal to or higher than the lower limit value, it is more likely to improve the sensitivity. On the other hand, by setting it to be equal to or lower than the upper limit value, it is more likely to achieve a balance with other structural units.

[0340] Other Structural Units

[0341] The (A1) component can have other structural units, in addition to the above-mentioned structural unit (a1) and structural unit (a10), as necessary.

[0342] As the other structural units, for example, there can be mentioned a structural unit (a2) containing a lactone ring-containing cyclic group, a -SO2- containing cyclic group, a carbonate ring-containing cyclic group; a structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group; a structural unit (a4) containing an acid non-dissociative aliphatic cyclic group; a structural unit (st) derived from styrene or a derivative thereof; and the like.

[0343] Regarding the structural unit (a2):

[0344] In addition to having structural unit (a1), component (A1) may further have structural unit (a2) containing lactone cyclic group, -SO2- cyclic group or carbonate cyclic group (wherein, structural units belonging to structural unit (a1) are not included).

[0345] When component (A1) is used to form the resist film, the lactone-containing cyclic group, -SO2-containing cyclic group, or carbonate-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate. Furthermore, by having the structural unit (a2), photolithography properties become better, 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.

[0346] "Lactone-containing cyclic group" indicates a cyclic group whose ring skeleton contains a ring containing -OC (=O)- (lactone ring). The lactone ring is designated as the first ring. In the case of only a lactone ring, it is called a monocyclic group; in the case of other ring structures, regardless of their structure, it is called a polycyclic group. Lactone-containing cyclic groups can be either monocyclic or polycyclic.

[0347] There are no particular limitations on the lactone-containing cyclic group in the structural unit (a2), and any lactone-containing cyclic group can be used. Specifically, examples can be given by groups represented by the following general formulas (a2-r-1) to (a2-r-7).

[0348]

Transformation 38

[0349]

[0350] [In the formula, Ra'] 21 Each of these can be independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group, or cyano group; R is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or -SO2-containing cyclic group; A is an alkylene group, oxygen atom, or sulfur atom with 1 to 5 carbon atoms, which may contain oxygen atoms (-O-) or sulfur atoms (-S-); n' is an integer from 0 to 2; and m' is 0 or 1.

[0351] In the general formulas (a2-r-1) to (a2-r-7), Ra' is used as... 21 The alkyl group in the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. This alkyl group is preferably straight-chain or branched. Specifically, 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.

[0352] As Ra' 21alkyl group in the alkyl group in the Ra 21 alkyl group exemplified in the alkyl group in the Ra

[0353] alkyl group in the Ra 21 halogen atom in the Ra

[0354] alkyl group in the Ra 21 halogen atom in the Ra 21 halogen atom in the Ra

[0355] alkyl group in the Ra 21 R" in the -COOR" and -OC(=O)R"

[0356] alkyl group in the R" alkyl group in the R"

[0357] alkyl group in the R" alkyl group in the R"

[0358] alkyl group in the R" alkyl group in the R"

[0359] lactone ring-containing group in the R" lactone ring-containing group in the R"

[0360] carbonate ring-containing group in the R" carbonate ring-containing group in the R"

[0361] As the -SO2-containing cyclic group in R", the same as the -SO2-containing cyclic group described later, specifically, there can be mentioned groups represented by General Formulae (a5-r-1) to (a5-r-4), respectively.

[0362] As Ra' 21 In the hydroxyalkyl group in Ra' 21 a group in which at least one hydrogen atom of the alkyl group in Ra' is substituted with a hydroxy group.

[0363] In the General Formulae (a2-r-2), (a2-r-3), and (a2-r-5), as the alkylene group having 1 to 5 carbons in A", a straight-chain or branched-chain alkylene group is preferred, and there can be mentioned methylene, ethylene, n-propylene, iso-propylene, and the like. In the case where the alkylene group contains an oxygen atom or a sulfur atom, as specific examples thereof, there can be mentioned groups in which the terminal or the carbon atoms of the alkylene group are intervened with -O- or -S-, for example, -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, and the like. As A", an alkylene group having 1 to 5 carbons or -O- is preferred, an alkylene group having 1 to 5 carbons is more preferred, and methylene is most preferred.

[0364] Specific examples of the groups represented by General Formulae (a2-r-1) to (a2-r-7) are shown below.

[0365] [Chemical Formula 39]

[0366]

[0367] [Chemical Formula 40]

[0368]

[0369] The "-SO2-containing cyclic group" means a cyclic group having a ring containing -SO2- in its ring skeleton, and specifically, it is a cyclic group in which the sulfur atom (S) in -SO2- forms a part of the ring skeleton of the cyclic group. In the ring skeleton, the ring containing -SO2- is counted as the first ring, and in the case where only this ring is present, it is called a monocyclic group, and in the case where other ring structures are also present, it is called a polycyclic group regardless of the structure thereof. The -SO2-containing cyclic group can be either a monocyclic group or a polycyclic group.

[0370] The -SO2-containing cyclic group is particularly preferably a cyclic group having a ring of -O-SO2- in its ring skeleton, i.e., a cyclic group having a sultone ring in which -O-S- of -O-SO2- forms a part of the ring skeleton.

[0371] As the alkyl group, alkoxy group, halogen atom, haloalkyl group, -COOR", -OC(=O)R", hydroxyalkyl group, and cyano group of Ra

[0372] [Chemical Formula 41]

[0373]

[0374] [In the formula, Ra 51 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxy group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone ring-containing cyclic group, a carbonate ring-containing cyclic group, or a -SO2- containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms which can contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and n' is an integer of 0 to 2.]

[0375] In the general formulae (a5-r-1) to (a5-r-2), A" is the same as A" in the general formulae (a2-r-2), (a2-r-3), and (a2-r-5).

[0376] As the alkyl group, alkoxy group, halogen atom, haloalkyl group, -COOR", -OC(=O)R", hydroxyalkyl group, and cyano group of Ra 51 the same groups as those exemplified in the description of Ra 21 of the general formulae (a2-r-1) to (a2-r-7).

[0377] Specific examples of the groups represented by the general formulae (a5-r-1) to (a5-r-4) are exemplified below. "Ac" in the formula represents an acetyl group.

[0378] [Chemical Formula 42]

[0379]

[0380] [Chemical Formula 43]

[0381]

[0382] [Chemical Formula 44]

[0383]

[0384] The "carbonate ring-containing cyclic group" means a cyclic group containing a -O-C(=O)-O- containing ring (carbonate ring) in its ring skeleton. The carbonate ring is noted as the first ring, and is referred to as a monocyclic group in the case of having only the carbonate ring, and as a polycyclic group in the case of having other ring structures regardless of the structure thereof. The carbonate ring-containing cyclic group can be a monocyclic group or a polycyclic group.

[0385] As the cyclic group containing a carbonate ring, there is no particular limitation, and any cyclic group containing a carbonate ring can be used. Specifically, the following groups represented by General Formulae (ax3-r-1) to (ax3-r-3) can be exemplified.

[0386] [Chem. 45]

[0387]

[0388] [In the formula, Ra x31 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxy group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a cyclic group containing a lactone ring, a cyclic group containing a carbonate ring, or a cyclic group containing -SO2-; A" is an alkylene group having 1 to 5 carbon atoms which can contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and p' is an integer of 0 to 3, and q' is 0 or 1.]

[0389] In General Formulae (ax3-r-2) to (ax3-r-3), A" is the same as A" in General Formulae (a2-r-2), (a2-r-3), and (a2-r-5).

[0390] As the alkyl group, alkoxy group, halogen atom, haloalkyl group, -COOR", -OC(=O)R", hydroxyalkyl group in Ra 31 , the same groups as those exemplified in the description of Ra 21 in General Formulae (a2-r-1) to (a2-r-7) can be exemplified, respectively.

[0391] Specific examples of the groups represented by General Formulae (ax3-r-1) to (ax3-r-3) are exemplified below.

[0392] [Chem. 46]

[0393]

[0394] As the structural unit (a2), among them, a structural unit derived from a propenoate ester in which a hydrogen atom bonded to a carbon atom at an α-position can be substituted with a substituent is preferable.

[0395] The structural unit (a2) is preferably a structural unit represented by General Formula (a2-1).

[0396] [Chem. 47]

[0397]

[0398] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ya 21 is a single bond or a divalent linking group. La21 -0-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, R' represents a hydrogen atom or a methyl group. Among them, in the case of -0-, Ya 21 is not -CO-. Ra 21 is not -CO-. Ra 21 is a lactone ring-containing group, a carbonate ring-containing group, or a -SO2- ring-containing group.

[0399] In the formula (a2-1), R is the same as described above. As R, a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a fluoroalkyl group having a carbon number of 1 to 5 is preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of industrial availability.

[0400] In the formula (a2-1), as Ya 21 is not -CO-. Ra 21 is not -CO-. Ra 21

[0401] • a divalent hydrocarbon group which can have a substituent:

[0402] In the case where Ya 21 is a divalent hydrocarbon group which can have a substituent, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0403] • an aliphatic hydrocarbon group in Ya 21

[0404] The aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. The aliphatic hydrocarbon group can be saturated or unsaturated, and is usually preferably a saturated aliphatic hydrocarbon group. As the aliphatic hydrocarbon group, a straight-chain or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having a ring in the structure, etc. can be exemplified.

[0405] • a straight-chain or branched aliphatic hydrocarbon group

[0406] The carbon number of the straight-chain aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3.

[0407] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specifically, a methylene group [-CH2-], an ethylene group [- (CH2)2-], a propylene group [- (CH2)3-], a butylene group [- (CH2)4-], a pentylene group [- (CH2)5-], etc. can be exemplified.

[0408] The carbon number of the branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 3 to 6, further preferably 3 or 4, and most preferably 3.

[0409] As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, and the like alkyl methylene group; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, and the like alkyl ethylene group; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, and the like alkyl propylene group; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and the like alkyl butylene group, and the like alkyl alky lene group can be exemplified. As the alkyl group in the alkyl alky lene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0410] The linear or branched aliphatic hydrocarbon group can have a substituent or can not have a substituent. As the substituent, a fluorine atom, a fluoroalkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, and the like can be exemplified.

[0411] Aliphatic hydrocarbon group having a ring in the structure

[0412] As the aliphatic hydrocarbon group having a ring in the structure, a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which can have a substituent, a group obtained by bonding the cyclic aliphatic hydrocarbon group to the terminal of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups, and the like can be exemplified. As the linear or branched aliphatic hydrocarbon group, the same aliphatic hydrocarbon group as described above can be exemplified.

[0413] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

[0414] The cyclic aliphatic hydrocarbon group can be a polycyclic group or a monocyclic group. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocyclic alkane is preferable, and as the monocyclic alkane, a monocyclic alkane having 3 to 6 carbon atoms is preferable, and specifically, a cyclopentane, a cyclohexane, and the like can be exemplified. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycyclic alkane is preferable, and as the polycyclic alkane, a polycyclic alkane having 7 to 12 carbon atoms is preferable, and specifically, an adamantane, a norbornane, an isobornane, a tricyclodecane, a tetracyclododecane, and the like can be exemplified.

[0415] The cyclic aliphatic hydrocarbon group can have a substituent or can not have a substituent. As the substituent, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, and the like can be exemplified.

[0416] As the substituent, an alkyl group having a carbon number of 1 to 5 is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group are more preferable.

[0417] As the substituent, an alkoxy group having a carbon number of 1 to 5 is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a t-butoxy group are more preferable, and a methoxy group, an ethoxy group are further preferable.

[0418] As the substituent, a halogen atom can be exemplified by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable.

[0419] As the substituent, a haloalkyl group can be exemplified by a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

[0420] A part of the carbon atoms constituting the ring structure of the cyclic aliphatic hydrocarbon group can also be substituted with a substituent containing a hetero atom. As the substituent containing a hetero atom, -0-, -C(=0)-0-, -S-, -S(=0)2-, -S(=0)2-0- are preferable.

[0421] The aromatic hydrocarbon group in Formula (1) is a hydrocarbon group having at least one aromatic ring. 21 The aromatic hydrocarbon group in Formula (1) is a hydrocarbon group having at least one aromatic ring.

[0422] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0423] The aromatic ring, if it is a cyclic conjugated system having 4n+2 π electrons, is not particularly limited, and can be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, particularly preferably 6 to 12. Among the carbon numbers, the carbon number not including the carbon number in the substituent.

[0424] As the aromatic ring, specifically, an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, and the like; an aromatic heterocyclic ring in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, and the like can be exemplified. As the hetero atom in the aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, and the like can be exemplified. As the aromatic heterocyclic ring, specifically, a pyridine ring, a thiophene ring, and the like can be exemplified.

[0425] Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from an aryl group (e.g., a group obtained by further removing one hydrogen atom from an aryl group among arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). 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.

[0426] In the aromatic hydrocarbon group, the hydrogen atoms present in the aromatic hydrocarbon group may be replaced by substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, etc.

[0427] The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0428] The alkoxy, halogen atom, and haloalkyl groups that are said to be substituents can be exemplified as substituents that replace the hydrogen atoms of the cyclic aliphatic hydrocarbon group.

[0429] • Divalent linking groups containing heteroatoms:

[0430] In Ya 21 In the case of a divalent linking group containing a heteroatom, examples of such linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and those with 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 - represents a group [where Y is a group that represents ...21 and Y 22 are each independently a divalent hydrocarbon group which can have a substituent, O is an oxygen atom, and m" is an integer of 0 to 3. As the divalent hydrocarbon group which can have a substituent, the same groups as those exemplified in the explanation of the divalent linking group in the above-mentioned formula (1) can be exemplified.

[0431] In the case where the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)-, the H thereof can be substituted with an alkyl group, an acyl group, or the like. The carbon number of this substituent (alkyl group, acyl group, or the like) is preferably 1 to 10, further preferably 1 to 8, particularly preferably 1 to 5.

[0432] General formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-O-Y 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -O-C(=O)-Y 22 -, or -Y 21 -S(=O)2-O-Y 22 -, -Y 21 and Y 22 are each independently a divalent hydrocarbon group which can have a substituent. As the divalent hydrocarbon group, the same groups as those exemplified in the explanation of the divalent hydrocarbon group which can have a substituent in the above-mentioned formula (1) can be exemplified. 21

[0433] As Y 21 , a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having a carbon number of 1 to 5 is further preferred, and methylene or ethylene is particularly preferred.

