Resist composition and method for forming resist pattern

Abstract

The present invention relates to a resist composition capable of generating an acid by exposure to light and capable of changing the solubility in a developing solution by the action of the acid, the resist composition contains a base material component (A) whose solubility in a developing solution can be changed by the action of an acid, an acid generator component (B) capable of generating an acid by exposure, and a plasticizer component (Z), and is characterized in that the base material component (A) contains a resin component (A1) having a structural unit (a1) and a structural unit (a2) and not containing an aromatic ring; the structural unit (a1) is a structural unit which is represented by general formula (a1-1) described in the description and contains an acid-decomposable group of which the polarity can be increased by the action of an acid, and the structural unit (a2) contains any one of a lactone-containing cyclic group, a-SO2-containing cyclic group, or a carbonate-containing cyclic group, and the structural unit (a1) is a structural unit which is represented by general formula (a1-1) described in the description and contains an acid-decomposable group of which the polarity can be increased by the action of an acid. The plasticizer component (Z) has a structural unit (z1) represented by general formula (z1-1) described in the description, and the content of the plasticizer component (Z) is 20 parts by mass or less with respect to 100 parts by mass of the resin component (A1).

Description

Technical Field

[0001] This invention relates to resist compositions and methods for forming resist patterns. Background Technology

[0002] In photolithography, for example, the following steps are performed: forming a resist film made of a resist material on a substrate, selectively exposing the resist film, and performing a development process, thereby forming a resist pattern of a predetermined shape on the resist film. A resist material whose exposed portion of the resist film can be dissolved in the developer is called a positive resist material, and a resist material whose exposed portion of the resist film is insoluble in the developer is called a negative resist material.

[0003] In recent years, advancements in photolithography technology have rapidly accelerated the miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display components. As a method for miniaturization, the wavelength (energy) of the exposure light source has typically been shortened. Specifically, ultraviolet light, represented by g-lines and i-lines, was previously used, but now KrF excimer lasers and ArF excimer lasers are being used for mass production of semiconductor devices. Furthermore, research has been conducted on shorter wavelengths (higher energy) than these excimer lasers, such as EUV (extreme ultraviolet), EB (electron beam), and X-rays.

[0004] For resist materials, photolithographic properties such as sensitivity to these exposure light sources and resolution that enables the reproduction of fine-sized patterns are required.

[0005] As a resist material that meets such requirements, a chemically amplified resist composition has been used in the past, which contains a substrate component whose solubility in the developer can be changed by the action of acid, and an acid-generating agent component that can generate acid by exposure.

[0006] When the developer described above is an alkaline developer (alkaline development process), a positive chemically amplified resist composition is typically used, which contains a resin component (base resin) whose solubility in the alkaline developer increases with the action of acid, and an acid-generating agent component. Regarding the resist film formed using such a resist composition, if selective exposure is performed during resist pattern formation, acid is generated in the exposed areas by the acid-generating agent component. The polarity of the base resin increases due to the action of this acid, and the exposed areas of the resist film become soluble in the alkaline developer. Therefore, by performing alkaline development, a positive pattern can be formed where the unexposed areas of the resist film remain as a pattern.

[0007] On the other hand, when such a chemically amplified resist composition is applied to a solvent development process using a developer containing an organic solvent (organic developer), if the polarity of the base resin increases, its solubility in the organic developer relatively decreases. Therefore, the unexposed portions of the resist film are dissolved and removed by the organic developer, forming a negative resist pattern where the exposed portions of the resist film remain as the pattern. Sometimes, this solvent development process that forms a negative resist pattern is called a negative development process.

[0008] To date, the base resins used in chemically amplified resist compositions, for example for KrF excimer lasers (248 nm), are highly transparent polyhydroxystyrene (PHS), and the hydroxyl groups of which are protected with acid-dissociable dissolution-inhibiting groups (PHS-based resins). Additionally, for ArF excimer lasers (193 nm), resins obtained by protecting the hydroxyl groups in the carboxyl groups of (meth)acrylic acid with acid-dissociable dissolution-inhibiting groups ((meth)acrylic acid-based resins) are used.

[0009] For example, Patent Document 1 describes the following: For the purpose of providing a resist composition with excellent photolithographic properties and adhesion and reducing residue, and a resist pattern forming method using the resist composition, a polymeric compound (C) containing a structural unit having an alcoholic hydroxyl group is used ((C) component).

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2012-168504 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] Recently, with the advancement of photolithography technology and the expansion of its application areas, there is an increasing need for technologies that can form fine patterns in good shape when manufacturing semiconductor components.

[0015] However, with further miniaturization of the patterns, the following problems arise: increasing the hardness of the pattern makes it easier for cracks to form in the resist pattern due to external stress, etc. Additionally, the desired resist pattern shape is difficult to obtain due to the influence of voids (pores) generated in the resist areas of the pattern. Furthermore, there is still room for improvement in order to achieve better resolution using conventional resist compositions.

[0016] The present invention was made in view of the above circumstances, and its objective is to provide a resist composition with excellent resolution and that is not prone to cracking or voids, and a method for forming a resist pattern using the resist composition.

[0017] Methods for solving problems

[0018] To address the aforementioned issues, the present invention employs the following configuration.

[0019] That is, the first aspect of the present invention is a photoresist composition that is capable of generating acid upon exposure and whose solubility in a developer solution can be changed by the action of the acid, said photoresist composition comprising:

[0020] The solubility of the substrate component in the developer solution can be changed by the action of acid (A), the acid-generating agent component that can generate acid through exposure (B), and

[0021] Plasticizer component (Z),

[0022] The aforementioned substrate component (A) comprises a resin component (A1) having structural units (a1) and (a2) and free of aromatic rings. The structural unit (a1) is a structural unit represented by the following general formula (a1-1) containing an acid-degradable group whose polarity can increase through the action of an acid. The structural unit (a2) comprises any one of a cyclic group containing a lactone, a cyclic group containing -SO2-, or a cyclic group containing a carbonate.

[0023] The aforementioned plasticizer component (Z) has a structural unit (z1) represented by the following general formula (z1-1).

[0024] The content of the plasticizer component (Z) is 20 parts by mass or less, relative to 100 parts by mass of the aforementioned resin component (A1).

[0025] [Chemical Formula 1]

[0026]

[0027] [In general formula (a1-1), R1 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. Va01 is a divalent linking group. na01 is an integer from 0 to 2. Ra01 is a chain-like alkyl group. Ya01 is a carbon atom. Xa01 is a group that forms a monocyclic alicyclic hydrocarbon group together with Ya01. Some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted.]

[0028] [Chemical Formula 2]

[0029]

[0030] In general 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. 0 It is a single bond or a divalent hydrocarbon group that may contain heteroatoms. Rz 0 It can be a hydrogen atom or a group represented by the following general formula (z1-r-1).

[0031] [Chemical Formula 3]

[0032]

[0033] In the general formula (z1-r-1), Rz 01 It is a hydrocarbon group that can have substituents. Rz 02 It consists of a hydrogen atom or a hydrocarbon group that may have substituents. Rz 01 With Rz 02 They can bond together to form a ring structure. * indicates a connecting bond.

[0034] The second aspect of the present invention is a method for forming a resist pattern, which includes the following steps: a step of forming a resist film on a support using the resist composition involved in the first aspect; a step of exposing the resist film; and a step of developing the resist film to form a resist pattern.

[0035] Invention Effects

[0036] According to the present invention, a resist composition with excellent resolution and that is not prone to cracking or voids, and a method for forming a resist pattern using the resist composition, can be provided. Detailed Implementation

[0037] In this specification and claims, "aliphatic" is a relative concept compared to aromatic, and is defined as non-aromatic groups, compounds, etc.

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

[0039] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0040] "Halogenated alkyl" is a group obtained by replacing some or all of the hydrogen atoms of an alkyl group with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0041] "Fluoroalkyl" or "fluoroalkylene" refers to a group obtained by replacing some or all of the hydrogen atoms of an alkyl or alkylene group with fluorine atoms.

[0042] "Structural unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer).

[0043] The cases described as "may have substituents" include both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH2-) is replaced by a divalent group.

[0044] "Exposure" is a concept that includes exposure to all forms of radiation.

[0045] The term "substrate component" refers to an organic compound with film-forming ability, preferably an organic compound with a molecular weight of 500 or higher. By ensuring the molecular weight of this organic compound is 500 or higher, film-forming ability is improved, and nanoscale resist patterns are easily formed. Organic compounds used as substrate components can be broadly categorized into non-polymers and polymers. As non-polymers, those with a molecular weight of 500 or higher and less than 4000 are typically used. The term "low molecular weight compound" refers to a non-polymer with a molecular weight of 500 or higher and less than 4000. As polymers, those with a molecular weight of 1000 or higher are typically used. The term "resin," "high molecular weight compound," or "polymer" refers to a polymer with a molecular weight of 1000 or higher. The molecular weight of the polymer is the weight-average molecular weight converted to polystyrene based on GPC (gel permeation chromatography).

[0046] The term "structural unit derived from acrylate" refers to a structural unit formed by the breaking of the olefinic double bonds in acrylate.

[0047] "Acrylates" are compounds obtained by replacing the hydrogen atom at the carboxyl terminus of acrylic acid (CH2=CH-COOH) with an organic group.

[0048] The hydrogen atom bonded to the α-carbon atom in acrylates can be replaced by a substituent. The substituent (R) that replaces the hydrogen atom bonded to the α-carbon atom... α0 () refers to atoms or groups other than hydrogen atoms, such as alkyl groups with 1 to 5 carbon atoms and haloalkyl groups with 1 to 5 carbon atoms. It also includes substituents (R). α0 Itaconic acid diester obtained by substituting a group containing an ester bond, and the substituent (R) α0 α-hydroxy acrylates are obtained by replacing hydroxyalkyl groups or groups modified from the hydroxyl group with hydroxyalkyl groups. It should be noted that, unless otherwise specified, the α-carbon atom of an acrylate refers to the carbon atom bonded to the carbonyl group of acrylic acid.

[0049] Hereinafter, acrylates obtained by replacing the hydrogen atom bonded to the carbon atom at the α-position with a substituent are sometimes referred to as α-substituted acrylates. In addition, the term "(α-substituted) acrylate" is sometimes used to include both acrylates and α-substituted acrylates.

[0050] In this specification and claims, depending on the structure shown in the chemical formula, sometimes a chiral carbon is present, resulting in enantiomers and diastereomers. In such cases, these isomers are represented by a single chemical formula. These isomers may be used alone or in mixtures.

[0051] (Resistant Composition)

[0052] The first aspect of the present invention relates to a photoresist composition capable of generating acid upon exposure and whose solubility in a developer solution is changeable by the action of acid. It comprises a substrate component (A) (hereinafter also referred to as "(A) component") whose solubility in a developer solution is changeable by the action of acid, an acid-generating agent component (B) (hereinafter also referred to as "(B) component") capable of generating acid upon exposure, and a plasticizer component (Z) (hereinafter also referred to as "(Z) component"). The aforementioned substrate component (A) comprises having structural units (a1) and (a2) and does not contain aromatic rings. The resin component (A1) (hereinafter also referred to as "(A1) component"), wherein the structural unit (a1) is a structural unit represented by general formula (a1-1) containing an acid-decomposable group whose polarity can be increased by the action of an acid, wherein the structural unit (a2) contains any one of a cyclic group containing a lactone, a cyclic group containing -SO2- or a cyclic group containing a carbonate, and the aforementioned plasticizer component (Z) has a structural unit (z1) represented by general formula (z1-1), wherein the content of the aforementioned plasticizer component (Z) is 20 parts by mass or less relative to 100 parts by mass of the aforementioned resin component (A1).

[0053] If such a resist composition is used to form a resist film, it is possible to form a resist film that simultaneously achieves crack resistance, porosity resistance, excellent resolution, and excellent photolithography properties.

[0054] If a resist film is formed using such a resist composition and the resist film is selectively exposed, acid is generated in the exposed areas of the resist film. The solubility of component (A) in the developer changes due to the action of this acid. On the other hand, in the unexposed areas of the resist film, the solubility of component (A) in the developer does not change. Therefore, a difference in solubility in the developer occurs between the exposed and unexposed areas of the resist film. Thus, if the resist film is developed, when the resist composition is positive, the exposed areas of the resist film are dissolved and removed to form a positive resist pattern; when the resist composition is negative, the unexposed areas of the resist film are dissolved and removed to form a negative resist pattern.

[0055] In this specification, a resist composition in which the exposed portion of the 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 the resist film is dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. The resist compositions involved in the embodiments of the present invention can be either positive or negative resist compositions. Furthermore, the resist compositions involved in the embodiments of the present invention can be used in an alkaline developing process using an alkaline developer during the developing process for forming a resist pattern, or in a solvent developing process using a developer containing an organic solvent (organic developer) during the developing process.

[0056] In the resist composition according to embodiments of the present invention, component (A), whose solubility in developer can be changed by the action of acid, comprises a resin component (A1) having structural units (a1) and (a2) and not containing aromatic rings. The structural unit (a1) is a structural unit containing an acid-degrading group represented by the general formula (a1-1), whose polarity can be increased by the action of acid. The structural unit (a2) comprises any one of a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate.