[0434] As Y 22 , a linear or branched aliphatic hydrocarbon group is preferred, and methylene, ethylene, or alkylmethylene is more preferred. The alkyl group in the alkylmethylene is preferably a linear alkyl group having a carbon number of 1 to 5, more preferably a linear alkyl group having a carbon number of 1 to 3, and most preferably a methyl group.

[0435] In the group represented by the formula -[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 the group represented by the formula -[Y 21 -C(=O)-O] m” -Y​22 -The group represented by the formula -Y is particularly preferred. 21 -C(=O)-OY 22 - represents a group. Preferably, it is represented by the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0436] Of the above, as Ya 21 Preferably, it is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched alkylene group, or a combination thereof.

[0437] In the aforementioned formula (a2-1), Ra 21 It contains a lactone cyclic group, a -SO2- cyclic group, or a carbonate cyclic group.

[0438] As Ra 21 The groups containing lactone cyclic groups, -SO2- cyclic groups, and carbonate cyclic groups can preferably be the groups represented by the general formulas (a2-r-1) to (a2-r-7), (a5-r-1) to (a5-r-4), and (ax3-r-1) to (ax3-r-3), respectively.

[0439] Preferably, the group contains a lactone cyclic group or a -SO2- cyclic group, and more preferably, a group represented by the general formula (a2-r-1), (a2-r-2), (a2-r-6), or (a5-r-1), respectively. Specifically, more preferably, any group represented by the chemical formula (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), or (r-sl-1-18), respectively.

[0440] The structural unit (a2) of component (A1) can be one or more types.

[0441] When component (A1) has structural unit (a2), the proportion of structural unit (a2) relative to the total (100 mol%) of all structural units constituting component (A1) is preferably 5 to 60 mol%, more preferably 10 to 60 mol%, even more preferably 20 to 55 mol%, and particularly preferably 30 to 50 mol%.

[0442] If the proportion of structural unit (a2) is above the lower limit of the preferable range, the effect of the structural unit (a2) can be sufficiently obtained by the above-mentioned effect, and if it is below the upper limit, a balance with other structural units can be achieved and various lithographic properties become good.

[0443] Regarding the structural unit (a3):

[0444] The (A1) component can further have a structural unit (a3) containing a polar-group-containing aliphatic hydrocarbon group (excluding a structural unit belonging to the structural unit (a1) or the structural unit (a2)) in addition to the structural unit (a1). By having the structural unit (a3) in the (A1) component, the hydrophilicity of the (A) component is increased, which contributes to the improvement of resolution. Furthermore, the acid diffusion length can be appropriately adjusted.

[0445] As the polar group, a hydroxy group, a cyano group, a carboxyl group, a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom, and the like can be exemplified, and a hydroxy group is particularly preferable.

[0446] As the aliphatic hydrocarbon group, a linear or branched hydrocarbon group (preferably an alkylene group) having a carbon number of 1 to 10, a cyclic aliphatic hydrocarbon group (cyclic group) can be exemplified. As the cyclic group, a monocyclic group or a polycyclic group can be used, and for example, a cyclic group mentioned several times in the resins for ArF excimer laser resist compositions can be appropriately selected and used.

[0447] In the case where the cyclic group is a monocyclic group, a carbon number of 3 to 10 is more preferable. Among them, a structural unit derived from an acrylate ester containing an aliphatic monocyclic group having a hydroxy 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 a fluorine atom is more preferable. 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, cyclooctane, and the like can be exemplified. Among these monocyclic groups, a group obtained by removing two or more hydrogen atoms from cyclopentane, a group obtained by removing two or more hydrogen atoms from cyclohexane are industrially preferable.

[0448] 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 ester containing an aliphatic polycyclic group in which a part of hydrogen atoms of an alkyl group of the aliphatic polycyclic group is substituted with a fluorine atom to obtain a hydroxyalkyl group is more preferable. As the polycyclic group, a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane, a tetracycloalkane, or the like can be exemplified. Specifically, a group obtained by removing two or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like can be exemplified. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, and a group obtained by removing two or more hydrogen atoms from tetracyclododecane are industrially preferable.

[0449] As the structural unit (a3), there is no particular limitation as long as it contains an aliphatic hydrocarbon group containing a polar group, and any structural unit can be used.

[0450] As the structural unit (a3), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at an α position can be substituted with a substituent, and a structural unit containing an aliphatic hydrocarbon group containing a polar group are preferable.

[0451] As the structural unit (a3), when the aliphatic hydrocarbon group containing a polar group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a structural unit derived from a hydroxyethyl ester of acrylic acid is preferable.

[0452] Further, as the structural unit (a3), when the aliphatic hydrocarbon group containing a polar group is a polycyclic group, a structural unit represented by formula (a3-1) below, a structural unit represented by formula (a3-2) below, and a structural unit represented by formula (a3-3) below can be preferably exemplified; and when the aliphatic hydrocarbon group containing a polar group is a monocyclic group, a structural unit represented by formula (a3-4) below can be preferably exemplified.

[0453] [Chem. 48]

[0454]

[0455] [In the formula, R is the same as described 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, and l is an integer of 0 to 5, and s is an integer of 1 to 3.]

[0456] In formula (a3-1), j is preferably 1 or 2, and further preferably 1. In the case where j is 2, it is preferable that the hydroxyl group is bonded to the 3- and 5-positions of the adamantyl group. In the case where j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group. j is preferably 1, and it is particularly preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.

[0457] In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5- or 6-position of the norbornyl group.

[0458] In formula (a3-3), t' is preferably 1. 1 is preferably 1. s is preferably 1. They are preferably bonded to the 2-norbornyl group or 3-norbornyl group at 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.

[0459] In formula (a3-4), t' is preferably 1 or 2. 1 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.

[0460] The structural unit (a3) possessed by the (Al) component can be one or two or more.

[0461] In the case where the (Al) component has the structural unit (a3), the proportion of the structural unit (a3) is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and further preferably 5 to 20 mol%, with respect to the total (100 mol%) of all the structural units constituting the (Al) component.

[0462] By making the proportion of the structural unit (a3) be the preferable lower limit value or more, the effect of containing the structural unit (a3) can be sufficiently obtained by the above-described effect, and by being the preferable upper limit value or less, a balance with other structural units can be obtained, and various lithography characteristics become good.

[0463] Regarding the structural unit (a4):

[0464] The (Al) component can further have, in addition to the structural unit (al), a structural unit (a4) containing an aliphatic cyclic group which is not dissociated by an acid.

[0465] By making the (Al) component have the structural unit (a4), the dry etching resistance of the resist pattern formed is improved. Furthermore, the hydrophobicity of the (A) component is improved. In particular in the case of a solvent developing process, the improvement in hydrophobicity contributes to the improvement in resolution, resist pattern shape, and the like.

[0466] The "cyclic group which is not dissociated by an acid" in the structural unit (a4) is a cyclic group which, when an acid is generated in the resist composition by exposure (for example, when an acid is generated from a structural unit which generates an acid by exposure or the (B) component), is not dissociated even under the action of the acid and remains directly in the structural unit.

[0467] As the structural unit (a4), for example, a structural unit derived from an acrylic acid ester containing an aliphatic ring group which is not dissociated by an acid, and the like are preferred. The ring group can use various groups known heretofore as a group for a resin component of a resist composition for an ArF excimer laser, a KrF excimer laser (preferably, an ArF excimer laser), and the like.

[0468] The ring group is particularly preferably at least one selected from the group consisting of tricyclodecyl group, adamantyl group, tetracyclododecyl group, isobornyl group, norbornyl group from the viewpoint of industrial availability and the like. These polycyclic ring groups can have a linear or branched alkyl group having a carbon number of 1 to 5 as a substituent.

[0469] As the structural unit (a4), specifically, structural units represented by the following general formulae (a4-1) to (a4-7), respectively, can be exemplified.

[0470] [Formula 49]

[0471]

[0472] [Note, R α The same as described above.

[0473] The structural unit (a4) possessed by the (Al) component can be one or two or more.

[0474] In the case where the (Al) component has the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 40 mol%, and more preferably 5 to 20 mol% with respect to the total (100 mol%) of all the structural units constituting the (Al) component.

[0475] By setting the proportion of the structural unit (a4) to be more than the lower limit of the preferred range, the effect of containing the structural unit (a4) can be sufficiently obtained, and on the other hand, by setting it to be less than the upper limit of the preferred range, a balance with other structural units can be easily obtained.

[0476] Regarding the structural unit (st):

[0477] The structural unit (st) is a structural unit derived from styrene or a styrene derivative. The "structural unit derived from styrene" means a structural unit constituted by cracking the olefinic double bond of styrene. The "structural unit derived from a styrene derivative" means a structural unit constituted by cracking the olefinic double bond of a styrene derivative.

[0478] The "styrene derivative" refers to a compound in which at least one hydrogen atom of styrene is substituted with a substituent. As the styrene derivative, for example, a compound in which a hydrogen atom at the α-position of styrene is substituted with a substituent, a compound in which one or more hydrogen atoms of the benzene ring of styrene is substituted with a substituent, a compound in which a hydrogen atom at the α-position of styrene and one or more hydrogen atoms of the benzene ring of styrene are substituted with a substituent, and the like can be exemplified.

[0479] As the substituent which substitutes the hydrogen atom at the α-position of the styrene, an alkyl group having a carbon number of 1 to 5 or a halogenated alkyl group having a carbon number of 1 to 5 can be exemplified.

[0480] As the alkyl group having a carbon number of 1 to 5, a linear or branched alkyl group having a carbon number of 1 to 5 is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like can be exemplified.

[0481] The halogenated alkyl group having a carbon number of 1 to 5 is a group in which a part or all of the hydrogen atoms of the alkyl group having a carbon number of 1 to 5 are substituted with a halogen atom. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified, and a fluorine atom is particularly preferable.

[0482] As the substituent which substitutes the hydrogen atom at the α-position of the styrene, an alkyl group having a carbon number of 1 to 5 or a fluorinated alkyl group having a carbon number of 1 to 5 is preferable, an alkyl group having a carbon number of 1 to 3 or a fluorinated alkyl group having a carbon number of 1 to 3 is more preferable, and a methyl group is further preferable from the viewpoint of industrial availability.

[0483] As the substituent which substitutes the hydrogen atom of the benzene ring of the styrene, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and the like can be exemplified.

[0484] As the alkyl group of the substituent, an alkyl group having a carbon number of 1 to 5 is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group are more preferable.

[0485] As the alkoxy group of the substituent, an alkoxy group having a carbon number of 1 to 5 is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group are more preferable, and a methoxy group, an ethoxy group are further preferable.

[0486] As the halogen atom of the substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified, and a fluorine atom is preferable.

[0487] As the halogenated alkyl group of the substituent, a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom can be exemplified.

[0488] As the substituent which substitutes the hydrogen atom of the benzene ring of the styrene, an alkyl group having a carbon number of 1 to 5 is preferable, and a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.

[0489] As the structural unit (st), a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which a hydrogen atom at an α-position of styrene is substituted with an alkyl group having 1 to 5 carbons or a halogenated alkyl group having 1 to 5 carbons is preferred, a structural unit derived from styrene or a structural unit derived from a styrene derivative in which a hydrogen atom at an α-position of styrene is substituted with a methyl group is more preferred, and a structural unit derived from styrene is further preferred.

[0490] The structural unit (st) possessed by the (Al) component can be one or two or more.

[0491] In the case where the (Al) component has the structural unit (st), the proportion of the structural unit (st) is preferably 1 to 30 mol%, and more preferably 3 to 30 mol% with respect to the total (100 mol%) of all the structural units constituting the (Al) component.

[0492] The (Al) component contained in the resist composition can be used alone or two or more can be used in combination.

[0493] In the resist composition of the present embodiment, the (Al) component can exemplify a high molecular compound having a repeating structure of the structural unit (al) and the structural unit (alO).

[0494] As the preferred (Al) component, a high molecular compound having a repeating structure of the structural unit (al), the structural unit (alO), and another structural unit can be exemplified. As the another structural unit, a structural unit (st) or the like can be exemplified.

[0495] In addition to the combination of the above two kinds of structural units, the structural units described above can be appropriately combined as the third or three or more kinds of structural units depending on the desired effect. As the combination of three or more kinds of structural units, a combination of the structural unit (al), the structural unit (alO), and the structural unit (st) or the like can be exemplified.

[0496] As the preferred examples of the (Al) component, a high molecular compound having a repeating structure of the structural unit (al) and the structural unit (alO), and a high molecular compound having a repeating structure of the structural unit (al), the structural unit (alO), and the structural unit (st) can be exemplified.

[0497] The (Al) component can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and polymerizing the same with the addition of a radical polymerization initiator such as azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (e.g., V-601 or the like), or the like thereto.

[0498] Alternatively, the (Al) component can be produced by dissolving a monomer from which the structural unit (al) is derived and, as necessary, a monomer from which a structural unit other than the structural unit (al) is derived in a polymerization solvent, polymerizing the same with the addition of a radical polymerization initiator as described above, and then performing a deprotection reaction.

[0499] Further, at the time of polymerization, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH can be used in combination, whereby a -C(CF3)2-OH group can be introduced at the terminal. As such, a copolymer of a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is replaced with a fluorine atom is effective for the reduction of development defects and the reduction of LER (line edge roughness: unevenness of the line side wall).

[0500] The weight average molecular weight (Mw) of the (Al) component (polystyrene conversion basis based on gel permeation chromatography (GPC)) is not particularly limited, and is preferably from 1000 to 50000, more preferably from 2000 to 30000, and further preferably from 3000 to 20000.

[0501] If the Mw of the (Al) component is below the preferable upper limit value of the range, it has sufficient solubility against a resist solvent for use as a resist, and if it is above the preferable lower limit value of the range, it has good dry etching resistance and a resist pattern cross-sectional shape.

[0502] The molecular weight distribution coefficient (Mw / Mn) of the (Al) component is not particularly limited, and is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0. Further, Mn represents the number average molecular weight.

[0503] • Regarding a base material component other than the (Al) component

[0504] In the resist composition of the present embodiment, as the (A) component, a base material component other than the (Al) component, the solubility of which against a developer changes due to the action of an acid, can be used in combination. As the base material component other than the (Al) component, there is no particular limitation, and any one can be arbitrarily selected from among a variety of compounds known heretofore as a base material component for a chemically amplified resist composition, and one high molecular compound or one low molecular compound can be used alone, or two or more can be used in combination.

[0505] The proportion of the (Al) component in the (A) component is preferably 25% by mass or more, more preferably 50% by mass or more, and further preferably 75% by mass or more, with respect to the total mass of the (A) component, and can be 100% by mass. If the proportion is 25% by mass or more, it becomes easy to form a resist pattern excellent in various lithography characteristics.

[0506] In the resist composition of the present embodiment, the content of the (A) component is preferably 20 mass% or more relative to the total mass (100 mass%) of the resist composition. By making the content of the (A) component 20 mass% or more, it becomes easy to form a resist film of a thick film (for example, a film thickness of 5 μm or more). The upper limit of the content of the (A) component is not particularly limited as long as it is a concentration at which a resist film can be formed, and for example, it can be 50 mass% or less. The content of the (A) component is preferably 20 to 50 mass%, more preferably 22 to 50 mass%, and further preferably 25 to 50 mass%.

[0507] <Z component>

[0508] The (Z) component is a plasticizer component having a structural unit (z1) represented by the following general formula (z1-1) and not containing an acid dissociation group. Here, the "acid dissociation group" refers to either (i) a group having an acid dissociation property in which a bond between the acid dissociation group and an atom adjacent to the acid dissociation group can be cleaved by the action of an acid, or (ii) a group in which, after a part of a bond is cleaved by the action of an acid, a decarboxylation reaction further occurs, whereby a bond between the acid dissociation group and an atom adjacent to the acid dissociation group can be cleaved.

[0509] That is, all of the structural units constituting the (Z) component do not contain an acid dissociation group. Therefore, the (Z) component does not undergo a deprotection reaction due to the action of an acid.

[0510] [Chemical Formula 50]

[0511]

[0512] [In the formula, R is a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a halogenated alkyl group having a carbon number of 1 to 5. Vz 0 is a single bond or a 2-valent hydrocarbon group which can contain a hetero atom. In this case, Vz 0 is a 2-valent hydrocarbon group which can contain a hetero atom, Vz 0 does not contain an acid dissociation group. Rz 0 is a hydrogen atom or a group represented by the following general formula (z1-r-1).

[0513] [Chemical Formula 51]

[0514]

[0515] [In the formula, Rz 01 is a hydrocarbon group which can have a substituent. Rz 02 is a hydrogen atom or a hydrocarbon group which can have a substituent. Rz 01 is a hydrogen atom or a hydrocarbon group which can have a substituent. Rz 02 can be bonded to each other to form a ring structure. In this case, Rz 01 is a hydrogen atom or a hydrocarbon group which can have a substituent. Rz02 It does not contain acid-dissociable groups. * indicates a bond.

[0516] Structural Unit (z1)

[0517] In the formula (z1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.

[0518] The alkyl group having 1 to 5 carbon atoms in R is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0519] The alkyl halogroup having 1 to 5 carbon atoms in R is a group obtained by substituting some or all of the hydrogen atoms of the alkyl halogroup having 1 to 5 carbon atoms with halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0520] 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, it is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, and even more preferably a hydrogen atom or a methyl group.

[0521] In the aforementioned equation (z1-1), Vz 0 Examples of divalent hydrocarbon groups that may contain heteroatoms in formula (a10-1) include Ya. x1 It can be a divalent hydrocarbon group with substituents or a divalent linking group containing heteroatoms.

[0522] Among them, Vz 0 In the case where Vz is a divalent hydrocarbon group that may contain heteroatoms, 0 It does not contain acid-dissociable groups.

[0523] Among them, as Vz 0 Preferably, it is a single bond, -C(=O)-OY 21 -or-C(=O)-OY 21 -OC(=O)-Y 22 -, more preferably a single bond. Y 21 and Y 22 Each can be a divalent hydrocarbon group that can have substituents. Examples of such divalent hydrocarbon groups include those related to Ya. 21 The same groups (which may be divalent hydrocarbon groups with substituents) are listed in the description of the divalent linking groups.

[0524] In the formula (z1-1), Rz 0 It is a hydrogen atom or a group represented by the general formula (z1-r-1).

[0525] In the formula (z1-r-1), Rz is used as... 01 The hydrocarbon group in Rz can have substituents, and examples include straight-chain or branched alkyl groups, or cyclic hydrocarbon groups. 01 The linear alkyl group in the form preferably has 1 to 10 carbon atoms, more preferably 1 to 5. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0526] As Rz 01 The branched alkyl group in the compound preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Examples of specific compounds include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl.

[0527] Composition of Rz 01 In this formula, a portion of the carbon atom of the straight-chain or branched alkyl group can be replaced by an oxygen atom (-O-). Specifically, in the formula (z1-r-1), Rz... 01 It does not contain acid-dissociable groups. Therefore, in the formula (z1-r-1), even when constituting Rz... 01 In cases where a portion of the carbon atom of the straight-chain or branched alkyl group is replaced by an oxygen atom (-O-), it also does not contain an acetal-type acid dissociative group represented by the formula (a1-r-1).

[0528] Rz 01 The mesocyclic hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0529] The aliphatic hydrocarbon group that is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane.

[0530] The aliphatic hydrocarbon group that is the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms. Examples of such polycyclic alkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0531] In Rz 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.

[0532] The aromatic ring is not particularly limited to a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. 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.

[0533] As the aromatic ring, specifically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, can be exemplified. As the hetero atom in the aromatic heterocyclic ring, oxygen atom, sulfur atom, nitrogen atom, and the like can be exemplified. As the aromatic heterocyclic ring, specifically, pyridine ring, thiophene ring, and the like can be exemplified.

[0534] As Rz 01 in the formula (z1-r-1), specifically, aromatic hydrocarbon groups in which one hydrogen atom is removed from the aromatic hydrocarbon ring or the aromatic heterocyclic ring (aryl group or heteroaryl group); groups in which one hydrogen atom is removed from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, and the like); groups in which one hydrogen atom of the aromatic hydrocarbon ring or the aromatic heterocyclic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, arylalkyl groups, and the like); and the like can be exemplified. The number of carbons of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0535] Rz 01 in the formula (z1-r-1) can have a substituent. As the substituent, Ra 3 in the formula (a1-r-1) can be exemplified. 05

[0536] In the formula (z1-r-1), the hydrocarbon group which can have a substituent in Rz 02 is the same hydrocarbon group as the hydrocarbon group which can have a substituent in Rz 01

[0537] In the formula (z1-r-1), in the case where Rz 01 and Rz 02 are bonded to each other to form a ring structure, as the ring structure, a group in which two hydrogen atoms are removed from a monocyclic alkane or a polycyclic alkane can be exemplified. As the monocyclic alkane, a monocyclic alkane having a carbon number of 3 to 6 is preferable, and specifically, cyclopentane, cyclohexane, and the like can be exemplified.

[0538] As the aliphatic hydrocarbon group of the polycyclic group, a group in which one hydrogen atom is removed from a polycyclic alkane is preferable, and as the polycyclic alkane, a polycyclic alkane having a carbon number of 7 to 12 is preferable, and specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like can be exemplified.

[0539] In the formula (z1-r-1), Rz 01 is preferably a straight-chain alkyl group or a straight-chain alkoxy group, and Rz 02 ​​is a hydrogen atom, or Rz 01 is bonded to each other to form a ring structure. 02 is bonded to each other to form a ring structure.

[0540] The structural unit (z1) possessed by the component (Z) can be one or two or more.

[0541] Among them, the component (Z) preferably has, as the structural unit (z1), a structural unit represented by the following general formula (z1-1-1) (hereinafter, sometimes referred to as "structural unit (z1-1-1)") and a structural unit represented by the following general formula (z1-1-2) (hereinafter, sometimes referred to as "structural unit (z1-1-2)").

[0542] [Formula 52]

[0543]

[0544] [In the formula, R 01 and R 02 are each independently a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a halogenated alkyl group having a carbon number of 1 to 5. Vz 01 is a single bond, -C(=O)-O-Y 21 - or -C(=O)-O-Y 21 -O-C(=O)-Y 22 -. Y 21 and Y 22 are each independently a 2-valent hydrocarbon group which can have a substituent, and 0 is an oxygen atom. Among them, in the case where Vz 01 is -C(=O)-O-Y 21 - or -C(=O)-O-Y 21 -O-C(=O)-Y 22 -, Vz 01 does not have an acid dissociable group. Rz 10 is a linear alkyl group, -Rz 11 -O-Rz 12 or a 1-valent alicyclic hydrocarbon group. Rz 11 is a linear alkylene group, Rz 12 is a linear alkyl group.]

[0545] In the formulae (z1-1-1) and (z1-1-2), R 01 and R 02 are the same as R in the formula (z1-1). Among them, R 01 is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group. R 02 is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0546] In the formula (z1-1-1), Vz 01 -C(=O)-O-Y 21 -C(=O)-O-Y 21 -O-C(=O)-Y 22 -C(=O)-O-Y 21 -C(=O)-O-Y 22 -C(=O)-O-Y

[0547] In the formula (z1-1-1), Vz 01 -C(=O)-O-Y

[0548] In the formula (z1-1-2), Rz 10 The number of carbon atoms in the straight-chain alkyl group is preferably from 1 to 10, more preferably from 1 to 5.

[0549] In the formula (z1-1-2), Rz 10 -C(=O)-O-Y 11 -C(=O)-O-Y 12 -C(=O)-O-Y 10 -C(=O)-O-Y 11 -C(=O)-O-Y

[0550] In the formula (z1-1-2), Rz 10 The monovalent alicyclic hydrocarbon group in Rz

[0551] The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. As the monocycloalkane, a monocycloalkane having from 3 to 6 carbon atoms is preferable, and specifically, cyclopentane, cyclohexane, and the like can be given.

[0552] The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane. As the polycycloalkane, a polycycloalkane having from 7 to 12 carbon atoms is preferable, and specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like can be given.

[0553] In the formula (z1-1-2), Rz1-1-2and Rz1-1-2independently represent a linear alkylene group, a linear alkyl group, or a monovalent alicyclic hydrocarbon group. Rz1-1-2

[0554] [Chemical Formula 53]

[0555]

[0556] [In the formula, R 21 and R 22 independently represent a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Rz 11 is a linear alkylene group. Rz 12 is a linear alkyl group. Rz 13 is a linear alkyl group or a monovalent alicyclic hydrocarbon group.]

[0557] In the formula (z1-1-21) and (z1-1-22), R 21 and R 22 are the same as R 02 in the formula (z1-1-2).

[0558] In the formula (z1-1-21), Rz 11 and Rz 12 are the same as Rz 11 and Rz 12 in the formula (z1-1-2).

[0559] In the formula (z1-1-21), the linear alkyl group or monovalent alicyclic hydrocarbon group in Rz 13 is the same as the linear alkyl group or monovalent alicyclic hydrocarbon group in Rz 10 in the formula (z1-1-2).

[0560] Specific examples of the structural unit (z1) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0561] [Chemical Formula 54]

[0562]

[0563] The proportion of the structural unit (z1) in the (Z) component is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and further preferably 70 to 100 mol%, relative to the total (100 mol%) of all the structural units constituting the (Z) component, and can be 100 mol%.

[0564] By making the proportion of the structural unit (z1) within the above-mentioned preferable range, it becomes easy to suppress the generation of cracks, and it becomes easy to suppress the occurrence of surface roughness at the time of etching.

[0565] In the case where the (Z) component contains the structural unit (z1-1-1) and the structural unit (z1-1-2) as the structural unit (z1), the proportion of the structural unit (z1-1-1) in the (Z) component is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, further preferably 5 to 20 mol%, relative to the total (100 mol%) of all the structural units constituting the (Z) component. In addition, the proportion of the structural unit (z1-1-2) in the (Z) component is preferably 70 to 99 mol%, more preferably 75 to 97 mol%, further preferably 80 to 95 mol%, relative to the total (100 mol%) of all the structural units constituting the (Z) component.

[0566] By making the proportions of the structural unit (z1-1-1) and (z1-1-2) within the above-mentioned preferable ranges, it becomes easy to suppress the generation of cracks, and it becomes easy to suppress the occurrence of surface roughness at the time of etching.

[0567] In the case where the (Z) component contains the structural unit (z1-1-1), the structural unit (z1-1-21), and the structural unit (z1-1-22) as the structural unit (z1), the proportion of the structural unit (z1-1-1) in the (Z) component is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, further preferably 5 to 20 mol%, relative to the total (100 mol%) of all the structural units constituting the (Z) component. In addition, the proportion of the structural unit (z1-1-21) in the (Z) component is preferably 10 to 99 mol%, more preferably 15 to 97 mol%, further preferably 20 to 95 mol%, further preferably 20 to 70 mol%, relative to the total (100 mol%) of all the structural units constituting the (Z) component. In addition, the proportion of the structural unit (z1-1-22) in the (Z) component is preferably 0 to 80 mol%, more preferably 10 to 75 mol%, further preferably 15 to 70 mol%, particularly preferably 20 to 65 mol%, relative to the total (100 mol%) of all the structural units constituting the (Z) component.

[0568] By making the proportions of the structural unit (z1-1-1), the structural unit (z1-1-21), and the structural unit (z1-1-22) within the above-mentioned preferable ranges, it becomes easy to suppress the generation of cracks, and it becomes easy to suppress the occurrence of surface roughness at the time of etching.

[0569]

[0570] ​In addition to the structural unit (z1) mentioned above, component (Z) may also have other structural units as needed.

[0571] Other structural units include the structural unit (a10), the structural unit (st), and the structural unit (a1).

[0572] When the (Z) component has structural unit (a10), the proportion of structural unit (a10) in the (Z) component is preferably 5 to 50 mol% relative to the total (100 mol%) of all structural units constituting the (Z) component, more preferably 5 to 40 mol%, and even more preferably 10 to 30 mol%.

[0573] Sensitivity is more easily improved by setting the proportion of the structural unit (a10) above the lower limit. On the other hand, it is easier to achieve a balance with other structural units by setting it below the upper limit.

[0574] When the (Z) component has structural units (st), the proportion of structural units (st) in the (Z) component relative to the total (100 mol%) of all structural units constituting the (Z) component is preferably 1 to 30 mol%, more preferably 3 to 30 mol%.

[0575] The (Z) component contained in the resist composition can be used alone or in combination with two or more components.

[0576] In the resist composition of this embodiment, component (Z) can be exemplified by a polymeric compound having a repeating structure of structural unit (z1).

[0577] Examples of preferred (Z) components include: polymeric compounds having repeating structures of structural units (z1-1-1) and (z1-1-21); and polymeric compounds having repeating structures of structural units (z1-1-1), (z1-1-21), and (z1-1-22).

[0578] The (Z) component can be manufactured by dissolving the monomers from which the structural units are derived in a polymerization solvent, wherein a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) is added to the solvent for polymerization.