[0057] Component (A) can also generate acid through exposure. In this case, component (A) becomes "a substrate component capable of generating acid through exposure, and whose solubility in the developer can be changed by the action of acid." When component (A) is a substrate component capable of generating acid through exposure, and whose solubility in the developer can be changed by the action of acid, the component (A1) described later is preferably a polymeric compound capable of generating acid through exposure, and whose solubility in the developer can be changed by the action of acid. As such a polymeric compound, a resin having structural units capable of generating acid through exposure can be used. As structural units capable of generating acid through exposure, known structural units can be used.

[0058] In the resist composition according to the embodiments of the present invention, the solubility of the substrate component (A) in the developer can be changed by the action of acid. Therefore, in the alkaline development process, the solubility of the resist film in the alkaline developer is increased during development.

[0059] Furthermore, in the resist composition according to the embodiments of the present invention, the acid-generating component (B) capable of generating acid by exposure can be, for example, known acid-generating components.

[0060] By including a specific amount of plasticizer component (Z) in the resist composition according to embodiments of the present invention, both crack resistance and suppression of void formation can be achieved simultaneously. This is presumably because the presence of plasticizer component (Z) in the resist film formed using the aforementioned resist composition can alleviate stress in the resist film.

[0061] Furthermore, since the structural unit (a1) contained in the substrate component (A) includes a monocyclic structure, a moderate plasticizing effect is achieved in the film through the combination of the plasticizer component (Z) and the acid-dissociating groups of the monocyclic structure in the substrate component (A). This mitigates the effects of external stress and reduces crack formation. In addition, products that are the main cause of void formation during resist film formation are easily released outside the resist film, suppressing void formation. Moreover, it is speculated that the moderate plasticizing effect increases the reactivity of the resist film, and the acid-dissociating groups of the monocyclic structure in the substrate component (A) improve the solubility of the developer, thus increasing resolution.

[0062] <(A)Component>

[0063] In the resist composition according to the embodiments of the present invention, the solubility of component (A) in the developer solution can be changed by the action of acid.

[0064] By using the (A1) component, the polarity of the substrate composition changes before and after exposure, thus enabling good development contrast not only in alkaline development processes but also in solvent development processes.

[0065] As component (A), at least component (A1) is used, and it may also be used together with other high molecular weight compounds and / or low molecular weight compounds.

[0066] When using an alkaline development process, the substrate component containing component (A1) is poorly soluble in the alkaline developer before exposure. If, for example, acid is generated from component (B) through exposure, the polarity increases due to the action of the acid, and the solubility in the alkaline developer increases. Therefore, in the formation of a resist pattern, if the resist film obtained by coating the resist composition onto a support is selectively exposed, the exposed portion of the resist film changes from poorly soluble to soluble in the alkaline developer, while the unexposed portion of the resist film remains unchanged and remains poorly soluble in the alkaline developer. Therefore, by performing alkaline development, a positive resist pattern can be formed.

[0067] On the other hand, when using a solvent-based development process, the substrate component containing component (A1) has high solubility in an organic developer before exposure. If, for example, acid is generated from component (B) through exposure, the polarity increases due to the action of the acid, and the solubility in the organic developer decreases. Therefore, in the formation of a resist pattern, if the resist film obtained by coating the resist composition onto a support is selectively exposed, the exposed portion of the resist film changes from soluble to insoluble in the organic developer, while the unexposed portion of the resist film remains unchanged and is still soluble. Therefore, by developing with an organic developer, a contrast can be imparted between the exposed and unexposed portions, and a negative resist pattern can be formed.

[0068] In the resist composition involved in the embodiments of the present invention, component (A) can be used alone or in combination with two or more components.

[0069] Regarding component (A1)

[0070] (A1) is a resin component whose solubility in the developer can be changed by the action of acid.

[0071] Component (A1) is a resin component having structural units (a1) and (a2) and not containing aromatic rings. The structural unit (a1) is a structural unit containing an acid-degradable group whose polarity can be increased by the action of an acid. The structural unit (a2) contains any one of a cyclic group containing a lactone, a cyclic group containing -SO2-, or a cyclic group containing a carbonate.

[0072] (A1) Components can also be components that, in addition to structural units (a1) and structural units (a2), have other structural units as needed.

[0073] Structural Unit (a1) >>

[0074] The structural unit (a1) is a structural unit containing an acid-decomposing group whose polarity can be increased by the action of an acid.

[0075] An "acid-decomposable group" is a group whose structure contains at least a portion of bonds that can be broken by the action of an acid, thus possessing acid-decomposability.

[0076] Examples of acid-decomposing groups that can increase polarity through the action of acids include groups that can decompose to produce polar groups through the action of acids.

[0077] Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonyl (-SO3H). Among these, polar groups containing -OH in their structure (hereinafter sometimes referred to as "polar groups containing OH") are preferred, carboxyl or hydroxyl groups are more preferred, and carboxyl groups are particularly preferred.

[0078] More specifically, examples of acid-dissociable groups include groups obtained by protecting the aforementioned polar groups with acid-dissociable groups (for example, groups obtained by protecting the hydrogen atoms of a polar group containing OH with an acid-dissociable group).

[0079] Here, "acid-dissociable group" refers to either of the following: (i) an acid-dissociable group whose bonds with the adjacent atoms can be broken by the action of an acid; or (ii) a group whose bonds can be broken by a further decarboxylation reaction after a portion of the bonds have been broken by the action of an acid.

[0080] The acid-dissociating groups that constitute the acid-dissociating groups must be groups with lower polarity than the polar groups generated through the dissociation of the acid-dissociating groups. Therefore, when the acid-dissociating groups dissociate under the action of acid, polar groups with higher polarity than the acid-dissociating groups are generated, thus increasing the polarity. As a result, the overall polarity of the (A1) component increases. Due to this increased polarity, the solubility in the developer changes accordingly: in the case of an alkaline developer, solubility increases, while in the case of an organic developer, solubility decreases.

[0081] As an acid-dissociating group, examples of acid-dissociating groups proposed so far include those of the base resins used in chemically amplified resist compositions.

[0082] Regarding the acid-dissociating groups proposed for the base resin used in chemically amplified resist compositions, examples of acid-dissociating groups include "acetal-type acid-dissociating groups," "tertiary alkyl ester-type acid-dissociating groups," and "tertiary alkoxycarbonyl acid-dissociating groups."

[0083] The (A1) component contains a structural unit (a1) representing the following general formula (a1-1) that contains an acid-decomposing group whose polarity can be increased by the action of an acid.

[0084] [Chemical Formula 4]

[0085]

[0086] [In general formula (a1-1), R1 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. Va01 is a divalent linking group. na01 is an integer from 0 to 2. Ra01 is a chain-like alkyl group. Ya01 is a carbon atom. Xa01 is a group that forms a monocyclic alicyclic hydrocarbon group together with Ya01. Some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted.]

[0087] In the aforementioned general formula (a1-1), the alkyl group represented by R1, having 1 to 5 carbon atoms, is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The haloalkyl group having 1 to 5 carbon atoms is a group obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred.

[0088] R1 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0089] In the aforementioned general formula (a1-1), the divalent linking group represented by Va01 is not particularly limited, and examples such as divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms are preferred.

[0090] The aliphatic hydrocarbon group that forms the divalent hydrocarbon group in VaO1 can be saturated or unsaturated, but is usually preferred to be saturated.

[0091] More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0092] The aforementioned linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0093] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0094] The aforementioned branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

[0095] 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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene 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.

[0096] Examples of aliphatic hydrocarbon groups containing rings in their structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups include groups identical to the aforementioned straight-chain or branched aliphatic hydrocarbon groups.

[0097] The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0098] The aforementioned alicyclic hydrocarbon group can be either polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane; the polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms; examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0099] When Va01 is a divalent linking group containing heteroatoms, examples of preferred linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- (H can be replaced by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and 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 Each can be an independent divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m” is an integer from 0 to 3, etc.

[0100] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H group can be replaced by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0101] 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 22Each is an independent divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups are the same groups listed in the description of the divalent linking groups in Va01 above (divalent hydrocarbon groups that may have substituents).

[0102] As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0103] As Y 22 Preferably, it is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0104] Formula-[Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as in formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably of the formula -Y 21 -C(=O)-OY 22 - represents a group. Preferably, it is of 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.

[0105] Of the above, VaO1 is preferably an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched alkylene group, or a combination thereof.

[0106] In the aforementioned general formula (a1-1), na01 is an integer from 0 to 2, preferably 0.

[0107] In the structural unit (a1) of the embodiments of the present invention, the acid-dissociating group that protects the carboxyl group in the above-mentioned polar group includes the acid-dissociating group represented by the following general formula (a1-r-1).

[0108] [Chemical Formula 5]

[0109]

[0110] [In formula (a1-r-1), Ra01 is a chain-like alkyl group. Ya01 is a carbon atom. Xa01 is a group that forms a monocyclic alicyclic hydrocarbon group with Ya01. Some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted. * indicates a connecting bond.]

[0111] In general formulas (a1-1) and (a1-r-1), the chain alkyl group represented by Ra01 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0112] In general formulas (a1-1) and (a1-r-1), the monocyclic alicyclic hydrocarbon group formed by Xa01 and Ya01 is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As this monocyclic alkane, it is preferably a monocyclic alkane with 3 to 12 carbon atoms, more preferably a monocyclic alkane with 3 to 8 carbon atoms, and even more preferably a monocyclic alkane with 3 to 6 carbon atoms. Specifically, examples include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cyclononane.

[0113] The following are specific examples of the groups represented by the aforementioned formula (a1-r-1).

[0114] [Chemical Formula 6]

[0115]

[0116] The following shows specific examples of the structural unit represented by the aforementioned equation (a1-1). In the following equations, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0117] [Chemical Formula 7]

[0118]

[0119] [Chemical Formula 8]

[0120]

[0121] The proportion of structural unit (a1) in the (A1) component is preferably 5 to 80 mol% relative to the total (100 mol%) of all structural units constituting the (A1) component, more preferably 5 to 75 mol%, even more preferably 10 to 70 mol%, even more preferably 10 to 60 mol%, and particularly preferably 40 to 60 mol%.

[0122] By setting the proportion of structural unit (a1) to the lower limit of the aforementioned preferred range or higher, lithographic properties such as sensitivity, resolution, and roughness are improved. On the other hand, if it is below the upper limit of the aforementioned preferred range, balance with other structural units can be achieved, resulting in better lithographic properties.

[0123] Regarding structural unit (a2):

[0124] In component (A1), in addition to structural unit (a1), there is also structural unit (a2) containing a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate (excluding structural units belonging to structural unit (a1)).

[0125] The cyclic groups containing lactones, -SO2-, or carbonates in the structural unit (a2) are effective in improving the adhesion between the resist film and the substrate when component (A1) is used to form the resist film. Furthermore, by having the structural unit (a2), effects such as appropriately adjusting the acid diffusion length, improving the adhesion between the resist film and the substrate, and appropriately adjusting the solubility during development can be achieved, thereby improving photolithography characteristics such as resolution.

[0126] The term "cyclic group containing lactone" refers to a cyclic group containing a ring (lactone ring) with -OC (=O)- in its ring skeleton. The lactone ring is considered 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 specific structure, it is called a polycyclic group. Cyclic groups containing lactones can be either monocyclic or polycyclic.

[0127] There are no particular limitations on the cyclic group containing lactone in the structural unit (a2), and any group can be used. Specifically, examples can be given of the groups represented by the following general formulas (a2-r-1) to (a2-r-7).

[0128] [Chemical Formula 9]

[0129]

[0130] [In the formula, Ra'] 21 Each of these elements is 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, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-; A is an alkylene group, oxygen atom, or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atom (-O-) or sulfur atom (-S-); n' is an integer from 0 to 2; and m' is 0 or 1.

[0131] * indicates a connection key.

[0132] In the aforementioned general formulas (a2-r-1) to (a2-r-7), Ra' 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.

[0133] As Ra' 21 The alkoxy group in the formula is preferably an alkoxy group having 1 to 6 carbon atoms. This alkoxy group is preferably linear or branched. Specifically, Ra' can be cited as an example. 21 The alkyl group listed is a group formed by alkyl groups bonded to an oxygen atom (-O-).

[0134] As Ra' 21 The halogen atoms in the atom can be fluorine, chlorine, bromine, iodine, etc., with fluorine atoms being preferred.

[0135] As Ra' 21 The haloalkyl group in the above example is Ra' 21 A group obtained by replacing some or all of the hydrogen atoms of the alkyl group with the aforementioned halogen atoms. The alkyl halogroup is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0136] Ra' 21 In -COOR” and -OC(=O)R”, R” can be a hydrogen atom, alkyl group, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-.

[0137] The alkyl group in "R" can be any of the following: linear, branched, or cyclic, and the number of carbon atoms is preferably 1 to 15.

[0138] When R” is a straight-chain or branched alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably methyl or ethyl.