[0579] Alternatively, the (Z) component can be manufactured by dissolving the monomer from which the structural unit (z1) is derived and the monomer from which structural units other than the structural unit (z1) are derived as needed in a polymerization solvent, wherein a free radical polymerization initiator as described above is added for polymerization.

[0580] In addition, at the time of polymerization, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH can be used in combination, whereby a -C(CF3)2-OH group can be introduced at the terminal. A copolymer of a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is replaced with a fluorine atom is effective in reducing defects in development, and reducing LER (line edge roughness: unevenness of the line side wall).

[0581] The weight average molecular weight (Mw) of the (Z) component (converted to polystyrene basis based on gel permeation chromatography (GPC)) is not particularly limited, and is preferably from 5,000 to 200,000, more preferably from 10,000 to 150,000, and further preferably from 15,000 to 100,000.

[0582] If the Mw of the (Z) component is within the above-mentioned preferable range, it becomes easy to suppress the generation of cracks, and it becomes easy to suppress the occurrence of surface roughness at the time of etching.

[0583] The molecular weight distribution coefficient (Mw / Mn) of the (Z) component is not particularly limited, and is preferably from 1.0 to 7.0, more preferably from 2.0 to 6.0, and particularly preferably from 3.0 to 6.0. In addition, Mn represents the number average molecular weight.

[0584] In the resist composition of the present embodiment, the (Z) component can be used alone or in combination with two or more.

[0585] In the resist composition of the present embodiment, the content of the (Z) component is 50 parts by mass or less, preferably from 1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, and further preferably from 10 to 20 parts by mass, relative to 100 parts by mass of the (Al) component.

[0586] By making the content of the (Z) component 50 parts by mass or less relative to 100 parts by mass of the (Al) component, it is possible to suppress the generation of cracks, and it is possible to suppress the occurrence of surface roughness at the time of etching.

[0587] Furthermore, by making the content of the (Z) component within the above-mentioned preferable range, it becomes easy to suppress the generation of cracks, and it becomes easy to suppress the occurrence of surface roughness at the time of etching.

[0588] <Other Components>

[0589] The resist composition of the present embodiment can further contain other components in addition to the above-mentioned (A) component and (Z) component. As the other components, for example, the (B) component, (D) component, (E) component, (F) component, (S) component, and the like shown below can be exemplified.

[0590] <Acid Generator Component (B)>

[0591] In addition to components (A) and (Z), the resist composition of this embodiment may further contain an acid-generating agent component (B) that generates acid through exposure (hereinafter referred to as "component (B)").

[0592] As for component (B), there are no particular limitations, and any acid-generating agent proposed so far as an acid-generating agent for chemically amplified resist compositions can be used.

[0593] Examples of such acid-producing agents include iodonium salts, sulfonium salts, and other ononium salts; sulfonate oxime esters; dialkyl or diarylsulfonyl diazomethanes, poly(disulfonyl)diazomethanes, and other diazomethanes; nitrobenzyl sulfonates, iminosulfonates, disulfones, and many other acid-producing agents.

[0594] As component (B), it is preferred to include a compound (B1) composed of onium salts (hereinafter referred to as "(B1) component").

[0595] Regarding ingredient (B1)

[0596] As a component (B1), examples include compounds represented by general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by general formula (b-2) (hereinafter also referred to as "(b-2) component"), or compounds represented by general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0597]

Transformation 55

[0598]

[0599] [In the formula, R] 101 and R 104 ~R 108 Each can be independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. R 104 With R 105 They can bond together to form a ring structure. R 102 It is a fluoroalkyl group or a fluorine atom with 1 to 5 carbon atoms. 101 It is a divalent linker or single bond containing an oxygen atom. V 101 ~V 103 Each can be independently a single bond, an alkylene group, or a fluoroalkylene group. L 101 ~L 102 Each can be a single bond or an oxygen atom, independently. L 103 ~L 105 Each can be a single bond, -CO-, or -SO2-, independently. m is an integer greater than or equal to 1, M' m+ It is an m-valent ononium cation.

[0600] {anion part}

[0601] • Anion in component (b-1)

[0602] In formula (b-1), R 101 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent.

[0603] The cyclic group which can have a substituent is:

[0604] The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group indicates a hydrocarbon group which does not have aromaticity. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, and is usually preferably saturated.

[0605] The aromatic hydrocarbon group in R 101 is a hydrocarbon group having an aromatic ring. The number of carbons of 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. Among the number of carbons, the number of carbons in a substituent is not included.

[0606] As the aromatic ring possessed by the aromatic hydrocarbon group in R 101 , specifically, there can be mentioned benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocycle in which a part of carbon atoms constituting these aromatic rings is substituted with a hetero atom, and the like. As the hetero atom in the aromatic heterocycle, there can be mentioned an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0607] As the aromatic hydrocarbon group in R 101 , specifically, there can be mentioned a group in which one hydrogen atom is removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, and the like), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, arylalkyl groups, and the like), and the like. The number of carbons of the alkylene group (alkyl chain in arylalkyl groups) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0608] The cyclic aliphatic hydrocarbon group in R 101 may be mentioned as an aliphatic hydrocarbon group having a ring in the structure.

[0609] As the aliphatic hydrocarbon group having a ring in the structure, there can be mentioned an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from an aliphatic hydrocarbon ring); a group in which an alicyclic hydrocarbon group is bonded to the terminal of a straight-chain or branched-chain aliphatic hydrocarbon group; a group in which an alicyclic hydrocarbon group is interposed in a straight-chain or branched-chain aliphatic hydrocarbon group; and the like.

[0610] The number of carbons of the alicyclic hydrocarbon group is preferably from 3 to 20, more preferably from 3 to 12.

[0611] The alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocyclic alkane is preferred. As the monocyclic alkane, a monocyclic alkane having a carbon number of from 3 to 6 is preferred, and specifically, cyclopentane, cyclohexane, and the like can be exemplified. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane is preferred, and as the polycyclic alkane, a polycyclic alkane having a carbon number of from 7 to 30 is preferred. Among them, as the polycyclic alkane, a polycyclic alkane having a polycyclic skeleton of the cross-linked ring type such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like; a polycyclic alkane having a polycyclic skeleton of the fused ring type such as a cyclic group having a steroid skeleton, and the like are more preferred.

[0612] Among them, as R 101 , a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or a polycyclic alkane is preferred, a group obtained by removing one hydrogen atom from a polycyclic alkane is more preferred, and adamantyl group, norbornyl group, and most preferably adamantyl group are particularly preferred.

[0613] The number of carbons of the linear aliphatic hydrocarbon group which can be bonded to the alicyclic hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 6, further preferably from 1 to 4, and most preferably from 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, methylene [-CH2-], ethylene [- (CH2)2-], propylene [- (CH2)3-], butylene [- (CH2)4-], pentylene [- (CH2)5-], and the like can be exemplified.

[0614] The branched aliphatic hydrocarbon group that can bond with the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6, further preferably 3 or 4, and most preferably 3. As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0615] In addition, R 101 The cyclic hydrocarbon group in the formula can contain heteroatoms, just like heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0616]

Transformation 56

[0617]

[0618] As R 101 Substituents in the cyclic group can include, for example, alkyl, alkoxy, halogen atom, haloalkyl, hydroxy, carbonyl, nitro, etc. The alkyl group used as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0619] The alkoxy group used as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0620] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred option.

[0621] Examples of alkyl halogens that can be used as substituents 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 replaced by the halogen atom.

[0622] The carbonyl group as a substituent is a group substituting a methylene group (-CH2-) constituting a cyclic hydrocarbon group.

[0623] The chain-like alkyl group which can have a substituent:

[0624] The chain-like alkyl group as R 101 may be either of a straight chain or a branched chain.

[0625] The straight chain alkyl group preferably has a carbon number of 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specifically, for example, there can be mentioned methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, and the like.

[0626] The branched chain alkyl group preferably has a carbon number of 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, for example, there can be mentioned 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like.

[0627] The chain-like alkenyl group which can have a substituent:

[0628] The chain-like alkenyl group as R 101 may be either of a straight chain or a branched chain, and preferably has a carbon number of 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. The straight chain alkenyl group, for example, can be mentioned ethenyl, propenyl (allyl), butynyl, and the like. The branched chain alkenyl group, for example, can be mentioned 1-methylethenyl, 2-methylethenyl, 1-methylpropenyl, 2-methylpropenyl, and the like.

[0629] The chain-like alkenyl group, among the above, is preferably a straight chain alkenyl group, more preferably ethenyl, propenyl, and particularly preferably ethenyl.

[0630] The substituent in the chain-like alkyl group or the chain-like alkenyl group as R 101 , for example, can be mentioned alkoxy, a halogen atom, a haloalkyl group, hydroxy, carbonyl, nitro, amino, a cyclic group in R 101 , and the like.

[0631] Among the above, R 101The cyclic group preferably has a substituent, and more preferably a cyclic hydrocarbon group having a substituent. More specifically, a group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group, a polycyclic alkane; a cyclic group having a lactone ring represented by the general formula (a2-r-1) to (a2-r-7); a cyclic group having -SO2- represented by the general formula (a5-r-1) to (a5-r-4); and the like are preferable.

[0632] In the formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom.

[0633] In the case where Y 101 is a divalent linking group containing an oxygen atom, this Y 101 may contain atoms other than an oxygen atom. As the atoms other than an oxygen atom, for example, a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, and the like can be exemplified.

[0634] As the divalent linking group containing an oxygen atom, for example, a non-hydrocarbon divalent linking group containing an oxygen atom such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), a carbonate bond (-O-C(=O)-O-), and the like; a combination of this non-hydrocarbon divalent linking group containing an oxygen atom and an alkylene group; and the like can be exemplified. In the combination, a sulfonyl group (-SO2-) can be further linked. As the above-mentioned divalent linking group containing an oxygen atom, for example, a linking group represented by the general formula (y-al-1) to (y-al-7) can be exemplified.

[0635] [Chem. 57]

[0636]

[0637] [In the formula, V 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, V 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0638] V 102 The divalent saturated hydrocarbon group in V

[0639] As the alkylene group in V 101 and V 102 , a linear alkylene group or a branched alkylene group can be used, and a linear alkylene group is preferable.

[0640] As the alkylene group in V 101 and V 102In the alkylene group in the formula (a1-r-1), one or more hydrogen atoms in the alkylene group can be substituted with a fluorine atom. As the alkylene group in the formula (a1-r-1), a methylene group [-CH2-], an alkylmethylene group, an ethylene group [-CH2CH2-], an alkyl ethylene group, a propylene group (n-propylene group) [-CH2CH2CH2-], an alkyl propylene group, a butylene group [-CH2CH2CH2CH2-], an alkyl butylene group, a pentylene group [-CH2CH2CH2CH2CH2-], and the like can be exemplified. As the alkylmethylene group in the formula (a1-r-1), specifically, a methylene group [-CH2-], -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, and the like alkylmethylene group, an ethylene group [-CH2CH2-], -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and the like alkyl ethylene group, a propylene group (n-propylene group) [-CH2CH2CH2-], -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, and the like alkyl propylene group, a butylene group [-CH2CH2CH2CH2-], -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and the like alkyl butylene group, a pentylene group [-CH2CH2CH2CH2CH2-], and the like can be exemplified.

[0641] In the formula (a1-r-1), V 101 is a single bond, an alkylene group, or a fluoroalkylene group. In the formula (a1-r-1), the alkylene group and the fluoroalkylene group in V 102 are preferably a carbon number of 1 to 4. As the fluoroalkylene group in V 3 , a group in which a part or all of the hydrogen atoms in the alkylene group in the formula (a1-r-1) are substituted with a fluorine atom can be exemplified. Among them, V 101 is preferably a single bond or a fluoroalkylene group having a carbon number of 1 to 4.

[0642] As Y 101 , a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond is preferable, and a linking group represented by the above formula (y-al-1) to (y-al-5), respectively, is more preferable.

[0643] In the formula (b-1), V 101 is a single bond, an alkylene group, or a fluoroalkylene group. In the formula (b-1), the alkylene group and the fluoroalkylene group in V 101 are preferably a carbon number of 1 to 4. As the fluoroalkylene group in V 101 , a group in which a part or all of the hydrogen atoms in the alkylene group in the formula (a1-r-1) are substituted with a fluorine atom can be exemplified. Among them, V 101 is preferably a single bond or a fluoroalkylene group having a carbon number of 1 to 4.

[0644] In the formula (b-1), R 102 is a fluorine atom or a fluoroalkyl group having a carbon number of 1 to 5. In the formula (b-1), R 102 is preferably a fluorine atom or a perfluoroalkyl group having a carbon number of 1 to 5, and more preferably a fluorine atom.

[0645] As a specific example of the anion section represented by the aforementioned formula (b-1), for example, in Y 101 In the case of a single bond, examples include fluoroalkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion; in Y 101 In the case of a divalent linking group containing an oxygen atom, anions represented by any one of the following formulas (an-1) to (an-3) can be cited.

[0646]

Chemistry 58

[0647]

[0648] [In the formula, R”] 101 It can be an aliphatic cyclic group that may have substituents, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), or a chain alkyl group that may have substituents. R” 102 It can be an aliphatic cyclic group that may have substituents, a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or a -SO2-containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4). R” 103 It can be an aromatic cyclic group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain-like alkenyl group that may have substituents. V” 101 It is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluoroalkylene group having 1 to 4 carbon atoms. R 102 It is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. v” is an independent integer from 0 to 3, q” is an independent integer from 0 to 20, and n” is 0 or 1.

[0649] R” 101 、R” 102 and R” 103 The aliphatic cyclic group that may have substituents is preferably R in formula (b-1). 101 The group exemplified is a cyclic aliphatic hydrocarbon group. Examples of substituents include those related to R in formula (b-1). 101 The same substituents are used for the substituted cyclic aliphatic hydrocarbon groups.

[0650] R” 103 The aromatic cyclic group that may have substituents is preferably R in formula (b-1). 101 The group exemplified is the aromatic hydrocarbon group in the cyclic hydrocarbon group. Examples of substituents include those corresponding to R in formula (b-1). 101 The same substituents that can replace the aromatic hydrocarbon group in the same group.

[0651] R”101 The chain-like alkyl group which can have a substituent in the formula (b-1) is preferably a group exemplified as the chain-like alkyl group in the formula (b-2). 101 The chain-like alkyl group which can have a substituent in the formula (b-1) is preferably a group exemplified as the chain-like alkyl group in the formula (b-2).