[0139] When R” is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes that can be substituted with fluorine atoms or fluorinated alkyl groups or are not substituted; groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0140] As the cyclic group containing lactone in "R", the same group as the group represented by each of the aforementioned general formulas (a2-r-1) to (a2-r-7) can be cited.

[0141] As the carbonate-containing cyclic group in "R", it is the same as the carbonate-containing cyclic groups described later. Specifically, the groups represented by general formulas (ax3-r-1) to (ax3-r-3) can be cited.

[0142] As the cyclic group containing -SO2- in "R", it is the same as the cyclic group containing -SO2- described later. Specifically, the groups represented by general formulas (a5-r-1) to (a5-r-4) can be cited.

[0143] As Ra' 21 The hydroxyalkyl group in the formula is preferably a hydroxyalkyl group having 1 to 6 carbon atoms. Specifically, the aforementioned Ra' can be cited as an example. 21 A group obtained by replacing at least one hydrogen atom of an alkyl group with a hydroxyl group.

[0144] In the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A” is preferably a straight-chain or branched alkylene group, such as methylene, ethylene, n-propylene, and isopropylene. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples include groups with -O- or -S- at the end of the aforementioned alkylene group or between carbon atoms, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. A” is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably methylene.

[0145] The following provides specific examples of the groups represented by the general formulas (a2-r-1) to (a2-r-7), as well as other cyclic groups containing lactones.

[0146] [Chemical Formula 10]

[0147]

[0148] [Chemical Formula 11]

[0149]

[0150] The term "cyclic group containing -SO2-" refers to a cyclic group containing a ring with -SO2- in its ring skeleton. Specifically, it refers to a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- in its ring skeleton is counted as the first ring. If only this ring is present, it is called a monocyclic group. If other ring structures are present, regardless of their structure, it is called a polycyclic group. Cyclic groups containing -SO2- can be either monocyclic or polycyclic.

[0151] Cyclic groups containing -SO2- are particularly preferred to be cyclic groups that contain -O-SO2- in their ring skeleton, that is, cyclic groups containing -OS- in -O-SO2- forming part of the sultone ring in the ring skeleton.

[0152] More specifically, examples can be given by the groups represented by the following general formulas (a5-r-1) to (a5-r-4), which are cyclic groups containing -SO2-.

[0153] [Chemical Formula 12]

[0154]

[0155] [In the formula, Ra'] 51 Each of the following groups is 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, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-; A is an alkylene group, oxygen atom, or sulfur atom with 1 to 5 carbon atoms, which may contain oxygen or sulfur atoms; n' is an integer from 0 to 2. * indicates a connecting bond.

[0156] In the aforementioned general formulas (a5-r-1) to (a5-r-2), A” is the same as A” in the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5).

[0157] As Ra' 51 The alkyl, alkoxy, halogen atom, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups mentioned above can be exemplified by Ra' in the aforementioned general formulas (a2-r-1) to (a2-r-7).21 The same groups listed in the description.

[0158] Specific examples of the groups represented by the general formulas (a5-r-1) to (a5-r-4) are given below. In the formulas, "Ac" represents an acetyl group. * indicates a linking bond.

[0159] [Chemical Formula 13]

[0160]

[0161] [Chemical Formula 14]

[0162]

[0163] [Chemical Formula 15]

[0164]

[0165] The term "cyclic group containing carbonate" refers to a cyclic group containing a ring (carbonate ring) with -OC (=O)-O- in its ring skeleton. The carbonate ring is considered the first ring. In the case of only a carbonate ring, it is called a monocyclic group; in the case of other ring structures, regardless of their specific structures, it is called a polycyclic group. Cyclic groups containing carbonate can be either monocyclic or polycyclic.

[0166] There are no particular limitations on the cyclic group containing carbonate, and any group can be used. Specifically, examples can be given of the groups represented by the following general formulas (ax3-r-1) to (ax3-r-3).

[0167] [Chemical Formula 16]

[0168]

[0169] [In the formula, Ra'] x31 Each group 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 can be a hydrogen atom, alkyl group, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-; A can be an alkylene group with 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, p' is an integer from 0 to 3, and q' is 0 or 1. * indicates a connecting bond.

[0170] In the aforementioned general formulas (ax3-r-2) to (ax3-r-3), A” is the same as A” in the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5).

[0171] As Ra' x31The alkyl, alkoxy, halogen atom, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups mentioned above can be exemplified by Ra' in the aforementioned general formulas (a2-r-1) to (a2-r-7). 21 The same groups listed in the description.

[0172] Specific examples of the groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are given below.

[0173] [Chemical Formula 17]

[0174]

[0175] Among them, the structural unit (a2) is preferably an acrylate-derived structural unit that is a substituent for the hydrogen atom bonded to the carbon atom at the α position.

[0176] Such a structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

[0177] [Chemical Formula 18]

[0178]

[0179] [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 It is a single bond or a divalent linker. La 21 The denoted as -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. Specifically, in La... 21 In the case of -O-, Ya 21 Not -CO-. Ra 21 It can be a cyclic group containing lactones, a cyclic group containing carbonates, or a cyclic group containing -SO2-.

[0180] In the aforementioned formula (a2-1), R is the same as R1 in the aforementioned general formula (a1-1). As R, it 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 particularly preferred to have a hydrogen atom or a methyl group.

[0181] In the aforementioned equation (a2-1), Ya is... 21 The divalent linking group in the linking group is not particularly limited, but preferred examples include divalent hydrocarbon groups that may have substituents and divalent linking groups that contain heteroatoms.

[0182] • Divalent hydrocarbon groups that may have substituents:

[0183] In Ya21 In the case of a divalent hydrocarbon group that may have substituents, the hydrocarbon group may be an aliphatic hydrocarbon group.

[0184] ··Ya 21 aliphatic hydrocarbon groups

[0185] Aliphatic hydrocarbon groups refer to hydrocarbon groups that are not aromatic. These aliphatic hydrocarbon groups can be saturated or unsaturated, but are usually preferred to be saturated.

[0186] Examples of aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0187] ...straight-chain or branched aliphatic hydrocarbon groups

[0188] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0189] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0190] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

[0191] 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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene 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.

[0192] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may or may not have substituents. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0193] ...aliphatic hydrocarbon groups containing rings in their structure

[0194] Examples of aliphatic hydrocarbon groups containing a ring in their structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain substituents containing heteroatoms in their ring structure, groups obtained by bonding the aforementioned cyclic aliphatic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups include the same aliphatic hydrocarbon groups as described above.

[0195] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0196] The cyclic aliphatic hydrocarbon group can be either a polycyclic or monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane; the polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms; examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0197] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0198] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0199] Regarding the alkoxy group used as the aforementioned substituent, it is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and even more preferably methoxy or ethoxy.

[0200] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being the preferred option.

[0201] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0202] In the case of cyclic aliphatic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure can be replaced with substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0203] • Divalent linking groups containing heteroatoms:

[0204] In Ya 21 In the case of a divalent linking group containing a heteroatom, examples of preferred linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and 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 Each can be an independent divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m” is an integer from 0 to 3, etc.

[0205] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H group can be replaced by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0206] 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 mentioned above, which are related to the aforementioned Ya. 21 The same groups listed in the description of the divalent linking groups (which may have substituents) are the same groups.

[0207] As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0208] As Y 22 Preferably, it is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0209] Formula-[Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as in formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably of the formula -Y 21 -C(=O)-OY 22 - represents a group. Preferably, it is of 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.

[0210] 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.

[0211] In the aforementioned equation (a2-1), Ra21 It can be a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate.

[0212] As Ra 21 The cyclic groups containing lactones, cyclic groups containing -SO2-, and cyclic groups containing carbonates can preferably be represented by the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the groups represented by the general formulas (a5-r-1) to (a5-r-4), and the groups represented by the general formulas (ax3-r-1) to (ax3-r-3).

[0213] Preferably, the cyclic group contains a lactone or a cyclic group contains -SO2-, and more preferably, it is a group represented by the aforementioned general formulas (a2-r-1), (a2-r-2), (a2-r-6), or (a5-r-1). Specifically, it is more preferably any group represented by the aforementioned chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r-lc-6-1), (r-sl-1-1), and (r-sl-1-18).

[0214] The following shows a preferred example of the structural unit represented by the aforementioned equation (a2-1). In the following equations, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0215] [Chemical Formula 19]

[0216]

[0217] The structural unit (a2) of component (A1) can be one type or two or more types.

[0218] When component (A1) has structural unit (a2), the proportion of structural unit (a2) is preferably 5 to 60 mol% relative to the total (100 mol%) of all structural units constituting component (A1), more preferably 10 to 60 mol%, even more preferably 20 to 55 mol%, and particularly preferably 30 to 50 mol%.

[0219] If the proportion of structural unit (a2) is above the preferred lower limit, the effects brought about by containing structural unit (a2) can be fully obtained due to the aforementioned effects. If it is below the upper limit, balance with other structural units can be achieved, and various lithographic properties become better.

[0220] Other Structural Units

[0221] (A1) Component can also be a component that has other structural units as needed, in addition to the above-mentioned structural units (a1) and structural units (a2).

[0222] Other structural units include, for example, structural units containing aliphatic hydrocarbon groups with polar groups (a3), etc.

[0223] In the resist composition of the embodiments of the present invention, the (A1) component preferably does not contain structural units (st) derived from styrene or styrene derivatives, or structural units derived from hydroxystyrene or hydroxystyrene derivatives, as this facilitates further improvement of the properties in ArF-based lithography.

[0224] Regarding structural unit (a3):

[0225] Component (A1) may also be a structural unit (a3) ​​containing an aliphatic hydrocarbon group with a polar group, in addition to structural units (a1) and (a2) (excluding structural units belonging to structural units (a1) or (a2)). That is, the aforementioned resin component (A1) preferably also has a structural unit (a3) ​​containing an aliphatic hydrocarbon group with a polar group.

[0226] By incorporating structural units (a3) ​​into component (A1), the hydrophilicity of component (A) is increased, which contributes to improved resolution. Furthermore, the acid diffusion length can be appropriately adjusted.

[0227] Examples of polar groups include hydroxyl, cyano, carboxyl, and hydroxyalkyl groups in which some hydrogen atoms of an alkyl group are replaced by fluorine atoms, with hydroxyl being particularly preferred.

[0228] Examples of aliphatic hydrocarbon groups include straight-chain or branched hydrocarbon groups (preferably alkylene groups) with 1 to 10 carbon atoms, and cyclic aliphatic hydrocarbon groups (cyclic groups). These cyclic groups can be monocyclic or polycyclic, and for example, can be appropriately selected and used from many cyclic groups proposed for resins used in resist compositions for ArF excimer lasers.

[0229] When the cyclic group is a monocyclic group, the number of carbon atoms is more preferably 3 to 10. More preferably, it is a structural unit derived from an acrylate-based monocyclic group comprising a hydroxyalkyl group containing a hydroxyl group, a cyano group, a carboxyl group, or an alkyl group, with some hydrogen atoms substituted by a fluorine atom. Examples of such monocyclic groups include groups obtained by removing two or more hydrogen atoms from monocyclic alkanes. Specifically, examples include groups obtained by removing two or more hydrogen atoms from monocyclic alkanes such as cyclopentane, cyclohexane, and cyclooctane. Among these monocyclic groups, groups obtained by removing two or more hydrogen atoms from cyclopentane and groups obtained by removing two or more hydrogen atoms from cyclohexane are industrially preferred.

[0230] When the cyclic group is a polycyclic group, the number of carbon atoms in the polycyclic group is more preferably 7 to 30. More preferably, it is a structural unit derived from an acrylate of an aliphatic polycyclic group comprising a hydroxyl alkyl group containing a hydroxyl, cyano, carboxyl, or alkyl group with some hydrogen atoms replaced by fluorine atoms. Examples of such polycyclic groups include groups obtained by removing two or more hydrogen atoms from bicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, etc. Specifically, examples include groups obtained by removing two or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Among these polycyclic groups, groups obtained by removing two or more hydrogen atoms from adamantane, groups obtained by removing two or more hydrogen atoms from norbornane, and groups obtained by removing two or more hydrogen atoms from tetracyclic dodecane are industrially preferred.

[0231] As a structural unit (a3), there are no particular restrictions as long as it is a structural unit containing an aliphatic hydrocarbon group with a polar group, any group can be used.

[0232] As a structural unit (a3), it is preferably a structural unit containing an aliphatic hydrocarbon group with a polar group, which is an acrylate-derived structural unit from which the hydrogen atom bonded to the carbon atom at the α-position can be replaced by a substituent.

[0233] As a structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a straight-chain or branched hydrocarbon group with 1 to 10 carbon atoms, it is preferably a structural unit derived from a hydroxyethyl ester of acrylic acid.

[0234] Furthermore, when the aliphatic hydrocarbon group containing a polar group is a polycyclic group, the structural units represented by formula (a3-1), (a3-2), and (a3-3) below are preferred structural units; when the aliphatic hydrocarbon group containing a polar group is a monocyclic group, the structural unit represented by formula (a3-4) is preferred structural unit.

[0235] [Chemical Formula 20]

[0236]

[0237] [In the formula, R is the same as before, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, l is an integer from 0 to 5, and s is an integer from 1 to 3.]

[0238] In formula (a3-1), j is preferably 1 or 2, more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3- and 5-positions of the adamantyl alkyl group. When j is 1, the hydroxyl group is preferably bonded to the 3-position of the adamantyl alkyl group.

[0239] j is preferably 1, and the hydroxyl group is particularly preferably bonded to the 3-position of the adamantyl group.

[0240] In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornel group.

[0241] In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. They are preferably bonded with 2-norbornyl or 3-norbornyl at the end of the carboxyl group of acrylic acid. The fluoroalkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.

[0242] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluoroalkyl alcohol is preferably bonded to the 3 or 5 position of the cyclohexyl group.

[0243] The structural unit (a3) ​​of component (A1) can be one type or two or more types.

[0244] When component (A1) has structural unit (a3), the proportion of structural unit (a3) ​​is preferably 1 to 30 mol% relative to the total (100 mol%) of all structural units constituting component (A1), more preferably 2 to 25 mol%, and even more preferably 5 to 20 mol%.

[0245] By setting the proportion of structural unit (a3) ​​to a preferred lower limit or above, the effects brought about by containing structural unit (a3) ​​can be fully obtained due to the aforementioned effects. If it is set to a preferred upper limit or below, balance with other structural units can be achieved, and various lithographic properties become better.

[0246] The (A1) component contained in the resist composition can be used alone or in combination with two or more components.

[0247] In the resist composition according to the embodiments of the present invention, the (A1) component can be a polymeric compound having a repeating structure of structural unit (a1) and structural unit (a2).

[0248] As a preferred component (A1), examples include polymeric compounds having repeating structures of structural unit (a1), structural unit (a2), and other structural units. Examples of the aforementioned other structural units include structural unit (a3), etc.

[0249] In addition to the two combinations of structural units mentioned above, the structural units described above can also be appropriately combined as a third or more structural units according to the desired effect. For example, combinations of structural units (a1), (a2), and (a3) ​​can be given as combinations of three or more structural units.

[0250] Preferred examples of component (A1) include polymeric compounds having repeating structures of structural units (a1) and (a2); and polymeric compounds having repeating structures of structural units (a1), (a2) and (a3).

[0251] Such (A1) components can be manufactured by dissolving monomers capable of deriving each structural unit in a polymerization solvent, and then adding free radical polymerization initiators such as azobisisobutyronitrile (AIBN) and dimethyl azobisisobutyrate (e.g., V-601) to the solvent for polymerization.

[0252] Alternatively, such a (A1) component can be manufactured by dissolving monomers capable of deriving structural units (a1) and (a2), and monomers capable of deriving structural units other than structural units (a1) and (a2) as needed, in a polymerization solvent, adding a free radical polymerization initiator as described above to the solvent, and then carrying out a deprotection reaction.

[0253] It should be noted that during polymerization, chain transfer agents such as HS-CH2-CH2-CH2-C(CF3)2-OH can also be used in combination to introduce -C(CF3)2-OH groups to the ends. Copolymers obtained by introducing hydroxyalkyl groups with some hydrogen atoms of the alkyl group replaced by fluorine atoms are effective in reducing development defects and LER (Line Edge Roughness: unevenness of the line sidewalls).

[0254] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion using gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.

[0255] If the Mw of component (A1) is below the preferred upper limit of the range, it has sufficient solubility in the resist solvent for use as a resist; if it is above the preferred lower limit of the range, it has good resistance to dry etching and good resist pattern cross-sectional shape.

[0256] The dispersion (Mw / Mn) of component (A1) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. It should be noted that Mn represents the number-average molecular weight.

[0257] • Regarding the base material components other than component (A1)

[0258] Regarding the resist composition according to embodiments of the present invention, a substrate component (A) that is not part of the aforementioned component (A1) and whose solubility in the developer solution can be changed by the action of acid may also be used as component (A). There are no particular limitations on the substrate component that is not part of the aforementioned component (A1). It may be selected and used arbitrarily from many components known conventionally as substrate components for chemically amplified resist compositions. One of the polymeric or low-molecular-weight compounds may be used alone, or two or more may be used in combination.

[0259] The proportion of component (A1) in component (A) relative to the total mass of component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may also be 100% by mass. If the aforementioned proportion is 25% by mass or more, it is easy to form various resist patterns with excellent photolithography properties.

[0260] In the resist composition according to the embodiments of the present invention, the content of component (A) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and even more preferably 8 to 16% by mass.

[0261] <(Z) component>

[0262] (Z) component is a plasticizer component having a structural unit (z1) represented by the following general formula (z1-1).

[0263] Structural unit (z1) preferably does not contain acid-dissociable groups. Here, "acid-dissociable groups" refers to both of the following: (i) acid-dissociable groups whose bonds with adjacent atoms can be broken by acid action; or (ii) groups whose bonds can be broken by further decarboxylation reaction after a portion of the bonds have been broken by acid action.

[0264] Preferably, the plasticizer component (Z) is free of acid-dissociable groups. That is, preferably, all structural units constituting component (Z) are free of acid-dissociable groups. By ensuring that all structural units constituting component (Z) are free of acid-dissociable groups, component (Z) will not undergo deprotection reactions due to the action of acids.

[0265] [Chemical Formula 21]

[0266]

[0267] [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. Vz] 0 It is a single bond or a divalent hydrocarbon group that may contain heteroatoms. Rz 0 It can be a hydrogen atom or a group represented by the following general formula (z1-r-1).

[0268] [Chemical Formula 22]

[0269]

[0270] In the formula (z1-r-1), Rz 01 It is a hydrocarbon group that can have substituents. Rz 02 It consists of a hydrogen atom or a hydrocarbon group that may have substituents. Rz 01 With Rz 02 They can bond together to form a ring structure. * indicates a connecting bond.

[0271] Structural Unit (z1)

[0272] In the aforementioned 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.

[0273] 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. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0274] The alkyl halogroup with 1 to 5 carbon atoms in R is a group obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl group with 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.

[0275] 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.

[0276] In the aforementioned equation (z1-1), Vz 0The divalent hydrocarbon group may contain heteroatoms. For example, divalent hydrocarbon groups that may have substituents or divalent hydrocarbon groups containing heteroatoms are preferred divalent hydrocarbon groups.

[0277] In Vz 0 In the case of a divalent hydrocarbon group that may have substituents, examples of such hydrocarbon groups include aliphatic hydrocarbon groups.

[0278] Aliphatic hydrocarbon groups refer to hydrocarbon groups that are not aromatic. These aliphatic hydrocarbon groups can be saturated or unsaturated, but are usually preferred to be saturated.

[0279] Examples of aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0280] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0281] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0282] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

[0283] 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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene 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.

[0284] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may or may not have substituents. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0285] Examples of aliphatic hydrocarbon groups containing a ring in their structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain substituents containing heteroatoms in their ring structure, groups obtained by bonding the aforementioned cyclic aliphatic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups that are intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups include the same aliphatic hydrocarbon groups as described above.

[0286] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0287] The cyclic aliphatic hydrocarbon group can be either a polycyclic or monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane; the polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms; examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0288] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0289] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0290] Regarding the alkoxy group used as the aforementioned substituent, it is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and even more preferably methoxy or ethoxy.

[0291] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being the preferred option.

[0292] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0293] In the case of cyclic aliphatic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure can be replaced with substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0294] In Vz 0 In the case of a divalent hydrocarbon group that can contain heteroatoms, Vz 0 Preferably, it does not contain acid-dissociable groups.

[0295] 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 is independently a divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include those mentioned above, which are related to the aforementioned Ya. 21 The same group listed in the description of the divalent linking group as "a divalent hydrocarbon group that may have substituents" is also included.

[0296] In the aforementioned equation (z1-1), Rz 0 It is a hydrogen atom or a group represented by the aforementioned general formula (z1-r-1).

[0297] In the aforementioned equation (z1-r-1), Rz 01 The hydrocarbon group in the formula may have substituents, such as straight-chain or branched alkyl groups or cyclic hydrocarbon groups.

[0298] Rz 01 The linear alkyl group in the form preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0299] As Rz 01 The branched alkyl group in the form preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl.

[0300] Composition of Rz 01 In this formula, a portion of the carbon atoms in the straight-chain or branched alkyl group can be replaced with oxygen atoms (-O-). However, in the aforementioned formula (z1-r-1), Rz 01 Preferably, it does not contain acid-dissociable groups. Therefore, in the aforementioned formula (z1-r-1), even when constituting Rz... 01In cases where a portion of the carbon atoms of the straight-chain or branched alkyl group are replaced with oxygen atoms (-O-), it is also preferable that the acetal-type acid dissociation group is not present.

[0301] Rz 01 The cyclic hydrocarbon group can be an aliphatic hydrocarbon group, or it can be a polycyclic group or a monocyclic group.

[0302] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0303] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be 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. Specifically, examples include adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0304] Rz 01 The cyclic hydrocarbon group in the hydrocarbon may have substituents. For example, -R can be considered as such a substituent. P1 -R P2 -OR P1 -R P2 -CO-R P1 -R P2 -CO-OR P1 -R P2 -O-CO-R P1 -R P2 -OH, -R P2 -CN or -R P2 -COOH (Hereinafter, these substituents will also be collectively referred to as "Ra") 05 ")wait.

[0305] Here, R P1 It can be a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms. Additionally, R... P2 It is a single bond, a divalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, or a divalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms. Among them, R... P1 and R P2 Some or all of the hydrogen atoms in the chain-like saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be replaced by fluorine atoms. The aforementioned aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents, or it may have one or more of various substituents.

[0306] Examples of monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl.

[0307] Examples of monocyclic aliphatic saturated hydrocarbon groups with 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclic [2.2.2]octyl, tricyclic [5.2.1.02,6]decyl, tricyclic [3.3.1.13,7]decyl, tetracyclic [6.2.1.13,6.02,7]dodecyl, and adamantyl.

[0308] In the aforementioned equation (z1-r-1), Rz 02 Hydrocarbon groups that may have substituents and Rz 01 The same applies to hydrocarbon groups that can have substituents.

[0309] In the aforementioned equation (z1-r-1), Rz 01 With Rz 02 When the compounds bond together to form a ring structure, examples of such a ring structure include groups obtained by removing two hydrogen atoms from monocyclic or polycyclic alkanes. Preferably, the monocyclic alkane has 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane.

[0310] The preferred polycyclic alkane is a polycyclic alkane with 7 to 12 carbon atoms, specifically examples include adamantane, norbornene, isobornene, tricyclodecane, and tetracyclododecane.

[0311] In the aforementioned formula (z1-r-1), it is preferred that Rz 01 It is a straight-chain alkyl or a straight-chain alkoxy group, and Rz 02 It is a hydrogen atom, or Rz 01 With Rz 02 They bond together to form a ring structure.

[0312] The structural unit (z1) of component (Z) can be one type or two or more types.

[0313] Among them, the (Z) component preferably has a structural unit (z1) represented by the following general formula (z1-1-1) (hereinafter, sometimes referred to as "structural unit (z1-1-1)") and a structural unit (z1-1-2) represented by the following general formula (z1-1-2) (hereinafter, sometimes referred to as "structural unit (z1-1-2)") as structural unit (z1).

[0314] [Chemical Formula 23]

[0315]

[0316] [In the formula, R] 01 and R 02 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Vz 01 For single bonds, -C(=O)-OY 21 -or-C(=O)-OY 21 -OC(=O)-Y 22 -. Y 21 and Y 22 Each is an independent divalent hydrocarbon group that can have substituents, and O is an oxygen atom. Rz 10 It is a straight-chain alkyl group, -Rz 11 -O-Rz 12 Or a monovalent alicyclic hydrocarbon group. Rz 11 It is a straight-chain alkylene group, Rz 12 It is a straight-chain alkyl group.

[0317] In the aforementioned equations (z1-1-1) and (z1-1-2), R 01 and R 02 The same applies to R in the aforementioned equation (z1-1). Wherein, R... 01 Preferably, it is a hydrogen atom, a methyl group, or a trifluoromethyl group; more preferably, it is a hydrogen atom or a methyl group; and even more preferably, it is a methyl group. R 02 Preferably, it is a hydrogen atom, a methyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0318] In the aforementioned equation (z1-1-1), Vz 01 -C(=O)-OY 21 -or-C(=O)-OY 21 -OC(=O)-Y 22 - In the case of Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and particularly preferably methylene or ethylene. As Y 22 Preferably, it is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0319] Among them, as Vz 01 Preferably, it is a single bond.

[0320] In the aforementioned equation (z1-1-2), Rz 10 The linear alkyl group in the form preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0321] In the aforementioned equation (z1-1-2), Rz 10 -Rz 11 -O-Rz 12 In the case of Rz 11 Preferably, it is a straight-chain alkylene group having 1 to 5 carbon atoms, more preferably a methylene or ethylene. Rz 12 Preferably, it is a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably methyl or ethyl.

[0322] In the aforementioned equation (z1-1-2), Rz 10 The monovalent alicyclic hydrocarbon group can be either a polycyclic group or a monocyclic group.