[0652] R" 103 The chain-like alkenyl group which can have a substituent in the formula (b-1) is preferably a group exemplified as the chain-like alkenyl group in the formula (b-2). 101 The chain-like alkenyl group which can have a substituent in the formula (b-1) is preferably a group exemplified as the chain-like alkenyl group in the formula (b-2).

[0653] The anion in the component (b-2)

[0654] In the formula (b-2), R 104 , R 105 are each independently a cyclic group which can have a substituent, a chain-like alkyl group which can have a substituent, or a chain-like alkenyl group which can have a substituent, and the same groups as R 101 in the formula (b-1) can be exemplified. Among them, R 104 , R 105 may be bonded to each other to form a ring.

[0655] R 104 , R 105 are preferably a chain-like alkyl group which can have a substituent, more preferably a straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain fluoroalkyl group.

[0656] The carbon number of the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and further preferably 1 to 3. For the reason that the solubility in the solvent for a resist is also good and the like, the carbon number of the chain-like alkyl group of R 104 , R 105 is more preferably smaller within the above range. Further, the more the number of hydrogen atoms substituted with fluorine atoms in the chain-like alkyl group of R 104 , R 105 is, the stronger the acid strength and the higher the transparency to high-energy light and electron rays of 250 nm or less, and thus it is preferred. The proportion of fluorine atoms in the chain-like alkyl group, that is, the fluorination rate is preferably 70 to 100%, further preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all the hydrogen atoms are substituted with fluorine atoms.

[0657] In the formula (b-2), V 102 , V 103 are each independently a single bond, an alkylene group, or a fluoroalkylene group, and the same groups as V 101 in the formula (b-1) can be exemplified.

[0658] In the formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0659] Anions in component (b-3)

[0660] In equation (b-3), R 106 ~R 108 Each can be independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples can be given for R in formula (b-1). 101 The same group.

[0661] In equation (b-3), L 103 ~L 105 Each can be a single bond, -CO-, or -SO2-, respectively.

[0662] Of the above, the anionic portion of component (B) is preferably the anion in component (b-1). More preferably, it is a fluoroalkyl sulfonate anion or an anion represented by any one of the above general formulas (an-1) to (an-3), and even more preferably, it is a fluoroalkyl sulfonate anion or an anion represented by any one of the general formulas (an-1) and (an-2).

[0663] {Cation Section}

[0664] In equations (b-1), (b-2), and (b-3), M' m+ This represents a monium cation with a valence of m. Preferably, it is a sulfonium cation or an iodonium cation.

[0665] m is an integer greater than or equal to 1.

[0666] As a preferred cation portion ((M') m+ ) 1 / m Examples of organic cations can be given by the following general formulas (ca-1) to (ca-4).

[0667]

Chemistry 59

[0668]

[0669] [In the formula, R] 201 ~R 207 and R 211 ~R 212 Each can be independently represented by an aryl, alkyl, or alkenyl group, which may have substituents. R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 They can also bond with each other to form a ring together with the sulfur atoms in the formula. R 208 ~R 209 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R210 is an aryl group which can have a substituent, an alkyl group which can have a substituent, an alkenyl group which can have a substituent, or a -SO2- containing cyclic group which can have a substituent. L 201 represents -C(=O)- or -C(=O)-O-. Y 201 each independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0670] In the above general formulae (ca-1) to (ca-4), R 201 ~R 207 and R 211 ~R 212 In the aryl group in R

[0671] In the aryl group in R 201 ~R 207 and R 211 ~R 212 The alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0672] In the alkenyl group in R 201 ~R 207 and R 211 ~R 212 The alkenyl group is preferably an alkyl group having 2 to 10 carbon atoms.

[0673] In the cyclic group which can have a substituent in R 201 ~R 207 and R 210 ~R 212 The substituent which the cyclic group can have is exemplified by an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and a group represented by the following general formulae (ca-r-1) to (ca-r-7), respectively.

[0674] [Chemical Formula 60]

[0675]

[0676] [In the formula, R' 201 each independently is a hydrogen atom, a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent.

[0677] The cyclic group which can have a substituent is exemplified by a cyclic hydrocarbon group.

[0678] The cyclic group which can have a substituent is exemplified by a cyclic hydrocarbon group. The cyclic hydrocarbon group can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. Further, the aliphatic hydrocarbon group can be saturated or unsaturated, and is usually saturated.

[0679] R' 201 The aromatic hydrocarbon group in the form is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this 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 carbon atoms in the substituents.

[0680] As R' 201 The aromatic rings contained in aromatic hydrocarbon groups can be specifically exemplified by benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles obtained by replacing part of the carbon atoms constituting these aromatic rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0681] As R' 201 The aromatic hydrocarbon group in the aromatic ring can be specifically exemplified by groups obtained by removing one hydrogen atom from the aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups obtained by substituting one hydrogen atom of the aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups). 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.

[0682] R' 201 Examples of cyclic aliphatic hydrocarbon groups in the structure include aliphatic hydrocarbon groups containing rings.

[0683] Examples of alicyclic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an alicyclic hydrocarbon ring); groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched alicyclic hydrocarbon group; and groups in between alicyclic hydrocarbon groups that are intermediate in a straight-chain or branched alicyclic hydrocarbon group.

[0684] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12.

[0685] The alicyclic hydrocarbon group can be either a polycyclic or monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, a monocyclic alkane with 3 to 6 carbon atoms is preferred; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane; as the polycyclic alkane, a polycyclic alkane with 7 to 30 carbon atoms is preferred. More preferably, as the polycyclic alkane, polycyclic alkanes with a cross-linked ring structure such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycyclic alkanes with a fused ring structure such as a cyclic group with a steroidal skeleton are preferred.

[0686] Among them, as R' 201 The cyclic aliphatic hydrocarbon group in the form is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, more preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, particularly preferably adamantyl or norbornyl, and most preferably adamantyl.

[0687] The linear or branched aliphatic hydrocarbon group that can bond with the alicyclic hydrocarbon group preferably has 1 to 10 carbons, more preferably 1 to 6 carbons, even more preferably 1 to 4 carbons, and particularly preferably 1 to 3 carbons.

[0688] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0689] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0690] In addition, R' 201 The cyclic hydrocarbon group in the formula can contain heteroatoms, just like heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16).

[0691] As R' 201 Substituents in the cyclic group can be, for example, alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, etc.

[0692] The alkyl group used as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0693] The alkoxy group used as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0694] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred option.

[0695] Examples of alkyl halogens that can be used as substituents 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 replaced by the halogen atom.

[0696] The carbonyl group, as a substituent, is a group that replaces the methylene (-CH2-) group that constitutes the cyclic hydrocarbon group.

[0697] Alkyl groups that may have substituents:

[0698] As R' 201 The chain alkyl group can be either straight-chain or branched.

[0699] As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, etc.

[0700] As a branched alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, 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.

[0701] Alkenyl groups that may have substituents in a chain-like structure:

[0702] As R' 201chain alkenyl group, can be either linear or branched, and preferably has a carbon number of 2 to 10, more preferably a carbon number of 2 to 5, further preferably a carbon number of 2 to 4, and particularly preferably a carbon number of 3. As a linear alkenyl group, for example, a vinyl group, a propenyl group (allyl group), a butynyl group, and the like can be given. As a branched alkenyl group, for example, a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, and the like can be given.

[0703] As the chain alkenyl group, among the above, a linear alkenyl group is preferred, more preferably a vinyl group, a propenyl group, and particularly preferably a vinyl group.

[0704] As R' 201 of the substituent of the chain alkyl group or the chain alkenyl group, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above-mentioned R' 201 , a cyclic group, and the like can be given.

[0705] R' 201 of the cyclic group which can have a substituent, the chain alkyl group which can have a substituent, or the chain alkenyl group which can have a substituent, in addition to the above-mentioned groups, as the cyclic group which can have a substituent or the chain alkyl group which can have a substituent, the same groups as the acid dissociable group represented by the above-mentioned formula (a1-r-2) can be given.

[0706] wherein R' 201 is preferably a cyclic group which can have a substituent, more preferably a cyclic hydrocarbon group which can have a substituent. More specifically, for example, a group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group, a polycyclic alkane; a lactone-containing cyclic group represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7); a -SO2- containing cyclic group represented by the above-mentioned general formulae (a5-r-1) to (a5-r-4); and the like can be given.

[0707] In the above-mentioned general formulae (ca-1) to (ca-4), in the case where R 201 to R 203 , R 206 to R 207 , R 211 to R 212 are bonded to each other to form a ring together with the sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R NThe ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. Preferably, the ring structure containing the sulfur atom in the formula is a three- to ten-membered ring, and particularly preferably a five- to seven-membered ring. Specific examples of the formed ring include thiophene rings, thiazole rings, benzothiophene rings, thiathracene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thiathracene rings, phenoxathiin rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0708] R 208 ~R 209 Each of the above independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, in R 208 ~R 209 When they are alkyl groups, they can bond with each other to form a ring.

[0709] R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a -SO2- cyclic group that may have a substituent.

[0710] As R 210 The aryl group in the aryl group can be exemplified by unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred.

[0711] As R 210 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group with 1 to 30 carbon atoms.

[0712] As R 210 The alkenyl group in the R group is preferably an alkenyl group with 2 to 10 carbon atoms. 210 The group may contain a substituent-containing -SO2-cyclic group, preferably a "-SO2-containing polycyclic group", and more preferably a group represented by the general formula (a5-r-1).

[0713] Y 201 Each can be independently represented as arylene, alkylene, or alkenyl.

[0714] Y 201 The aryl group in the equation can be exemplified by R in the above equation (b-1). 101 The aromatic hydrocarbon group in the example is a group obtained by removing one hydrogen atom from the aryl group.

[0715] Y 201 The alkylene and alkenylene groups in the above formula (b-1) can be exemplified by R. 101 The group obtained by removing one hydrogen atom from the chain alkyl or chain alkenyl groups exemplified in the text.

[0716] In the formula (ca-4), x is 1 or 2.

[0717] W 201 is a linking group with a valence of (x + 1), that is, a divalent or trivalent linking group.

[0718] As W 201 the divalent linking group in, preferably a divalent hydrocarbon group which may have substituents, can be exemplified by the same divalent hydrocarbon group with substituents as Ya in the above general formula (a2-1). 21 W 201 The divalent linking group in can be any of linear, branched, or cyclic, preferably cyclic. Among them, a group obtained by combining two carbonyl groups at both ends of an arylene group is preferred. As the arylene group, phenylenyl, naphthylenyl, etc. can be exemplified, and phenylenyl is particularly preferred.

[0719] As W 201 the trivalent linking group in, can be exemplified by a group obtained by removing one hydrogen atom from the divalent linking group in the above W, a group obtained by bonding the divalent linking group to the divalent linking group again, etc. As W 201 the trivalent linking group in, preferably a group obtained by bonding two carbonyl groups to an arylene group. 201 Specific examples of the preferred cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-70), respectively.

[0720]

Chemical Formula 61

[0721]

Chemical Formula 62

[0722] <00​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0733]

[0734] [In the formula, R 201 is a hydrogen atom or a substituent, and as the substituent, the same group as the R 201 ~R 207 and R 210 ~R 212 are the same group.]

[0735] As the preferred cation represented by the formula (ca-2), specifically, diphenyliodonium cation, bis (4-tert-butylphenyl) iodonium cation, and the like can be exemplified.

[0736] As the preferred cation represented by the formula (ca-3), specifically, cations represented by the following formulas (ca-3-1) to (ca-3-6), respectively, can be exemplified.

[0737] [Chem. 67]

[0738]

[0739] As the preferred cation represented by the formula (ca-4), specifically, cations represented by the following formulas (ca-4-1) to (ca-4-2), respectively, can be exemplified.

[0740] [Chem. 68]

[0741]

[0742] Among the above, the cation portion ((M m+ ) 1 / m is preferably a cation represented by the general formula (ca-1). From the viewpoint of maintaining transparency in a thick resist film, in the general formula (ca-1), it is preferred that at least one of R 202 ~R 203 be an alkyl group or an alkenyl group, more preferably that two or more of R 202 ~R 203 be an alkyl group or an alkenyl group, and further preferably that two or more of R 202 ~R 203 be an alkyl group. In the case where two or more of R 202 ~R 203 be an alkyl group or an alkenyl group, these two groups can also be bonded to each other to form a ring together with the sulfur atom in the formula. As the cation represented by the general formula (ca-1), a cation represented by any one of the above formulas (ca-1-55) to (ca-1-68) is preferred, and a cation represented by any one of the above formulas (ca-1-63) to (ca-1-68) is more preferred.

[0743] Among them, as component (B1), compounds represented by the following general formula (b1-1) are particularly preferred.

[0744]

Transformation 69

[0745]

[0746] [In the formula, Rb] 201 It is an aryl group that can have substituents. Rb 202 and Rb 203 Each can be independently an alkyl group that may have substituents or an alkenyl group that may have substituents. Rb 202 and Rb 203 They can bond with each other and form a ring together with the sulfur atoms in the formula. R 101 It can be a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. R 102 It is a fluoroalkyl group or a fluorine atom with 1 to 5 carbon atoms. 101 It is a divalent linking group or single bond containing an oxygen atom. V 101 It is a single bond, an alkylene group, or a fluoroalkylene group.

[0747] In the aforementioned formula (b1-1), Rb 201 The aryl group that may have substituents in the formula (ca-1) is related to R. 201 The aryl groups that can have substituents are the same aryl groups. Among them, as Rb... 201 Phenyl or naphthyl is preferred, and phenyl is more preferred.

[0748] In the aforementioned formula (b1-1), Rb 202 and Rb 203 The alkyl group or alkenyl group that may have substituents in the formula (ca-1) is related to R. 202 and R 203 The alkyl or alkenyl groups that may have substituents are the same group. Wherein, as Rb 202 and Rb 203 Preferably, it is a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably Rb. 202 and Rb 203 They combine with each other to form 5-membered or 6-membered rings together with the sulfur atoms in the formula.

[0749] In the aforementioned formula (b1-1), R 101 R 102 Y 101 and V 101 With R in equation (b-1) 101 R 102 Y 101 and V101 is the same group.

[0750] • Regarding the (B2) component

[0751] The (B) component can also contain an acid generator component that does not belong to the above (B1) component (hereinafter referred to as "(B2) component"). The (B2) component is not particularly limited as long as it generates an acid by exposure and does not belong to the above (B1) component, and can be arbitrarily selected from publicly known components. As the (B2) component, for example, sulfonic acid oxime ester-based acid generators; dia!kyl or diaryl sulfonyl diazomethane-based, poly(bis-sulfonyl) diazomethane-based, and the like can be exemplified. Various acid generators such as nitrobenzyl sulfonate-based acid generators, imino sulfonate-based acid generators, disulfone-based acid generators, and the like can be exemplified.