[0323] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0324] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be 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. Specifically, examples include adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0325] The (Z) component preferably includes structural units represented by the following general formula (z1-2-21) (hereinafter, sometimes referred to as "structural unit (z1-2-21)") and structural units represented by the following general formula (z1-2-22) (hereinafter, sometimes referred to as "structural unit (z1-2-22)") as structural units (z1-1-2).

[0326] [Chemical Formula 24]

[0327]

[0328] [In the formula, R] 21 and R 22 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Rz 11 It is a linear alkylene group. Rz 12 It is a straight-chain alkyl group. Rz 13 It is a straight-chain alkyl group or a monovalent alicyclic hydrocarbon group.

[0329] In the aforementioned equations (z1-1-21) and (z1-1-22), R 21 and R 22 R in the aforementioned equation (z1-1-2) 02 same.

[0330] In the aforementioned equation (z1-1-21), Rz 11 and Rz 12 Rz in the aforementioned equation (z1-1-2) 11 and Rz 12 same.

[0331] In the aforementioned equation (z1-1-21), Rz 13 The straight-chain alkyl group or monovalent alicyclic hydrocarbon group in the above formula (z1-1-2) is related to Rz. 10 The same applies to straight-chain alkyl groups or monovalent alicyclic hydrocarbon groups.

[0332] The following shows a specific example of the structural unit (z1). In the following equations, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0333] [Chemical Formula 25]

[0334]

[0335] The proportion of structural unit (z1) in component (Z) is preferably 50 to 100 mol% relative to the total (100 mol%) of all structural units constituting component (Z), more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, and may also be 100 mol%.

[0336] By keeping the proportion of the structural unit (z1) within the aforementioned preferred range, it is easy to suppress the generation of cracks and voids.

[0337] When component (Z) contains the aforementioned structural units (z1-1-1) and (z1-1-2) as structural units (z1), the proportion of structural unit (z1-1-1) in component (Z) is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, and even more preferably 5 to 20 mol%, relative to the total (100 mol%) of all structural units constituting component (Z). Furthermore, the proportion of structural unit (z1-1-2) in component (Z) is preferably 70 to 99 mol%, more preferably 75 to 97 mol%, and even more preferably 80 to 95 mol%, relative to the total (100 mol%) of all structural units constituting component (Z).

[0338] By keeping the ratio of structural units (z1-1-1) and (z1-1-2) within the aforementioned preferred range, it is easy to suppress the generation of cracks and voids.

[0339] When component (Z) contains the aforementioned structural units (z1-1-1), (z1-1-21), and (z1-1-22) as structural units (z1), the proportion of structural unit (z1-1-1) in component (Z) is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, and even more preferably 5 to 20 mol%, relative to the total (100 mol%) of all structural units constituting component (Z). Furthermore, the proportion of structural unit (z1-1-21) in component (Z) is preferably 10 to 99 mol%, more preferably 15 to 97 mol%, even more preferably 20 to 95 mol%, and even more preferably 20 to 70 mol%, relative to the total (100 mol%) of all structural units constituting component (Z). Furthermore, relative to the total (100 mol%) of all structural units constituting the (Z) component, the proportion of structural units (z1-1-22) in the (Z) component is preferably 0 to 80 mol%, more preferably 10 to 75 mol%, even more preferably 15 to 70 mol%, and even more preferably 20 to 65 mol%.

[0340] By keeping the proportions of structural unit (z1-1-1), structural unit (z1-1-21), and structural unit (z1-1-22) within the aforementioned preferred range, it is easy to suppress the generation of cracks and voids.

[0341] Other Structural Units

[0342] (Z) Components can also be components that have other structural units besides the structural unit (z1) mentioned above, as needed.

[0343] Other structural units that can be cited include the aforementioned structural units (a1), (a3), etc.

[0344] When component (Z) has structural unit (a1), the proportion of structural unit (a1) in component (Z) is preferably 10 to 60 mol% relative to the total (100 mol%) of all structural units constituting component (Z), more preferably 20 to 55 mol%, and even more preferably 30 to 50 mol%.

[0345] By setting the proportion of structural unit (a1) above the lower limit, it is easier to further improve sensitivity. On the other hand, by setting it below the upper limit, it is easier to achieve balance with other structural units.

[0346] The (Z) component contained in the resist composition can be used alone or in combination with two or more components.

[0347] In the resist composition according to the embodiments of the present invention, component (Z) can be a polymeric compound having a repeating structure of structural unit (z1).

[0348] As a preferred (Z) component, examples 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).

[0349] Such (Z) components can be manufactured by dissolving monomers capable of deriving each structural unit in a polymerization solvent, and then adding free radical polymerization initiators such as azobisisobutyronitrile (AIBN) and dimethyl azobisisobutyrate (e.g., V-601) to the solvent for polymerization.

[0350] Alternatively, such a (Z) component can be manufactured by dissolving a monomer capable of deriving structural unit (z1) and a monomer capable of deriving structural units other than structural unit (z1) as needed in a polymerization solvent, and then adding a free radical polymerization initiator as described above to perform polymerization.

[0351] It should be noted that during polymerization, chain transfer agents such as HS-CH2-CH2-CH2-C(CF3)2-OH can also be used in combination to introduce -C(CF3)2-OH groups to the ends. Copolymers obtained by introducing hydroxyalkyl groups with some hydrogen atoms of the alkyl group replaced by fluorine atoms are effective in reducing development defects and LER (line edge roughness: unevenness of the line sidewalls).

[0352] The weight-average molecular weight (Mw) of component (Z) (based on polystyrene conversion using gel permeation chromatography (GPC)) is not particularly limited, but is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, and even more preferably 15,000 to 100,000.

[0353] If the Mw of the (Z) component is within the above-mentioned preferred range, it is easy to suppress the generation of cracks and voids.

[0354] The dispersion (Mw / Mn) of component (Z) is not particularly limited, but is preferably 1.0 to 7.0, more preferably 2.0 to 6.0, and particularly preferably 3.0 to 6.0. It should be noted that Mn represents the number-average molecular weight.

[0355] In the resist composition involved in the embodiments of the present invention, component (Z) can be used alone or in combination with two or more components.

[0356] In the resist composition according to the embodiments of the present invention, the content of the aforementioned plasticizer component (Z) is 20 parts by mass or less relative to 100 parts by mass of resin component (A1).

[0357] In the resist composition according to embodiments of the present invention, the content of component (Z) is preferably 20 parts by mass or less relative to 100 parts by mass of the resin component (A1) in the resist composition. If the content of component (Z) is greater than 20 parts by mass, although the generation of cracks and voids can be suppressed, the resolution will decrease. On the other hand, the content of plasticizer component (Z) is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the resin component (A1). By making the content of component (Z) 0.05 parts by mass or more, the generation of cracks and voids can be easily suppressed. For example, the content of component (Z) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the resin component (A1) in the resist composition.

[0358] <Other Ingredients>

[0359] In addition to components (A) and (Z) described above, the resist composition according to embodiments of the present invention may further contain other components. Examples of such other components include components (B), (D), (E), (F), and (S) shown below.

[0360] Acid-generating component (B)

[0361] In addition to components (A) and (Z), the resist composition according to the embodiments of the present invention also contains an acid-generating component (B) (hereinafter referred to as "component (B)") that is capable of generating acid through exposure.

[0362] As for component (B), there are no particular limitations, and any component that has been proposed up to date as an acid-generating agent for chemically amplified resist compositions may be used.

[0363] Examples of such acid-producing agents include onium salt-based acid-producing agents such as iodonium salts and sulfonium salts; oxime sulfonate-based acid-producing agents; diazomethane-based acid-producing agents such as dialkyl or diarylsulfonyl diazomethanes and poly(disulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid-producing agents; iminosulfonate-based acid-producing agents; and disulfone-based acid-producing agents.

[0364] As component (B), it preferably contains an ionic compound, and more preferably contains a compound (B1) formed from an onium salt (hereinafter referred to as "(B1) component").

[0365] Regarding ingredient (B1)

[0366] As a component (B1), for example, compounds represented by the general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by the general formula (b-2) (hereinafter also referred to as "(b-2) component") or compounds represented by the general formula (b-3) (hereinafter also referred to as "(b-3) component") can be cited.

[0367] [Chemical Formula 26]

[0368]

[0369] [In the formula, R] 101 and R 104 ~R 108 Each can be independently 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 104 With R 105 They can bond together to form a ring structure. R 102 It is a fluoroalkyl group or 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 is independently a single bond, alkylene, or fluoroalkylene. L 101 ~L 102 Each is an independent single bond or oxygen atom. L 103 ~L 105 Each is independently a single bond, -CO-, or -SO2-. m is an integer greater than or equal to 1, M' m + It is an m-valent ononium cation.

[0370] {Anion Section}

[0371] Anions in component (b-1)

[0372] In equation (b-1), 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.

[0373] Cyclic groups that may have substituents:

[0374] The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0375] R 101The 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, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0376] As R 101 The aromatic rings contained in aromatic hydrocarbon groups include, specifically, those of benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles obtained by replacing some carbon atoms in these aromatic rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0377] As R 101 The aromatic hydrocarbon group in the aromatic ring can be specifically exemplified by groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups). The aforementioned alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0378] R 101 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain rings in their structure.

[0379] Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups with an alicyclic hydrocarbon group located in the middle of a straight-chain or branched aliphatic hydrocarbon group.

[0380] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0381] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a 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, it is preferably a monocyclic alkane with 3 to 6 carbon atoms; specifically, cyclopentane, cyclohexane, etc., are examples. 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, it is preferably a polycyclic alkane with 7 to 30 carbon atoms. More preferably, it is a polycyclic alkane with a bridging ring system, such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycyclic alkane with a condensed ring system, such as a cyclic group with a steroidal skeleton.

[0382] Among them, as R 101 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 a 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.

[0383] The linear aliphatic hydrocarbon group that can bond with an alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As a linear aliphatic hydrocarbon group, a linear alkylene group is preferred; specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0384] 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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene 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.

[0385] Additionally, R 101 The cyclic hydrocarbon group in the formula can contain heteroatoms, such as heterocycles. Specifically, examples include the cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), and the heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0386] [Chemical Formula 27]

[0387]

[0388] As R 101 Substituents in the cyclic group, for example, include alkyl, alkoxy, halogen atom, haloalkyl, hydroxy, carbonyl, nitro, etc.

[0389] Regarding the alkyl group used as a substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0390] Regarding the alkoxy group as a substituent, it is preferred to be 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.

[0391] Regarding halogen atoms used as substituents, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred choice.

[0392] Regarding alkyl halogens as substituents, examples include alkyl groups with 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 aforementioned halogen atoms.

[0393] The carbonyl group, as a substituent, is a group that substitutes the methylene (-CH2-) group that constitutes the cyclic hydrocarbon group.

[0394] Alkyl groups that may have substituents:

[0395] As R 101 The alkyl group can be either straight-chain or branched. As a straight-chain alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. 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, and dodecyl.

[0396] 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, 4-methylpentyl, etc.

[0397] Alkenyl groups that may have substituents in a chain-like structure:

[0398] As R 101The chain-like alkenyl group can be of any shape, either straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0399] Of the above, the alkenyl group is preferably a linear alkenyl group, more preferably a vinyl or propenyl group, and particularly preferably a vinyl group.

[0400] As R 101 Substituents in the chain-like alkyl or alkenyl group, for example, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, and the above R 101 Cyclic groups, etc.

[0401] Of the above, R 101 Preferably, it is a cyclic group that can have substituents, and more preferably a cyclic hydrocarbon group that can have substituents. More specifically, it is preferably a group obtained by removing one or more hydrogen atoms from phenyl, naphthyl, or polycyclic alkanes; a cyclic group containing a lactone represented by each of the aforementioned general formulas (a2-r-1) to (a2-r-7); or a cyclic group containing -SO2- represented by each of the aforementioned general formulas (a5-r-1) to (a5-r-4).

[0402] In equation (b-1), Y 101 It is a single bond or a divalent linker containing an oxygen atom.

[0403] In Y 101 In the case where the Y is a divalent linking group containing an oxygen atom, 101 It can also contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.

[0404] Examples of non-hydrocarbon-based linking groups containing oxygen atoms include oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-OC(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-OC(=O)-O-); combinations of these non-hydrocarbon-based linking groups containing oxygen atoms with alkylene groups. A sulfonyl group (-SO2-) may also be further linked in this combination. Examples of such non-hydrocarbon-based linking groups containing oxygen atoms include the linking groups represented by the following general formulas (y-al-1) to (y-al-7).

[0405] [Chemical Formula 28]

[0406]

[0407] [In the formula, V'] 101 It is a single bond or an alkylene group having 1 to 5 carbon atoms, V' 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0408] V' 102 The divalent saturated hydrocarbon group is preferably an alkylene group with 1 to 30 carbon atoms, more preferably an alkylene group with 1 to 10 carbon atoms, and even more preferably an alkylene group with 1 to 5 carbon atoms.

[0409] As V' 101 and V' 102 The alkylene groups in the form can be straight-chain alkylene groups or branched alkylene groups, with straight-chain alkylene groups being preferred.

[0410] As V' 101 and V' 102 Specifically, examples of alkylene groups include methylene [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; ethylene [-CH2CH2-]; and alkylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3). CH2- and other alkyl-ethylenes; 1,3-propylene (n-propylene) [-CH2CH2CH2-]; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and other alkyl-1,3-propylenes; 1,4-butylene [-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkyl-1,4-butylenes; 1,5-pentylene [-CH2CH2CH2CH2CH2-], etc.

[0411] Additionally, V' 101 or V' 102 In the aforementioned alkylene group, a portion of the methylene group can be replaced with a divalent aliphatic cyclic group having 3 to 12 carbon atoms. This aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group).

[0412] The cyclic aliphatic hydrocarbon group can be a polycyclic group or a monocyclic group.

[0413] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0414] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be 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. Specifically, examples include adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0415] The cyclic aliphatic hydrocarbon group may have substituents. Examples of such substituents include Ra as described above. 05 The same group.

[0416] As a divalent aliphatic cyclic group, it is more preferably cyclohexylene, 1,5-adamantylene, or 2,6-adamantylene.

[0417] As Y 101 Preferably, it is a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, and more preferably, it is a linking group represented by each of the above formulas (y-al-1) to (y-al-5).

[0418] In equation (b-1), V 101 It is a single bond, an alkylene group, or a fluoroalkylene group. V 101 The alkylene and fluoroalkylene groups preferably have 1 to 4 carbon atoms. As V 101 Fluorinated alkylene groups, such as V, can be cited as examples. 101 A group obtained by replacing some or all of the hydrogen atoms of the alkylene group with fluorine atoms. Wherein, V 101 Preferably, it is a single bond or a straight-chain fluoroalkylene group having 1 to 4 carbon atoms.

[0419] In equation (b-1), R 102 It is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R 102 Preferably, it is a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0420] As a specific example of the anion portion 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 and perfluorobutane sulfonate anion; in Y 101 In the case of a divalent linker containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) can be cited.

[0421] [Chemical Formula 29]

[0422]

[0423] [In the formula, R”] 101 It can be an aliphatic cyclic group that may have substituents, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-16), or a chain-like alkyl group that may have substituents. R” 102 This can be an aliphatic cyclic group that may have substituents, a cyclic group containing a lactone represented by each of the aforementioned general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or a cyclic group containing -SO2- represented by each of the aforementioned 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.

[0424] R” 101 、R” 102 and R” 103 The aliphatic cyclic group that may have substituents is preferably R in the aforementioned formula (b-1). 101 Examples of substituents include cyclic aliphatic hydrocarbon groups. Examples of substituents include those that can be used with respect to R in the aforementioned formula (b-1). 101 The same substituents replace the cyclic aliphatic hydrocarbon groups in the same way.

[0425] R” 103 The aromatic cyclic group that may have substituents is preferably R in the aforementioned formula (b-1). 101 Examples of substituents include aromatic hydrocarbon groups in cyclic hydrocarbon groups. Examples of substituents include those that can be used with respect to R in the aforementioned formula (b-1). 101 The aromatic hydrocarbon group in the same substituent is substituted by the same substituent.

[0426] R” 101 The alkyl group that may have substituents is preferably R in the aforementioned formula (b-1). 101 The chain-like alkyl group is exemplified by the group.

[0427] R” 103 The chain-like alkenyl group that may have substituents is preferably R in the aforementioned formula (b-1). 101 The chain-like alkenyl group is exemplified by the group.

[0428] Anions in component (b-2)

[0429] In equation (b-2), R 104 R 105 Each can be independently 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, and examples of R in formula (b-1) can be given respectively. 101 The same group. Among them, R... 104 R 105 They can bond together to form a ring.

[0430] R 104 R 105 Preferably, it is a chain alkyl group that may have substituents, more preferably a straight-chain or branched alkyl group, or a straight-chain or branched fluoroalkyl group.

[0431] The chain-like alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms. Due to its good solubility in resist solvents, etc., R 104 R 105 The fewer carbon atoms in the chain-like alkyl group within the aforementioned range, the better. Additionally, R... 104 R 105 In a chain-like alkyl group, the more hydrogen atoms replaced by fluorine atoms, the stronger the acid. Furthermore, it offers improved transparency for high-energy light and electron beams below 250 nm, making it a preferred choice. The proportion of fluorine atoms in the aforementioned chain-like alkyl group, i.e., the fluorination rate, is preferably 70-100%, more preferably 90-100%, and most preferably a perfluoroalkyl group obtained where all hydrogen atoms are replaced by fluorine atoms.

[0432] In equation (b-2), V 102 V 103 Each is independently a single bond, an alkylene group, or a fluoroalkylene group, and examples of V in formula (b-1) can be given. 101 The same group.

[0433] In equation (b-2), L 101 L 102 Each is an independent single bond or oxygen atom.

[0434] Anions in component (b-3)

[0435] In equation (b-3), R 106 ~R 108 Each can be independently 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, and examples of R in formula (b-1) can be given respectively.101 The same group.

[0436] In equation (b-3), L 103 ~L 105 Each can be a single bond, -CO-, or -SO2-.

[0437] Of the above, the anionic portion of component (B) is preferably the anion of component (b-1). More preferably, it is a fluoroalkyl sulfonate anion or an anion represented by any 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 of the general formulas (an-1) and (an-2).

[0438] {Cation Section}

[0439] In the aforementioned 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.

[0440] m is an integer greater than or equal to 1.

[0441] As a preferred cation portion ((M') m + ) 1 / m Examples of organic cations represented by the general formulas (ca-1) to (ca-3) can be cited below.

[0442] [Chemical Formula 30]

[0443]

[0444] [In the formula, R] 201 ~R 207 Each can independently represent an aryl, alkyl, or alkenyl group that may have substituents. R 201 ~R 203 R 206 ~R 207 They can bond with each other and form a ring together with the sulfur atoms in the formula. R 208 ~R 209 Each can independently represent an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. 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 cyclic group containing -SO2- that may have a substituent. L 201 This represents -C(=O)- or -C(=O)-O-.

[0445] In the above general formulas (ca-1) to (ca-3), R is... 201 ~R 207The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0446] As R 201 ~R 207 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0447] As R 201 ~R 207 The alkenyl group in the form of carbon atoms preferably has a carbon number of 2 to 10.

[0448] As R 201 ~R 207 The substituents that may be present include, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, aryl, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0449] [Chemical Formula 31]

[0450]

[0451] [In the formula, R'] 201 Each group can be an independent hydrogen atom, 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.

[0452] Cyclic groups that may have substituents:

[0453] The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0454] 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.

[0455] As R' 201 The aromatic rings contained in aromatic hydrocarbon groups include, specifically, those of benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles obtained by replacing some carbon atoms in these aromatic rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0456] As R' 201The aromatic hydrocarbon group in the aromatic ring can be specifically categorized as a group obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), or a group obtained by substituting one hydrogen atom of the aforementioned aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups). The aforementioned 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.

[0457] R' 201 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain rings in their structure.

[0458] Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups with an alicyclic hydrocarbon group located in the middle of a straight-chain or branched aliphatic hydrocarbon group.

[0459] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 12.

[0460] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a 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, it is preferably a monocyclic alkane with 3 to 6 carbon atoms; specifically, cyclopentane, cyclohexane, etc., are examples. 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, it is preferably a polycyclic alkane with 7 to 30 carbon atoms. More preferably, it is a polycyclic alkane with a bridging ring system, such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycyclic alkane with a condensed ring system, such as a cyclic group with a steroidal skeleton.

[0461] 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 a 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.

[0462] The aliphatic hydrocarbon group that can bond with the alicyclic hydrocarbon group, whether straight-chain or branched, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0463] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0464] 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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene 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.

[0465] Additionally, R' 201 The cyclic hydrocarbon group in the formula can contain heteroatoms, such as heterocycles. Specifically, examples include the cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the aforementioned chemical formulas (r-hr-1) to (r-hr-16).

[0466] As R' 201 Substituents in the cyclic group, for example, include alkyl, alkoxy, halogen atom, haloalkyl, hydroxy, carbonyl, nitro, etc.

[0467] Regarding the alkyl group used as a substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0468] Regarding the alkoxy group as a substituent, it is preferred to be 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.

[0469] Regarding halogen atoms used as substituents, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred choice.

[0470] Regarding alkyl halogens as substituents, examples include alkyl groups with 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 aforementioned halogen atoms.

[0471] The carbonyl group, as a substituent, is a group that substitutes the methylene (-CH2-) group that constitutes the cyclic hydrocarbon group.

[0472] Alkyl groups that may have substituents:

[0473] As R' 201 The alkyl group is a chain, which can be either straight-chain or branched.

[0474] As a straight-chain alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. 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, and dodecyl.

[0475] 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.

[0476] Alkenyl groups that may have substituents in a chain-like structure:

[0477] As R' 201 The chain-like alkenyl group can be of any shape, either straight-chain or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of straight-chain alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0478] Of the above, the alkenyl group is preferably a linear alkenyl group, more preferably a vinyl or propenyl group, and particularly preferably a vinyl group.

[0479] As R' 201Substituents in the chain-like alkyl or alkenyl group, for example, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, and the above R' 201 Cyclic groups, etc.

[0480] Regarding R' 201 In addition to the groups described above, other groups that are the same as the acid-dissociable groups represented by the above formula (a1-r-1) can also be cited as cyclic groups or alkyl groups that may have substituents.

[0481] Among them, R' 201 Preferably, it is a cyclic group that may have substituents, and more preferably a cyclic hydrocarbon group that may have substituents. More specifically, for example, it is preferably a group obtained by removing one or more hydrogen atoms from phenyl, naphthyl, or polycyclic alkanes; a cyclic group containing a lactone represented by each of the aforementioned general formulas (a2-r-1) to (a2-r-7); a cyclic group containing -SO2- represented by each of the aforementioned general formulas (a5-r-1) to (a5-r-4), etc.

[0482] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 R 206 ~R 207 When they bond together and form a ring with the sulfur atom in the formula, they can be intermediates such as sulfur atoms, oxygen atoms, nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) N )-(the R N The ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. The ring skeleton containing the sulfur atom in the formula is preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-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, phenoxathia rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0483] R 208 ~R 209 Each alkyl group 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 the case of alkyl groups, they can bond together to form a ring.

[0484] 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 cyclic group containing -SO2- that may have a substituent.

[0485] As R 210 The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0486] As R 210 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0487] As R 210 The alkenyl group in the form of carbon atoms preferably has a carbon number of 2 to 10.

[0488] As R 210 The cyclic group containing -SO2- may have substituents, preferably a "polycyclic group containing -SO2-", and more preferably a group represented by the above general formula (a5-r-1).

[0489] As preferred cations represented by the aforementioned formula (ca-1), examples include the cations represented by the following chemical formulas (ca-1-1) to (ca-1-68).

[0490] [Chemical Formula 32]

[0491]

[0492] [Chemical Formula 33]

[0493]

[0494] [Chemical Formula 34]

[0495]

[0496] [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0497] [Chemical Formula 35]

[0498]

[0499] [Chemical Formula 36]

[0500]

[0501] [Chemical Formula 37]

[0502]

[0503] [In the formula, R”] 201 It is a hydrogen atom or a substituent, which, as the substituent, is related to the aforementioned R. 201 ~R 207The same applies to substituents that can be present.

[0504] Preferred cations represented by the aforementioned formula (ca-2) include, specifically, diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.

[0505] As preferred cations represented by the aforementioned formula (ca-3), examples include the cations represented by each of the following formulas (ca-3-1) to (ca-3-6).

[0506] [Chemical Formula 38]

[0507]

[0508] Of the above, the cation portion ((M') m + ) 1 / m The cation is preferably a cation represented by the general formula (ca-1). As a cation represented by the general formula (ca-1), it is preferably a cation represented by any of the above formulas (ca-1-1) to (ca-1-54), and more preferably a cation represented by any of the above formulas (ca-1-1) to (ca-1-15).

[0509] Regarding ingredient (B2)

[0510] (B) Component may contain an acid-generating agent that is not part of Component (B1) above (hereinafter referred to as "Component (B2)"). Component (B2) is not particularly limited as long as it can generate acid through exposure and is not part of Component (B1) above, and can be arbitrarily selected from known components. Examples of Component (B2) include, for example, oxime sulfonate acid-generating agents; dialkyl or diarylsulfonyl diazomethanes, poly(disulfonyl)diazomethanes, and other diazomethane acid-generating agents; nitrobenzyl sulfonate acid-generating agents, iminosulfonate acid-generating agents, disulfone acid-generating agents, and many other components.

[0511] In the resist composition involved in the embodiments of the present invention, component (B) can be used alone or in combination with two or more components.

[0512] In the resist composition according to the embodiments of the present invention, the content of component (B) is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass.

[0513] By ensuring that the content of component (B) is within the aforementioned preferred range, sufficient pattern formation can be achieved. Furthermore, when the components of the resist composition are dissolved in an organic solvent, a homogeneous solution is readily obtained, resulting in good storage stability of the resist composition, which is therefore preferred.