[0752] In the resist composition of the present embodiment, the (B) component can be used alone in one kind, or two or more kinds can be used in combination.

[0753] In the case where the resist composition contains the (B) component, the content of the (B) component in the resist composition is preferably less than 50 parts by mass, more preferably 0.1 to 40 parts by mass, and further preferably 0.3 to 25 parts by mass, relative to 100 parts by mass of the (A) component.

[0754] By having the content of the (B) component in the above-mentioned preferable range, pattern formation can be sufficiently performed. In addition, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability of the resist composition becomes good, and thus is preferable.

[0755] < Base Component (D) >

[0756] The resist composition of the present embodiment can further contain, in addition to the (A) component and the (Z) component, a base component that captures an acid generated by exposure, i.e., controls the diffusion of the acid ((D) component). The (D) component is a component that functions as a quencher of an acid generated by exposure (an acid diffusion control agent) in the resist composition.

[0757] As the (D) component, for example, a photodegradable base (D1) that loses the acid diffusion control property by decomposition by exposure (hereinafter referred to as "(D1) component"), a nitrogen-containing organic compound (D2) that does not belong to the (D1) component (hereinafter referred to as "(D2) component"), and the like can be exemplified. Among them, from the viewpoint of maintaining the sensitivity in a thick resist film, the nitrogen-containing organic compound (D2) ((D2) component) is preferable. In the (D2) component, from the viewpoint of maintaining the transparency in a thick resist film, a chain alkyl amine is preferable.

[0758] • Regarding the (D1) component

[0759] By providing the resist composition containing the (D1) component, the contrast between the exposed portion and the unexposed portion of the resist film can be further improved at the time of forming a resist pattern. As the (D1) component, there is no particular limitation as long as it loses the acid diffusion controllability by decomposition by exposure, and it 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").

[0760] The (d1-1) to (d1-3) components lose the acid diffusion controllability (basicity) by decomposition in the exposed portion of the resist film and thus cannot function as a quencher, but function as a quencher in the unexposed portion of the resist film.

[0761] [Formula 70]

[0762]

[0763] [In the formula, Rd 1 ~Rd 4 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent. Among them, Rd 2 in the formula (d1-2) is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent. Yd 1 is a single bond or a divalent linking group. m is an integer of 1 or more, and M m+ are each independently an organic cation of m valence.

[0764] {(d1-1) component}

[0765] Anionic portion

[0766] In the formula (d1-1), Rd 1 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent, and the same groups as R 201 can be exemplified.

[0767] Among them, Rd 1, preferably an aromatic hydrocarbon group which can have a substituent, an aliphatic cyclic group which can have a substituent, or a chain alkyl group which can have a substituent. As the substituent which these groups can have, a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluoroalkyl group, a lactone ring-containing cyclic group represented by the above general formulae (a2-r-1) to (a2-r-7) respectively, an ether bond, an ester bond, or a combination thereof can be exemplified. In the case where an ether bond or an ester bond is included as a substituent, an alkylene group can be included as the substituent in this case, and a linking group represented by the above formulae (y-al-1) to (y-al-5) respectively is preferred.

[0768] As the aromatic hydrocarbon group, a polycyclic structure including a phenyl group, a naphthyl group, or a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and a ring structure other than this) can be preferably exemplified.

[0769] As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like is more preferred.

[0770] As the chain alkyl group, a straight chain alkyl group having a carbon number of 1 to 10 can be exemplified, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like; a branched chain alkyl group such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, and the like.

[0771] In the case where the chain alkyl group is a fluoroalkyl group having a fluorine atom or a fluoroalkyl group as a substituent, the carbon number of the fluoroalkyl group is preferably 1 to 11, more preferably 1 to 8, and further preferably 1 to 4. The fluoroalkyl group can contain atoms other than a fluorine atom. As the atoms other than a fluorine atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like can be exemplified.

[0772] As Rd 1 , a fluoroalkyl group in which hydrogen atoms constituting a part or all of a straight chain alkyl group are substituted with fluorine atoms is preferred, and a fluoroalkyl group in which all of the hydrogen atoms constituting a straight chain alkyl group are substituted with fluorine atoms (a straight chain perfluoroalkyl group) is particularly preferred.

[0773] Preferred specific examples of the anion portion of the (d1-1) component are shown below.

[0774] [Chemical Formula 71]

[0775] [Chemical Formula 74] [Chemical Formula 75]

[0776] ··Anion portion

[0777] In formula (d1-1), M m+ is an organic cation of m valence.

[0778] As the organic cation of M m+ , the same organic cations as those represented by the general formulas (ca-1) to (ca-4), respectively, can be preferably exemplified, more preferably the cation represented by the general formula (ca-1), and further preferably the cations represented by the formulas (ca-1-1) to (ca-1-70), respectively.

[0779] The (d1-1) component can be used alone or in combination with two or more.

[0780] {(d1-2) component}

[0781] Anion portion

[0782] In formula (d1-2), Rd 2 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent, and the same groups as those of Rd 201 in the formula (d1-1) can be exemplified.

[0783] In formula (d1-2), Rd 2 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent, and the same groups as those of Rd 201 in the formula (d1-1) can be exemplified.

[0784] As Rd 2 , a chain alkyl group which can have a substituent or an aliphatic cyclic group which can have a substituent is preferable. As the chain alkyl group, the number of carbons is preferably 1 to 10, and more preferably 3 to 10. As the aliphatic cyclic group, a group (which can have a substituent) obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; a group obtained by removing one or more hydrogen atoms from camphor or the like is more preferable.

[0785] The hydrocarbon group of Rd 2 may have a substituent, and as the substituent, the same groups as those which the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd 1 in the formula (d1-1) can have can be exemplified.

[0786] Preferred specific examples of the anion portion of the (d1-2) component are shown below.

[0787] [Chemical 72]

[0788]

[0789] Cation portion

[0790] In formula (dl-2), M m+ is an m-valent organic cation, and is the same as M m+ in formula (dl-1).

[0791] The component (dl-2) can be used alone or in combination of two or more.

[0792] The component (dl-3)

[0793] An anion portion

[0794] In formula (dl-3), Rd 3 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent, and the same groups as R 201 in formula (dl-1) can be exemplified, and is preferably a cyclic group, a chain alkyl group, or a chain alkenyl group which contains a fluorine atom. Among them, a fluorinated alkyl group is preferred, and a fluorinated alkyl group which is the same as R 1 in formula (dl-1) is more preferred.

[0795] In formula (dl-3), Rd 4 is a cyclic group which can have a substituent, a chain alkyl group which can have a substituent, or a chain alkenyl group which can have a substituent, and the same groups as R 201 in formula (dl-1) can be exemplified.

[0796] Among them, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group which can have a substituent are preferred.

[0797] The alkyl group in Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like can be exemplified. The alkyl group of Rd 4 may have a part of hydrogen atoms thereof substituted with a hydroxyl group, a cyano group, or the like.

[0798] The alkoxy group in Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and as the alkoxy group having 1 to 5 carbon atoms, specifically, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a t-butoxy group can be exemplified. Among them, a methoxy group and an ethoxy group are preferred.

[0799] The alkenyl group in Rd 4 may be exemplified by the same groups as the alkenyl group in R 201 in formula (dl-1), and is preferably a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, a 2-methylpropenyl group. These groups can further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.

[0800] Rd 4 The cyclic base in the example can be related to the R' 201 The same cyclic group is preferred, preferably an alicyclic group obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane, or an aromatic group such as phenyl or naphthyl. In Rd 4 In the case of alicyclic groups, the photolithography properties are improved by ensuring good solubility of the resist composition in organic solvents. Furthermore, in Rd... 4 When the resist group is aromatic, the resist composition exhibits excellent light absorption efficiency and good sensitivity and lithographic properties in photolithography using EUV or other light sources.

[0801] In equation (d1-3), Yd 1 It is a single bond or a divalent linker.

[0802] As Yd 1 The divalent linking group in the formula (a2-1) is not particularly limited, and examples include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that can have substituents, and divalent linking groups containing heteroatoms. Examples of these can be found in relation to Ya in the above formula (a2-1). 21 The description of the divalent linking group is the same as that of the divalent hydrocarbon group that may have substituents and the divalent linking group containing heteroatoms.

[0803] As Yd 1 Preferably, it is a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. As an alkylene group, it is more preferably a straight-chain or branched alkylene group, and even more preferably a methylene or ethylene group.

[0804] The following shows a preferred example of the anionic portion of the (d1-3) component.

[0805]

Transformation 73

[0806]

[0807]

Chemistry 74

[0808]

[0809] • Cation section

[0810] In equation (d1-3), M m+ An organic cation with a valence of m, and M in formula (d1-1) m+ same.

[0811] (d1-3) Components can be used alone or in combination of two or more.

[0812] The (D1) component can be used alone or in combination of two or more of the above-described (d1-1) to (d1-3) components.

[0813] In the case where the resist composition contains the (D1) component, the content of the (D1) component is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 5 to 10 parts by mass, relative to 100 parts by mass of the (A) component in the resist composition.

[0814] If the content of the (D1) component is equal to or more than the lower limit of the preferable range, particularly good lithography properties and resist pattern shape are easily obtained. On the other hand, if it is equal to or less than the upper limit of the preferable range, sensitivity is favorably maintained, and throughput is also excellent.

[0815] Method for producing the (D1) component:

[0816] The method for producing the (d1-1) component and the (d1-2) component is not particularly limited, and can be produced by a publicly known method.

[0817] Further, the method for producing the (d1-3) component is not particularly limited, and can be produced, for example, in the same manner as the method described in US 2012-0149916.

[0818] • Regarding the (D2) component

[0819] As the (D) component, it is preferable to contain a nitrogen-containing organic compound component (hereinafter referred to as "(D2) component") which does not belong to the above-described (D1) component.

[0820] As the (D2) component, there is no particular limitation as long as it functions as an acid diffusion controller and does not belong to the (D1) component, and any of publicly known components can be used. Among them, it is preferable to be an aliphatic amine, and more particularly preferably an aliphatic secondary amine or an aliphatic tertiary amine.

[0821] The aliphatic amine refers to an amine having one or more aliphatic groups, and the aliphatic group preferably has a carbon number of 1 to 12.

[0822] As the aliphatic amine, an amine (alkyl amine or alkyl alcohol amine) in which at least one hydrogen atom of ammonia NH3 is substituted with an alkyl group or a hydroxyalkyl group having a carbon number of 12 or less, or a cyclic amine can be exemplified.

[0823] As specific examples of the alkylamines and the alkylolamines, there can be mentioned monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, etc.; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine, etc.; 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, tri-n-dodecylamine, etc.; alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, etc. Among these, further preferred are trialkylamines having a carbon number of 5 to 10, and particularly preferred are tri-n-pentylamine or tri-n-octylamine.

[0824] As the cyclic amines, for example, there can be mentioned heterocyclic compounds containing a nitrogen atom as a hetero atom. As the heterocyclic compounds, there can be either monocyclic compounds (aliphatic monocyclic amines) or polycyclic compounds (aliphatic polycyclic amines).

[0825] As the aliphatic monocyclic amines, specifically, there can be mentioned piperidine, piperazine, etc. As the aliphatic polycyclic amines, preferred are those having a carbon number of 6 to 10, and specifically, there can be mentioned 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1, 4-diazabicyclo [2.2.2] octane, etc.

[0826] As other aliphatic amines, there can be mentioned tri (2-methoxy methoxy ethyl) amine, tri {2- (2-methoxy ethoxy) ethyl} amine, tri {2- (2-methoxy ethoxy methoxy) ethyl} amine, tri {2- (1-methoxy ethoxy) ethyl} amine, tri {2- (1-ethoxy ethoxy) ethyl} amine, tri {2- (1-ethoxy propoxy) ethyl} amine, tri [2- {2- (2-hydroxy ethoxy) ethoxy} ethyl] amine, triethanolamine triacetate, etc., and preferred is triethanolamine triacetate.

[0827] Further, as the (D2) component, an aromatic amine can be used.

[0828] As the aromatic amines, there can be mentioned 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2, 6-diisopropylphenylamine, n-tert-butoxycarbonylpyrrolidine, etc.

[0829] As the (D2) component, from the viewpoint of maintaining transparency in the thick film resist, an aliphatic amine is preferred, a chain aliphatic amine is more preferred, and a chain alkyl amine is further preferred. The chain alkyl amine has a chain alkyl group, and the carbon number of the chain alkyl group is preferably 5 to 10. Among these, a dialkyl amine or a trialkyl amine having a straight chain alkyl group having a carbon number of 5 to 10 is preferred, and a trialkyl amine is more preferred.

[0830] (D2) component can be used alone or two or more kinds can be used in combination.

[0831] In the case where the resist composition contains the (D2) component, it is generally used in a range of 0.005 to 5 parts by mass with respect to 100 parts by mass of the (A) component in the resist composition. By being set to the above range, the resist pattern shape, standing time stability, and the like are improved.

[0832] "Compound (E) selected from at least one kind of the group consisting of organic carboxylic acids and phosphorus-containing oxyacids and derivatives thereof"

[0833] For the purpose of preventing sensitivity deterioration or improving the resist pattern shape, standing time stability, and the like, a compound (E) (hereinafter referred to as "(E) component") selected from at least one kind of the group consisting of organic carboxylic acids and phosphorus-containing oxyacids and derivatives thereof can be contained in the resist composition of the present embodiment as an arbitrary component.

[0834] As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like are preferable.

[0835] As the phosphorus-containing oxyacid, phosphoric acid, phosphonic acid, phosphinic acid, and the like can be exemplified, and among these, phosphonic acid is particularly preferable.

[0836] As the derivative of the phosphorus-containing oxyacid, for example, esters and the like obtained by substituting the hydrogen atom of the above oxyacid with a hydrocarbon group can be exemplified, and as the hydrocarbon group, an alkyl group having a carbon number of 1 to 5, an aryl group having a carbon number of 6 to 15, and the like can be exemplified.

[0837] As the derivative of the phosphonic acid, phosphonic acid di-n-butyl ester, diphenyl phosphonate, and the like can be exemplified.

[0838] As the derivative of the phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenyl phosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and the like can be exemplified.

[0839] As the derivative of the phosphinic acid, phosphinic acid ester or phenyl phosphinic acid, and the like can be exemplified.

[0840] In the resist composition of the present embodiment, the (E) component can be used alone or two or more kinds can be used in combination.

[0841] In the case where the resist composition contains the (E) component, it is generally used in a range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) component.

[0842] "Fluorine additive component (F)"

[0843] In order to impart water repellency to the resist film or in order to improve lithographic properties, the resist composition of the present embodiment can contain a fluorine additive component (hereinafter referred to as "(F) component").

[0844] As the (F) component, for example, a fluorine-containing high molecular compound described in Japanese Patent Application Publication No. 2010-002870, Japanese Patent Application Publication No. 2010-032994, Japanese Patent Application Publication No. 2010-277043, Japanese Patent Application Publication No. 2011-13569, Japanese Patent Application Publication No. 2011-128226 can be used.

[0845] As the (F) component, more specifically, a polymer having a structural unit (f1) represented by the following general formula (f1-1) can be exemplified. As the polymer, a polymer (homopolymer) composed of only the structural unit (f1) represented by the following 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) are preferred. Here, as the structural unit (a1) to be copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate, a structural unit derived from 1-methyl-1-adamantyl (meth) acrylate are preferred.

[0846] [Chemical Formula 75]

[0847]

[0848] [In the formula, R is the same as described above, Rf 102 and Rf 103 independently represent a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 5, or a halogenated alkyl group having a carbon number of 1 to 5, Rf 102 and Rf 103 may be the same or different. nf 1 is an integer of 1 to 5, Rf 101 is an organic group containing a fluorine atom.]

[0849] In formula (f1-1), R bonded to the carbon atom at the α position is the same as described above. As R, a hydrogen atom or a methyl group is preferred.

[0850] In formula (f1-1), as Rf 102 and Rf 103 , a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified, and a fluorine atom is particularly preferred. As Rf 102 and Rf 103 having a carbon number of 1 to 5, the same groups as the alkyl group having a carbon number of 1 to 5 described above for R can be exemplified, and a methyl group or an ethyl group is preferred.102 and Rf 103 halogenated alkyl group having a carbon number of 1 to 5, specifically, a group in which a part or all of hydrogen atoms of an alkyl group having a carbon number of 1 to 5 are substituted with halogen atoms can be exemplified. As the halogen atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified, and a fluorine atom is particularly preferable. Among them, as Rf 102 and Rf 103 a hydrogen atom, a fluorine atom, or an alkyl group having a carbon number of 1 to 5, preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group.

[0851] In formula (f1-1), nf 1 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0852] In formula (f1-1), Rf 101 is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom.

[0853] As the hydrocarbon group containing a fluorine atom, it can be any one of a straight chain, a branched chain, or a ring, and preferably has a carbon number of 1 to 20, more preferably a carbon number of 1 to 15, and particularly preferably a carbon number of 1 to 10.

[0854] Further, the hydrocarbon group containing a fluorine atom preferably has 25% or more of the hydrogen atoms in the hydrocarbon group fluorinated, more preferably 50% or more of the hydrogen atoms fluorinated, and particularly preferably 60% or more of the hydrogen atoms fluorinated, in order to improve the hydrophobicity of the resist film at the time of immersion exposure.

[0855] Among them, as Rf 101 more preferably a fluorinated hydrocarbon group having a carbon number of 1 to 6, and particularly preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF2-CF3.

[0856] The weight average molecular weight (Mw) of the (F) component (polystyrene conversion basis based on gel permeation chromatography) is preferably 1000 to 50000, more preferably 5000 to 40000, and most preferably 10000 to 30000. If it is below the upper limit of the range, it has sufficient solubility against a solvent for a resist for use as a resist, and if it is above the lower limit of the range, the water repellency of the resist film is good.

[0857] The molecular weight distribution coefficient (Mw / Mn) of the (F) component is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0858] In the resist composition of the present embodiment, the (F) component can be used alone as one kind, or two or more kinds can be used in combination.

[0859] In the case where the resist composition contains the (F) component, the (F) component is generally used at a content of 0.5 to 10 parts by mass per 100 parts by mass of the (A) component.

[0860] "Organic Solvent Component (S)"

[0861] 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").

[0862] As the (S) component, any component can be appropriately selected from substances conventionally known as solvents for chemically amplified resist compositions, as long as it can dissolve each component used to form a uniform solution.

[0863] For example, as the (S) component, mention can be made of lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; derivatives of polyhydric alcohols such as monoalkyl ethers or monophenyl ethers of the polyhydric alcohols or the compounds having an ester bond [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; esters; aromatic organic solvents such as anisole, ethyl benzyl ether, methyl tolyl ether, diphenyl ether, dibenzyl ether, phenyl ethyl ether, butyl phenyl ether, ethyl benzene, diethyl benzene, amyl benzene, cumene, toluene, xylene, isopropyl toluene, mesitylene; dimethyl sulfoxide (DMSO), and the like.

[0864] In the resist composition of the present embodiment, the (S) component can be used alone as one kind or as a mixed solvent of two or more kinds. Among these, at least one selected from the group consisting of PGMEA, PGME, γ-butyrolactone, EL, butyl acetate, and cyclohexanone is preferred, and at least one selected from the group consisting of PGMEA, PGME, and butyl acetate is more preferred.

[0865] Further, as the (S) component, a mixed solvent obtained by mixing PGMEA with a polar solvent is also preferred. The blending ratio (mass ratio) of the mixed solvent can be appropriately determined in consideration of the compatibility of PGMEA with the polar solvent and the like, and is preferably set to a range of 1:9 to 9:1, and more preferably to a range of 2:8 to 8:2.

[0866] More specifically, in the case of blending EL, butyl acetate or cyclohexanone as the polar solvent, the mass ratio of PGMEA:EL, butyl acetate or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Further, in the case of blending PGME as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, further preferably 3:7 to 7:3. Furthermore, a mixed solvent of PGMEA and PGME and butyl acetate is also preferable.

[0867] Further, as the (S) component, a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mass ratio of the former to the latter is preferably set to 70:30 to 95:5.

[0868] The amount of use of the (S) component is set in such a manner that the solid content concentration of the resist composition is 25% by mass or more. In the present specification, the solid content in the resist composition refers to components other than the (S) component. The solid content concentration of the resist composition is calculated by the following formula.

[0869] Solid content concentration (% by mass) = (total mass of components other than the (S) component) / (total mass of the resist composition) x 100

[0870] For example, in the case where the resist composition is composed of the (A) component, the (Z) component, the (B) component, the (D) component and the (S) component, the solid content concentration (% by mass) = [((A) component + (Z) component + (B) component + (D) component) / ((A) component + (Z) component + (B) component + (D) component) + (S) component] x 100.

[0871] By setting the solid content concentration of the resist composition to 25% by mass or more, in the case where the resist composition is applied to a substrate to form a resist film, a thick resist film (for example, a film thickness of 5 μm or more, preferably 7 μm or more) can be formed. The solid content concentration of the resist composition is not particularly limited as long as it is 25% by mass or more, and can be appropriately determined depending on the desired film thickness of the resist film. Generally, the higher the solid content concentration, the thicker the film thickness of the resist film.

[0872] The upper limit of the solid content concentration of the resist composition is not particularly limited as long as it is a concentration at which the solid content can be dissolved. The solid content concentration of the resist composition is, for example, 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less.

[0873] Examples of the range of solid component concentration in the resist composition include, for example, 25–60% by mass, 25–55% by mass, or 25–50% by mass.

[0874] The resist composition of this embodiment may further contain additives with a commensurate nature, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halo agents, dyes, etc., as desired.

[0875] After dissolving the aforementioned resist material in component (S), the resist composition of this embodiment can also remove 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 made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of both a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include, for example, the substances described in Japanese Patent Application Publication No. 2016-155121.

[0876] The solid component concentration of the resist composition described above is 25% by mass or more, and it contains a plasticizer component (Z).

[0877] Since the solid content concentration of the resist composition in this embodiment is 25% by mass or more, a thick resist film (e.g., 5 μm or more thick) can be formed by coating it onto a substrate. In such thick resist films, cracks are easily formed in the resist pattern. Furthermore, since light has difficulty reaching the bottom, it is difficult to maintain the sensitivity during exposure, making it difficult to form a resist pattern with a good shape.

[0878] In the resist composition of this embodiment, by including a plasticizer component (Z), both crack resistance and suppression of surface roughness during etching can be achieved. This is presumably because, by including the plasticizer component (Z) in the resist film formed using the resist composition, the stress in the resist film is mitigated. Furthermore, the plasticizer component (Z) does not contain acid-dissociable groups. Therefore, it is presumed that the plasticizer component (Z) present in the resist film does not undergo a deprotection reaction during etching, and the deprotected material does not volatilize from the resist film. As a result, it is presumed that the occurrence of surface roughness during etching is suppressed.

[0879] Furthermore, in the resist composition of this embodiment, the substrate component (A) has structural units (a1) and (a10), which not only improves crack resistance and suppresses surface roughness during etching, but also improves sensitivity and resolution.

[0880] (Resist Pattern Formation Method)

[0881] The resist pattern forming method of the second aspect of the present application is a method having the following steps: a step of forming a resist film on a support using the resist composition of the above-described embodiment; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

[0882] As an embodiment of the above-described resist pattern forming method, for example, a resist pattern forming method performed as described below can be exemplified.

[0883] First, the resist composition of the above-described embodiment is applied on a support with a spin coater or the like, and a baking (post apply bake (PAB)) treatment is performed at a temperature condition of, for example, 80 to 150°C for 40 to 120 seconds, preferably for 60 to 90 seconds to form a resist film.

[0884] Next, the resist film is selectively exposed, for example, using an electron beam drawing device, an EUV exposure device, or the like, by exposure through a mask (mask pattern) forming a prescribed pattern, or drawing based on direct irradiation of electron rays without the mask pattern, and a baking (post exposure bake (PEB)) treatment is performed at a temperature condition of, for example, 80 to 150°C for 40 to 120 seconds, preferably for 60 to 90 seconds.

[0885] Next, a developing treatment is performed on the resist film. In the case of an alkali developing process, the developing treatment is performed using an alkali developing solution, and in the case of a solvent developing process, the developing treatment is performed using a developing solution containing an organic solvent (organic developing solution).

[0886] After the developing treatment, a rinsing treatment is preferably performed. In the case of an alkali developing process, a water rinsing using pure water is preferably performed, and in the case of a solvent developing process, a rinsing solution containing an organic solvent is preferably used.

[0887] In the case of a solvent developing process, after the developing treatment or the rinsing treatment, a treatment for removing the developing solution or the rinsing solution adhering to the pattern by a supercritical fluid can be performed.

[0888] Drying is performed after the developing treatment or the rinsing treatment. Furthermore, a baking treatment (post baking) can be performed after the above-described developing treatment, as the case can be.

[0889] As described above, a resist pattern can be formed.

[0890] The support is not particularly limited, and a conventionally known support can be used. For example, a substrate for electronic parts, a support on which a prescribed wiring pattern is formed, and the like can be given. More specifically, a silicon wafer, a metal substrate made of copper, chromium, iron, aluminum, or the like, or a glass substrate, and the like can be given. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used.

[0891] Further, as the support, a support on which an inorganic and / or organic film is provided on the above-described substrate can be given. As the inorganic film, an inorganic antireflection film (inorganic BARC) can be given. As the organic film, an organic antireflection film (organic BARC), a lower organic film in a multilayer resist method, and the like can be given.

[0892] Here, the multilayer resist method refers to a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and a resist pattern formed on the upper resist film is used as a mask to pattern the lower organic film, and is considered to be capable of forming a pattern with a high aspect ratio. That is, according to the multilayer resist method, the desired thickness can be ensured by the lower organic film, and thus the resist film can be thinned, and a fine pattern with a high aspect ratio can be formed.

[0893] In the multilayer resist method, basically, a method in which a two-layer structure of an upper resist film and a lower organic film is adopted (2-layer resist method) and a method in which a multilayer structure of three or more layers in which one or more intermediate layers (metal thin film or the like) are provided between the upper resist film and the lower organic film is adopted (3-layer resist method) are distinguished.

[0894] In the resist pattern forming method of the present embodiment, since the above-described embodiment of the resist composition is used, a thick resist film can be formed in the process (i). The film thickness of the resist film is preferably 5 μm or more, more preferably 7 μm or more, and further preferably 8 μm or more. The upper limit of the film thickness of the resist film is, for example, 30 μm or less. As the range of the film thickness of the resist film formed in the process (i), for example, 5 to 30 μm can be given, preferably 7 to 20 μm, more preferably 7 to 15 μm, and further preferably 8 to 12 μm. The film thickness of the resist film can be adjusted according to the solid content concentration of the resist composition used in the process (i). That is, the higher the solid content concentration of the resist composition, the higher film thickness of the resist film can be formed.

[0895] The wavelength used in the exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet rays), VUV (vacuum ultraviolet rays), EB (electron beam), X-rays, soft X-rays, and the like can be used. The resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB, or EUV, is more highly useful for KrF excimer laser or ArF excimer laser, and is particularly highly useful for KrF excimer laser. That is, the resist pattern forming method of the present embodiment is particularly useful in a case where the process of exposing the resist film includes an operation of exposing the resist film to KrF excimer laser.

[0896] The exposure method of the resist film can be a general exposure (dry exposure) performed in air, an inert gas such as nitrogen, or the like, or can be liquid immersion exposure (Liquid Immersion Lithography).

[0897] Liquid immersion exposure refers to an exposure method in which a solvent (liquid immersion medium) having a refractive index larger than that of air is filled in advance between a resist film and a lens at the lowermost position of an exposure apparatus, and exposure (immersion exposure) is performed in this state.

[0898] As the liquid immersion medium, a solvent having a refractive index larger than that of air and smaller than that of the exposed resist film is preferred. The refractive index of the solvent is not particularly limited as long as it is within the above range.

[0899] As the solvent having a refractive index larger than that of air and smaller than that of the resist film, for example, water, a fluorine-based inert liquid, a silicon-based solvent, a hydrocarbon-based solvent, and the like can be exemplified. Among them, a fluorine-based inert liquid is preferred.

[0900] As a specific example of the fluorine-based inert liquid, a liquid in which a fluorine-based compound such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, C5H3F7, or the like is a main component can be exemplified. A liquid having a boiling point of 70 to 180°C is preferred, and a liquid having a boiling point of 80 to 160°C is more preferred. If the fluorine-based inert liquid has a boiling point within the above range, the removal of the medium for liquid immersion after the exposure can be performed by a simple method, and thus is preferred.