[0514] Alkali Components (D)

[0515] In addition to components (A), (B), and (Z), the resist composition according to embodiments of the present invention may also contain an alkaline component ((D) component) that traps acid generated by exposure (i.e., controls acid diffusion). Component (D) is a component that functions in the resist composition as a quencher (acid diffusion control agent) for trapping acid generated by exposure.

[0516] Examples of (D) components include, for example, photodisintegrating bases (D1) that decompose upon exposure and lose their acid diffusion control (hereinafter referred to as "(D1) component"), and nitrogen-containing organic compounds (D2) that do not belong to the (D1) component (hereinafter referred to as "(D2) component"). Among these, from the viewpoint of resolution, photodisintegrating bases (D1) ((D1) component) are preferred.

[0517] Regarding component (D1)

[0518] By preparing a resist composition containing (D1), the contrast between the exposed and unexposed areas of the resist film can be further improved during the formation of resist patterns, thereby increasing the resolution.

[0519] As component (D1), there is no particular limitation as long as it is a component that decomposes and loses its acid diffusion control by exposure, but preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), compounds represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component") and compounds represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component").

[0520] The components (d1-1) to (d1-3) do not function as quenchers in the exposed portion of the resist film due to decomposition and loss of acid diffusion control (alkalinity), but function as quenchers in the unexposed portion of the resist film.

[0521] [Chemical Formula 39]

[0522]

[0523] [In the formula, Rd] 1 ~Rd 4 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. Wherein, Rd in formula (d1-2) 2 There are no bonded fluorine atoms on the carbon atom adjacent to the S atom in Yd. 1It is a single bond or a divalent linker. m is an integer greater than or equal to 1, M m+ Each is an organic cation with an independent valence of m.

[0524] {(d1-1)Component}

[0525] Anion section

[0526] In equation (d1-1), Rd 1 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, respectively, examples of which are related to the aforementioned R'. 201 The same group.

[0527] Among them, as Rd 1 Preferably, the substituent is an aromatic hydrocarbon group, an aliphatic cyclic group, or a chain alkyl group. Examples of substituents that may be present in these groups include hydroxyl, oxo, alkyl, aryl, fluorine, fluoroalkyl, cyclic groups containing lactones represented by each of the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. In cases where ether bonds or ester bonds are included as substituents, alkylene groups may also be inserted; in this case, the linking group represented by each of the above formulas (y-al-1) to (y-al-5) is preferred.

[0528] As the aforementioned aromatic hydrocarbon group, phenyl, naphthyl, and polycyclic structures containing a bicyclooctane skeleton (polycyclic structures formed by a bicyclooctane skeleton and other ring structures) are preferred examples.

[0529] More preferably, the aliphatic cyclic group is a group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0530] As for the aforementioned chain-like alkyl group, it is preferred that the number of carbon atoms is 1 to 10. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0531] When the aforementioned chain-like alkyl group is a fluoroalkyl group having fluorine atoms or fluoroalkyl groups as substituents, the number of carbon atoms in the fluoroalkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluoroalkyl group may also contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0532] As Rd 1 Preferably, it is a fluoroalkyl group obtained by replacing some or all of the hydrogen atoms of the linear alkyl group with fluorine atoms, and particularly preferably a fluoroalkyl group (linear perfluoroalkyl group) obtained by replacing all the hydrogen atoms of the linear alkyl group with fluorine atoms.

[0533] The following shows a preferred example of the anionic portion of component (d1-1).

[0534] [Chemical Formula 40]

[0535]

[0536] • Cation section

[0537] In equation (d1-1), M m+ It is an organic cation with an m valence.

[0538] As M m+ The organic cations are preferably the same as those represented by the aforementioned general formulas (ca-1) to (ca-3), more preferably the cations represented by the aforementioned general formula (ca-1), and even more preferably the cations represented by the aforementioned formulas (ca-1-1) to (ca-1-68).

[0539] (d1-1) Components can be used alone or in combination of two or more.

[0540] {(d1-2)Component}

[0541] Anion section

[0542] In equation (d1-2), Rd 2 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; examples include those related to the aforementioned R'. 201 The same group.

[0543] Among them, in Rd 2 The carbon atom adjacent to the S atom in the (d1-2) component has no bonded fluorine atom (it is not substituted by fluorine). Therefore, the anion of the (d1-2) component becomes a moderately weak acid anion, which enhances its quenching ability as a (D) component.

[0544] As Rd 2Preferably, it is a chain-like alkyl group that may have substituents, or an aliphatic cyclic group that may have substituents. As a chain-like alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 3 to 10. As an aliphatic cyclic group, it is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents); or a group obtained by removing one or more hydrogen atoms from camphor, etc.

[0545] Rd 2 The hydrocarbon group can also have substituents, and examples of such substituents include Rd in the aforementioned formula (d1-1). 1 The hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) can have the same substituents as the hydrocarbon group.

[0546] The following shows a preferred example of the anionic portion of component (d1-2).

[0547] [Chemical Formula 41]

[0548]

[0549] • Cation section

[0550] In equation (d1-2), M m+ An organic cation with a valence of m, and M in the aforementioned formula (d1-1) m+ same.

[0551] (d1-2) Components can be used alone or in combination of two or more.

[0552] {(d1-3)Component}

[0553] Anion section

[0554] In equation (d1-3), Rd 3 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; examples include those related to the aforementioned R'. 201 The same group is preferably a cyclic group containing a fluorine atom, a chain-like alkyl group, or a chain-like alkenyl group. Fluorinated alkyl groups are preferred, and more preferably those similar to the aforementioned Rd. 1 The same fluoroalkyl group.

[0555] In equation (d1-3), Rd 4 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; examples include those related to the aforementioned R'. 201 The same group.

[0556] Preferably, the groups are alkyl, alkoxy, alkenyl, or cyclic groups that may have substituents.

[0557] Rd 4 The alkyl group 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, and neopentyl. 4 Some of the hydrogen atoms in an alkyl group can be replaced by hydroxyl, cyano, etc.

[0558] Rd 4 The alkoxy group is preferably an alkoxy group with 1 to 5 carbon atoms. Specifically, examples of alkoxy groups with 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy. Among these, methoxy and ethoxy are preferred.

[0559] Rd 4 Examples of alkenyl groups in R' are those mentioned above. 201 The alkenyl group in the group is the same as that in the group, preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may also have alkyl groups with 1 to 5 carbon atoms or haloalkyl groups with 1 to 5 carbon atoms as substituents.

[0560] Rd 4 Examples of cyclic groups in R' are those mentioned above. 201 The cyclic group in Rd is the same as the cyclic group, 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. 4 When the resist group is alicyclic, the resist composition dissolves well in organic solvents, thereby improving photolithography properties. Furthermore, in Rd... 4 When the resist group is aromatic, the resist composition exhibits excellent light absorption efficiency and improved sensitivity and lithographic properties in photolithography using EUV or similar light sources.

[0561] In equation (d1-3), Yd 1 It is a single bond or a divalent linker.

[0562] As Yd 1 The divalent linking group in the formula (a2-1) is not particularly limited and can include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that may have substituents, divalent linking groups containing heteroatoms, etc. Examples of such groups include those related to Ya in the above formula (a2-1). 21 The description of the divalent linking group in the text lists divalent hydrocarbon groups that may have substituents, divalent linking groups that contain heteroatoms, and the same groups.

[0563] 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.

[0564] The following shows a preferred example of the anionic portion of the (d1-3) component.

[0565] [Chemical Formula 42]

[0566]

[0567] [Chemical Formula 43]

[0568]

[0569] • Cation section

[0570] In equation (d1-3), M m+ An organic cation with a valence of m, and M in the aforementioned formula (d1-1) m+ same.

[0571] (d1-3) Components can be used alone or in combination of two or more.

[0572] (D1) Component can be any one of the above components (d1-1) to (d1-3), or it can be a combination of two or more.

[0573] When the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.05 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 0.1 to 10 parts by mass, and even more preferably 0.2 to 5 parts by mass.

[0574] If the content of component (D1) is above the preferred lower limit, it is easy to obtain particularly good photolithography properties and resist pattern shape. On the other hand, if it is below the upper limit, sensitivity can be well maintained and throughput is also excellent.

[0575] (D1) Manufacturing method:

[0576] The manufacturing methods for the aforementioned (d1-1) and (d1-2) components are not particularly limited and can be manufactured using known methods.

[0577] Furthermore, there are no particular limitations on the manufacturing method of components (d1-3). For example, they can be manufactured by operating in the same manner as the method described in US 2012-0149916.

[0578] Regarding component (D2)

[0579] As component (D), it is preferable to contain a nitrogen-containing organic compound component that does not belong to component (D1) above (hereinafter referred to as "component (D2)").

[0580] As for component (D2), there are no particular limitations as long as it functions as an acid diffusion control agent and is not part of component (D1), and it can be selected from known components. Among them, aliphatic amines are preferred, and aliphatic secondary amines and aliphatic tertiary amines are particularly preferred.

[0581] Aliphatic amines are amines having one or more aliphatic groups, preferably with 1 to 12 carbon atoms in the aliphatic group.

[0582] Examples of aliphatic amines include amines (alkylamines or alkylolamines) obtained by replacing at least one hydrogen atom of ammonia (NH3) with an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms, or cyclic amines.

[0583] Specific examples of alkylamines and alkylolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octylamine, and tri-octylamine. Among these, trialkylamines having 5 to 10 carbon atoms are further preferred, and tri-n-pentylamine or tri-octylamine are particularly preferred.

[0584] Examples of cyclic amines include, for instance, heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds can be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines).

[0585] Examples of aliphatic monocyclic amines include piperidine and piperazine.

[0586] As an aliphatic polycyclic amine, it is preferred to be an aliphatic polycyclic amine with 6 to 10 carbon atoms. Specifically, examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0587] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tri{2-(2-methoxyethoxy)ethyl}amine, tri{2-(2-methoxyethoxymethoxy)ethyl}amine, tri{2-(1-methoxyethoxy)ethyl}amine, tri{2-(1-ethoxyethoxy)ethyl}amine, tri{2-(1-ethoxypropoxy)ethyl}amine, tri[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0588] In addition, aromatic amines can also be used as (D2) components.

[0589] Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, etc.

[0590] From the viewpoint of acid diffusion control (basicity), aliphatic amines are preferred as the (D2) component, more preferably chain-like aliphatic amines, and even more preferably chain-like alkylamines. The chain-like alkylamines preferably have 5 to 10 carbon atoms in their chain-like alkyl groups. Among these, dialkylamines or trialkylamines having straight-chain alkyl groups with 5 to 10 carbon atoms are preferred, and trialkylamines are more preferably preferred.

[0591] (D2) Components can be used alone or in combination of two or more.

[0592] When the resist composition contains component (D2), the content of component (D2) in the resist composition is generally used in the range of 0.005 to 5 parts by mass relative to 100 parts by mass of component (A). By setting it to the above range, the resist pattern shape, stability over time, etc., are improved.

[0593] Choose at least one compound (E) from the group consisting of organic carboxylic acids and oxyacids of phosphorus and their derivatives.

[0594] In the resist composition according to the embodiments of the present invention, for the purpose of preventing sensitivity degradation, improving the resist pattern shape, and improving stability over time, at least one compound (E) selected from the group consisting of organic carboxylic acids and oxyacids of phosphorus and their derivatives (hereinafter referred to as "(E) component") may be included as an optional component.

[0595] As organic carboxylic acids, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are preferred.

[0596] Examples of oxyacids containing phosphorus include phosphoric acid, phosphonic acid, and hypophosphonic acid, among which phosphonic acid is particularly preferred.

[0597] As derivatives of phosphorus-containing oxyacids, examples include esters obtained by replacing the hydrogen atoms of the aforementioned oxyacids with hydrocarbon groups, and examples of the aforementioned hydrocarbon groups include alkyl groups with 1 to 5 carbon atoms and aryl groups with 6 to 15 carbon atoms.

[0598] Examples of phosphoric acid derivatives include dibutyl phosphate, diphenyl phosphate, and other phosphate esters.

[0599] Examples of phosphonic acid derivatives include dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and other phosphonate esters.

[0600] Examples of derivatives of hypophosphonic acid include hypophosphonate esters and phenylhydatilic acid.

[0601] In the resist composition involved in the embodiments of the present invention, component (E) can be used alone or in combination with two or more components.

[0602] When the resist composition contains component (E), the content of component (E) is generally used in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A).

[0603] Fluorine Additives (F)

[0604] The resist composition in this embodiment may also contain a fluorinated additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. Component (F) is used to impart water resistance to the resist film, thereby improving photolithography properties by being used as a resin different from component (A).

[0605] As component (F), for example, fluorine-containing polymers described in Japanese Patent Application Publication Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 may be used.

[0606] More specifically, as component (F), a polymer having a structural unit (f1) represented by the following general formula (f1-1) can be cited. Preferably, such a polymer (homopolymer) is formed solely from the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) with the aforementioned structural unit (a1); or a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the aforementioned structural unit (a1). Here, the aforementioned structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl methacrylate or a structural unit derived from 1-methyl-1-adamantyl methacrylate.