[0901] As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of an alkyl group are replaced with fluorine atoms is particularly preferred. As the perfluoroalkyl compound, specifically, a perfluoroalkyl ether compound or a perfluoroalkyl amine compound can be exemplified.

[0902] Further, specifically, as the perfluoroalkyl ether compound, perfluoro(2-butyl-tetrahydrofuran) (boiling point 102°C) can be exemplified, and as the perfluoroalkyl amine compound, perfluorotributylamine (boiling point 174°C) can be exemplified.

[0903] As the immersion liquid medium, from the viewpoints of cost, safety, environmental problems, and versatility, it is preferable to use water.

[0904] As the alkaline developer used for the development treatment in the alkaline development process, for example, 0.1 to 10 mass% of a tetramethylammonium hydroxide (TMAH) aqueous solution can be exemplified.

[0905] As the organic solvent contained in the organic developer used for the development treatment in the solvent development process, an organic solvent capable of dissolving the (A) component (the (A) component before exposure) can be appropriately selected from publicly known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents can be exemplified.

[0906] A ketone solvent is an organic solvent including C-C(=0)-C in the structure. An ester solvent is an organic solvent including C-C(=0)-0-C in the structure. An alcohol solvent is an organic solvent including an alcohol hydroxyl group in the structure. The "alcohol hydroxyl group" indicates a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. A nitrile solvent is an organic solvent including a nitrile group in the structure. An amide solvent is an organic solvent including an amide group in the structure. An ether solvent is an organic solvent including C-O-C in the structure.

[0907] Among the organic solvents, there are organic solvents including a plurality of functional groups having the characteristics of each of the above-described solvents in the structure, in which case, the organic solvent belongs to all of the solvent categories having the functional groups. For example, diethylene glycol monomethyl ether belongs to either of the alcohol solvents or the ether solvents in the above-described classification.

[0908] A hydrocarbon solvent is a hydrocarbon solvent composed of a halogenatable hydrocarbon, and does not have a substituent other than a halogen atom. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified, and a fluorine atom is preferable.

[0909] As the organic solvent contained in the organic developer, among the above, a polar solvent is preferable, and a ketone solvent, an ester solvent, a nitrile solvent, and the like are preferable.

[0910] As the ketone-based solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, diacetonc alcohol, ionone, diacetonc alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), and the like can be exemplified. Among these, as the ketone-based solvent, methyl amyl ketone (2-heptanone) is preferred.

[0911] As the ester-based solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like can be exemplified. Among these, as the ester-based solvent, butyl acetate is preferred.

[0912] As the nitrile-based solvent, for example, acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like can be exemplified.

[0913] In the organic developer, a known additive can be blended as needed. As the additive, for example, a surfactant can be exemplified. As the surfactant, there is no particular limitation, and for example, an ionic, nonionic, fluorine-based and / or silicon-based surfactant, and the like can be used. As the surfactant, a nonionic surfactant is preferred, a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferred.

[0914] In the case of blending the surfactant, the blending amount thereof is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the organic developer.

[0915] The developing treatment can be performed by a known developing method, and for example, a method in which the support is immersed in the developer for a certain period of time (immersion method), a method in which the developer is carried on the surface of the support by surface tension and left for a certain period of time (puddle method), a method in which the developer is sprayed to the surface of the support (spray method), a method in which the developer is continuously coated onto the support rotating at a certain speed while the developer is scanned from a nozzle at a certain speed (dynamic distribution method), and the like can be exemplified.

[0916] As the organic solvent contained in the rinsing solution used for the rinsing treatment after the developing treatment in the solvent developing process, for example, an organic solvent which is difficult to dissolve the resist pattern among the organic solvents exemplified as the organic solvent for the organic developer can be appropriately selected. At least one solvent selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, and an ether-based solvent is generally used. Among these, at least one selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, and an amide-based solvent is preferred, at least one selected from an alcohol-based solvent and an ester-based solvent is more preferred, and an alcohol-based solvent is particularly preferred.

[0917] The alcohol-based solvent used in the rinsing solution is preferably a monohydric alcohol having a carbon number of 6 to 8, and the monohydric alcohol can be any one of a straight chain, a branched chain, or a cyclic. Specifically, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like can be exemplified. Among these, 1-hexanol, 2-heptanol, 2-hexanol are preferred, and 1-hexanol, 2-hexanol are more preferred.

[0918] These organic solvents can be used alone as any one of them or in combination of two or more. In addition, they can be used in combination with an organic solvent other than the above or water. Among these, in terms of developing characteristics, the blending amount of water in the rinsing solution is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less, relative to the total amount of the rinsing solution.

[0919] The rinsing solution can be mixed with known additives as needed. Examples of such additives include surfactants. Surfactants can be the same as those described above, preferably nonionic surfactants, more preferably nonionic fluorinated surfactants, or nonionic silicone surfactants.

[0920] When a surfactant is added, the amount added is typically 0.001 to 5% by mass relative to the total amount of rinsing solution, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0921] Rinsing treatment (cleaning treatment) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing methods include continuously applying rinsing solution onto a support rotating at a certain speed (spin coating), immersing the support in rinsing solution for a certain time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0922] According to the resist pattern forming method of this embodiment described above, since the resist composition of the first solution described above is used, it is possible to form a resist pattern with fewer cracks and suppressed surface roughness during etching.

[0923] The above-described resist patterning method is useful as a method for manufacturing three-dimensional structural devices.

[0924] Example

[0925] The present invention will be further described in detail below through examples, but the present invention is not limited to these examples.

[0926] <Example of manufacturing plasticizer component (Z)>

[0927] The compounds shown in Table 1 were used in the molar ratios shown in Table 1 to synthesize polymers Z-1 to Z-10, Z-101 and Z-102 by free radical polymerization.

[0928] will utilize 13 The copolymerization ratios (the proportions (molar ratios) of the structural units in the polymers Z-1 to Z-10, Z-101 and Z-102 obtained by C-NMR, and the mass-average molecular weight (Mw) and molecular weight distribution coefficient (Mw / Mn) converted to polystyrene standards obtained by GPC measurements of the obtained polymers Z-1 to Z-10, Z-101 and Z-102 are recorded in Table 1.

[0929]

Transformation 76

[0930]

[0931] [Table 1]

[0932]

[0933] Preparation of resist composition

[0934] (Examples 1 to 21, Comparative Examples 1 to 6)

[0935] Each of the resist compositions of the examples was prepared by mixing and dissolving each of the components shown in Tables 2 to 4.

[0936] [Table 2]

[0937]

[0938] [Table 3]

[0939]

[0940] [Table 4]

[0941]

[0942] In Tables 2 to 4, each of the abbreviations has the following meaning. The values in the brackets are the amounts of admixture (parts by mass). The solid content concentration was calculated by the following formula: solid content concentration (mass %) = [((A) component + (B) component + (D) component + (Z) component) / ((A) component + (B) component + (D) component + (Z) component + (S) component)] x 100.

[0943] (A)-1: A high molecular compound represented by the following chemical formula (A-1). The weight average molecular weight (Mw) converted to a polystyrene standard, which was measured by GPC, was 10000, and the molecular weight distribution coefficient (Mw / Mn) was 1.4. The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was 1 / m / n = 60 / 15 / 25, which was measured by C-NMR. 13 C-NMR. The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was 1 / m / n = 60 / 15 / 25.

[0944] (A)-2: A high molecular compound represented by the following chemical formula (A-1). The weight average molecular weight (Mw) converted to a polystyrene standard, which was measured by GPC, was 10000, and the molecular weight distribution coefficient (Mw / Mn) was 1.4. The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was 1 / m / n = 60 / 25 / 15, which was measured by C-NMR. 13 C-NMR. The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was 1 / m / n = 60 / 15 / 25.

[0945] [Chemical 77]

[0946]

[0947] (B)-1: An acid-producing agent consisting of a compound represented by the following chemical formula (B-1).

[0948] (B)-2: An acid-producing agent consisting of a compound represented by the following chemical formula (B-2).

[0949] (B)-3: An acid-producing agent consisting of a compound represented by the following chemical formula (B-3).

[0950] (B)-4: An acid-producing agent consisting of a compound represented by the following chemical formula (B-4).

[0951] (B)-5: An acid-producing agent consisting of a compound represented by the following chemical formula (B-5).

[0952] (B)-6: An acid-producing agent consisting of a compound represented by the following chemical formula (B-6).

[0953]

Transformation 78

[0954]

[0955] (D)-1: A nitrogen-containing organic compound consisting of a compound represented by the following chemical formula (D-1).

[0956]

Transformation 79

[0957]

[0958] (Z)-1~(Z)-10: The polymers Z-1~Z-10.

[0959] (Z)-101: The polymer Z-101.

[0960] (Z)-102: The polymer Z-102.

[0961] (S)-1: Propylene glycol monomethyl ether

[0962] (S)-2: Propylene glycol monomethyl ether acetate

[0963] (S)-3: Butyl acetate

[0964] <Formation of resist pattern>

[0965] Process (i):

[0966] On an 8-inch silicon wafer that had undergone hexamethyldisilazane (HMDS) treatment at 110°C for 60 seconds, the resist compositions of each example were applied using a spin coater. The wafers were then pre-baked (PAB) at 150°C for 90 seconds on a hot plate to dry, thereby forming a resist film with a thickness of 15 μm.

[0967] Process (ii):

[0968] Next, the resist film was selectively irradiated with a KrF excimer laser (248 nm) through a mask pattern (binary mask) using a KrF exposure device NSR-S203B (Nikon Corporation; NA (numerical aperture) = 0.60, σ = 0.68).

[0969] Then, it undergoes a post-exposure heating (PEB) treatment at 110°C for 90 seconds.

[0970] Process (iii):

[0971] Next, alkaline development was performed using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as the developer at 23°C for 60 seconds.

[0972] Then, bake at 100°C for 60 seconds.

[0973] The result is the formation of isolated spaced patterns with a spacing width of 5 μm.

[0974] [Resolution Evaluation]

[0975] Determine the optimal exposure value Eop (μC / cm) for forming a 5μm isolated spacing pattern in the above <Resist Pattern Formation>. 2 Furthermore, using the optimal exposure value Eop as the exposure value, a 3μm isolated spacer pattern was formed in the same manner as in the <Resist Pattern Formation> described above. The pattern shape of the 3μm isolated spacer pattern was observed using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.), and evaluated based on the following evaluation criteria. These are shown as "resolution" in Tables 5 to 7.

[0976] Evaluation Criteria

[0977] A: The pattern is reliably formed onto the substrate.

[0978] B: A slight curled edge shape was observed.

[0979] C: Cannot form a pattern.

[0980] [Crack Resistance Evaluation]

[0981] The silicon wafer on which the isolated space pattern was formed by the above-mentioned "formation of resist pattern" was put into the chamber of a scanning electron microscope S-9380 (manufactured by Hitachi High-Technologies Corporation) and vacuum treatment was performed for 60 seconds under a pressure of 0.0001 Pa. The silicon wafer after the vacuum treatment was observed using an optical microscope and the number of cracks was counted. The number of cracks was evaluated based on the following evaluation criteria. The results are shown as "cracks" in Tables 5 to 7.

[0982] Evaluation Criteria

[0983] A: 0 cracks

[0984] B: 1 to 5 cracks

[0985] C: 6 or more cracks

[0986] [evaluation of surface roughness after etching]

[0987] Dry etching of the isolated space pattern formed using the above-mentioned "formation of resist pattern" was performed using an etching device manufactured by Tokyo Ohka Kogyo Co., Ltd. under the following conditions.

[0988] Conditions:

[0989] Type and flow rate of etching gas: mixed gas of tetrafluoromethane 30 cc / min and trifluoromethane 30 cc / min and helium 100 cc / min

[0990] Pressure: 300 mmTorr

[0991] Power: 600 w

[0992] Time: 120 seconds

[0993] The cross section of the isolated space pattern after dry etching was observed using a scanning electron microscope (product name: S4500; manufactured by Hitachi High-Technologies Corporation) and the presence or absence of surface roughness in the cross section of the pattern was evaluated by visual observation. The results are shown in Tables 5 to 7.

[0994] [Table 5]

[0995]

[0996] [Table 6]

[0997]

[0998] [Table 7]

[0999]

[1000] From the results shown in Tables 5 to 7, it is confirmed that the resist compositions of Examples 1 to 21 have good resolution, generation of cracks is suppressed, and occurrence of surface roughness at the time of etching is suppressed. Although the preferred embodiments of the present application have been described above, the present application is not limited to these embodiments. Additional, omission, substitution and other changes can be made to the constitution within the scope of the gist of the present application. The present application is not limited by the above description, but only by the scope of the appended claims.

Claims

1. A photoresist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, characterized in that, contains: a resin component (A1) having a structural unit (a1) having an acid-decomposable group which is increased by the action of a polar factor acid and a structural unit (a10) represented by the following general formula (a10-1); a plasticizer component (Z) having a structural unit (z1) represented by the following general formula (z1-1), which does not have an acid dissociable group, the content of the plasticizer component (Z) is 50 parts by mass or less relative to 100 parts by mass of the resin component (A1), the weight average molecular weight Mw of the plasticizer component (Z) based on polystyrene as measured by gel permeation chromatography is 5000 to 200000, the solid content concentration is 25% by mass or more, 【Chemical Formula 1】 wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbons, or a halogenated alkyl group having 1 to 5 carbons, Ya x1 is a single bond or a divalent linking group, Wa x1 is an aromatic hydrocarbon group which can have a substituent, n ax1 is an integer of 1 or more, 【Chemical Formula 2】 wherein R is a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a halogenated alkyl group having a carbon number of 1 to 5, and Vz 0 is a single bond or a 2-valent hydrocarbon group which can contain a hetero atom, wherein Vz 0 is a 2-valent hydrocarbon group which can contain a hetero atom, wherein Vz 0 does not contain an acid dissociable group, and Rz 0 is a group represented by the following general formula (z1-r-1), 【Chemical Formula 3】 wherein Rz 01 is a hydrocarbon group which can have a substituent, Rz 02 is a hydrogen atom or a hydrocarbon group which can have a substituent, Rz 01 and Rz 02 may be bonded to each other to form a ring structure, wherein Rz 01 and Rz 02 does not contain an acid dissociable group, and * is a bond.

2. The resist composition of claim 1, wherein the content of the plasticizer component (Z) is 1 to 30 parts by mass relative to 100 parts by mass of the resin component (A1).

3. A resist pattern forming method characterized by, has: a step of forming a resist film using the resist composition according to claim 1 or 2 on a support; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

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