[0607] [Chemical Formula 44]

[0608]

[0609] [In the formula, R is the same as before, Rf] 102 and Rf 103 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms, Rf 102 and Rf 103 They can be the same or different. nf 1 Rf is an integer from 1 to 5. 101 [This refers to an organic group containing a fluorine atom.]

[0610] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. R is preferably a hydrogen atom or a methyl group.

[0611] In equation (f1-1), Rf 102 and Rf 103 Halogen atoms can be fluorine, chlorine, bromine, iodine, etc., with fluorine atoms being particularly preferred. As Rf 102 and Rf 103 The alkyl group having 1 to 5 carbon atoms can be exemplified by alkyl groups having the same 1 to 5 carbon atoms as the alkyl group R described above, and is preferably methyl or ethyl. As Rf 102 and Rf 103 The alkyl group having 1 to 5 carbon atoms is specifically a group obtained by substituting some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms, with fluorine being particularly preferred. Among these, Rf... 102 and Rf 103 Preferably, it is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom, a fluorine atom, a methyl atom, or an ethyl atom.

[0612] In equation (f1-1), nf 1 It is an integer from 1 to 5, preferably an integer from 1 to 3, and more preferably 1 or 2.

[0613] In equation (f1-1), Rf 101 It is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom.

[0614] The hydrocarbon group containing fluorine atoms can be any of the following: straight-chain, branched, or cyclic. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10.

[0615] Furthermore, regarding the hydrocarbon group containing fluorine atoms, it is preferable that more than 25% of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably more than 50%, and from the perspective of improving the hydrophobicity of the resist film during immersion exposure, it is particularly preferable that more than 60% are fluorinated.

[0616] Among them, as Rf 101 More preferably, it is a fluoroalkyl group with 1 to 6 carbon atoms, and particularly preferably trifluoromethyl, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF3.

[0617] The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion using gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in solvents for use as a resist; if it is above the lower limit of this range, the resist film has good water resistance.

[0618] The dispersion (Mw / Mn) of component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0619] In the resist composition involved in the embodiments of the present invention, component (F) can be used alone or in combination with two or more components.

[0620] When the resist composition contains component (F), the content of component (F) is usually used in a ratio of 0.5 to 10 parts by mass relative to 100 parts by mass of component (A).

[0621] Organic Solvent Components (S)

[0622] The resist composition according to the embodiments of the present invention can be manufactured by dissolving the resist material in an organic solvent component (hereinafter referred to as "(S) component").

[0623] In the resist composition according to the embodiments of the present invention, component (S) can be used alone or in the form of a mixture of two or more solvents. Preferably, it is PGMEA, PGME, γ-butyrolactone, EL, or cyclohexanone.

[0624] Furthermore, as component (S), a mixed solvent prepared by mixing PGMEA with a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined taking into account factors such as the compatibility of PGMEA with the polar solvent.

[0625] As component (S), at least one of the solvents selected from PGMEA and EL, mixed with γ-butyrolactone, is also preferred. In this case, the mass ratio of the former to the latter is preferably set to 70:30 to 95:5.

[0626] The amount of component (S) used is not particularly limited, and can be appropriately set to a concentration that allows it to be coated onto a substrate or the like, depending on the thickness of the coating film. Component (S) is usually used in a concentration of solid components in the resist composition within the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0627] In the resist composition according to embodiments of the present invention, additives having miscibility may be added as desired, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halo agents, dyes, etc.

[0628] Regarding the resist composition according to embodiments of the present invention, after dissolving the aforementioned resist material in component (S), impurities can be removed using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition can be filtered using a filter formed of a polyimide porous membrane, a filter formed of a polyamide-imide porous membrane, or a filter formed of both a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the aforementioned polyimide porous membrane and polyamide-imide porous membrane include, for instance, the porous membrane described in Japanese Patent Application Publication No. 2016-155121.

[0629] The resist composition described above in the embodiments of the present invention contains a plasticizer component (Z) of 20 parts by mass or less relative to 100 parts by mass of the resin component (A1).

[0630] Since the resist composition according to the embodiments of the present invention contains a plasticizer component (Z), it is able to suppress the formation of cracks and voids. In addition, since the content of the aforementioned plasticizer component (Z) is 20 parts by mass or less, it is able to maintain the resolution well and suppress the formation of cracks and voids.

[0631] By including a plasticizer component (Z) in the resist composition according to embodiments of the present invention, both crack resistance and suppression of void formation can be achieved. This is presumably because the presence of the plasticizer component (Z) in the resist film formed using the aforementioned resist composition can alleviate stress in the resist film.

[0632] Furthermore, regarding the resist composition according to the embodiments of the present invention, since the substrate component (A) has structural units (a1) and (a2), it not only has the effect of crack resistance and suppression of void formation, but also improves sensitivity and resolution.

[0633] (Resist Pattern Formation Method)

[0634] The second aspect of the present invention relates to a resist pattern forming method comprising the following steps: a step of forming a resist film on a support using the resist composition of the above embodiment; a step of exposing the aforementioned resist film; and a step of developing the exposed resist film to form a resist pattern.

[0635] As one embodiment of such a resist pattern forming method, a resist pattern forming method as follows can be cited as an example.

[0636] First, the resist composition of the above embodiment is applied to the support using a spin coater or the like, and then baked (PAB) at a temperature of, for example, 80 to 150°C for 40 to 120 seconds (preferably 60 to 90 seconds) to form a resist film.

[0637] Next, the resist film is selectively exposed using an exposure apparatus such as an electron beam tracing apparatus or an ArF exposure apparatus, by means of exposure through a mask with a predetermined pattern (mask pattern) or by direct electron beam irradiation without the mask pattern. Then, it is baked (post-exposure baking (PEB)) at a temperature of, for example, 80 to 150°C for 40 to 120 seconds (preferably 60 to 90 seconds).

[0638] Next, the aforementioned resist film is subjected to a development process. For the development process, an alkaline developer is used in the case of an alkaline development process, and a developer containing an organic solvent (organic developer) is used in the case of a solvent development process.

[0639] After development, rinsing is preferably performed. Regarding rinsing, in the case of alkaline development, rinsing with pure water is preferred, while in the case of solvent development, rinsing with a rinsing solution containing organic solvents is preferred.

[0640] In the case of solvent development process, after the aforementioned development or rinsing treatment, a process can be performed to remove the developer or rinsing solution adhering to the pattern using a supercritical fluid.

[0641] After development or rinsing, the product is dried. Alternatively, depending on the circumstances, baking (post-baking) may be performed after the above development process.

[0642] There are no particular limitations on the support structure; conventionally known supports can be used, such as substrates for electronic components or substrates on which a prescribed wiring pattern is formed. More specifically, examples include silicon wafers, metal substrates made of copper, chromium, iron, aluminum, or glass substrates. Materials used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.

[0643] There are no particular limitations on the wavelength used in the exposure; ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, and other types of radiation can be used.

[0644] Regarding the exposure method of the resist film, it can be the usual exposure (dry exposure) in inactive gases such as air and nitrogen, or liquid immersion lithography.

[0645] Immersion exposure is an exposure method in which the resist film is filled with a solvent (immersion medium) with a refractive index greater than that of air, and the space between the lens at the bottom of the exposure device is filled before exposure (immersion exposure).

[0646] As the immersion medium, a solvent with a refractive index that is greater than that of air and less than that of the resist film to be exposed is preferred. Examples include water, fluorine-based inactive liquids, silicon-based solvents, and hydrocarbon-based solvents.

[0647] Water is preferred as the immersion medium.

[0648] Examples of alkaline developing solutions used in alkaline developing processes include 0.1 to 10% by mass aqueous solutions of tetramethylammonium hydroxide (TMAH).

[0649] The organic solvent contained in the organic developer used in the solvent development process can be any organic solvent that can dissolve component (A) (the component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents, can be cited.

[0650] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0651] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0652] In organic-based developers, known additives can be incorporated as needed. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic, nonionic fluorinated, and / or silicone surfactants can be used.

[0653] The developing process can be carried out using known developing methods, such as the following: immersing the support in the developing solution for a certain time (immersion method); using surface tension to cause the developing solution to accumulate on the surface of the support and remain stationary for a certain time (spinning immersion method); spraying the developing solution onto the surface of the support (spraying method); continuously spraying the developing solution onto a support rotating at a certain speed while scanning with a developing solution spray nozzle at a certain speed (dynamic distribution method); and so on.

[0654] The organic solvent contained in the rinsing solution used for rinsing after development in the solvent developing process can be, for example, an organic solvent that does not easily dissolve the resist pattern, among the organic solvents mentioned above that are used in the aforementioned organic-based developers. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used.

[0655] These organic solvents can be used alone or in combination of two or more. Alternatively, they can be mixed with other organic solvents mentioned above, or with water.

[0656] The rinsing treatment (washing treatment) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing treatment methods include: continuously spraying rinsing solution onto a support rotating at a certain speed (rotation coating); immersing the support in rinsing solution for a certain period of time (immersion method); spraying rinsing solution onto the surface of the support (spraying method); and so on.

[0657] The resist pattern forming method according to the embodiments of the present invention described above, since the above-described resist composition is used, can achieve high sensitivity and form resist patterns with excellent photolithographic characteristics such as resolution and roughness.

[0658] The resist compositions of the above embodiments and the various materials used in the pattern forming methods of the above embodiments (e.g., resist solvents, developers, rinsing solutions, compositions for forming antireflective films, compositions for forming surface coatings, etc.) preferably do not contain impurities such as metals, halogen-containing metal salts, acids, alkalis, sulfur-containing or phosphorus-containing components. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or their salts. The content of these impurities is preferably 200 ppb or less, more preferably 1 ppb or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free of them (below the detection limit of the measuring device).

[0659] Example

[0660] The present invention will be described in more detail below through examples, but the present invention is not limited to these examples.

[0661] <Example of manufacturing plasticizer component (Z)>

[0662] Polymers Z-1 to Z-4 were synthesized by free radical polymerization using the compounds shown in Table 1 at the molar ratios shown in Table 1.

[0663] Regarding the obtained polymers Z-1 to Z-4, we will utilize... 13 The copolymer composition ratio (the proportion of each structural unit in the polymer compound (molar ratio)) determined by C-NMR, the mass-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) converted to standard polystyrene by GPC determination are recorded in Table 1.

[0664] [Chemical Formula 45]

[0665]

[0666] [Table 1]

[0667] Table 1

[0668]

[0669] [Preparation of the resist composition]

[0670] <Preparation of the Anti-corrosion Composition 1>

[0671] The components shown in Tables 2-4 were mixed and dissolved in a mixed solvent (S-1) of 500 parts by mass of propylene glycol monomethyl ether acetate and 333 parts by mass of propylene glycol monomethyl ether, with a solid component concentration of about 10.9 (mass%), to prepare the resist compositions of each example.

[0672] <Preparation of the Anti-corrosion Composition 2>

[0673] The components shown in Tables 2-4 were mixed and dissolved with a mixed solvent (S-2) of 320 parts by mass of propylene glycol monomethyl ether acetate and 213 parts by mass of propylene glycol monomethyl ether, with a solid component concentration of about 16.0 (mass%), respectively, to prepare the resist compositions of each example.

[0674] [Table 2]

[0675] Table 2

[0676]

[0677] [Table 3]

[0678] Table 3

[0679]

[0680] [Table 4]

[0681] Table 4

[0682]

[0683] In Tables 2-4, each abbreviation has the following meaning. The value in [] is the amount of the compound (parts by mass). The concentration of solid components is calculated by solid component concentration (mass%) = [((A) component + (B) component + (D) component + (Z) component) / ((A) component + (B) component + (D) component + (Z) component + (S) component)] × 100.

[0684] A1-1: The polymer represented by the chemical formula A1-1 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,100, and its dispersity (Mw / Mn) is 1.65. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0685] A1-2: The polymer represented by the chemical formula A1-2 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,400, and its dispersity (Mw / Mn) is 1.60. (Using...) 13The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 40 / 20.

[0686] A1-3: The polymer represented by the chemical formula A1-3 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,000, and its dispersity (Mw / Mn) is 1.62. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 30 / 50 / 20.

[0687] A1-4: The polymer represented by the chemical formula A1-4 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,200, and its dispersity (Mw / Mn) is 1.58. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 30 / 60 / 10.

[0688] A1-5: The polymer represented by the chemical formula A1-5 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 8,500, and its dispersity (Mw / Mn) is 1.78. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0689] A1-6: The polymer represented by the chemical formula A1-6 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,500, and its dispersity (Mw / Mn) is 1.65. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0690] A1-7: The polymer represented by the chemical formula A1-7 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 6,800, and its dispersity (Mw / Mn) is 1.62. (Using...) 13 The copolymer composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) obtained by C-NMR is l / m = 50 / 50.

[0691] A1-8: The following chemical formula A1-8 represents a polymer compound. The weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,100, and the dispersity (Mw / Mn) is 1.60. (Using...) 13The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0692] A1-9: The following chemical formula A1-9 represents a polymer compound. The weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 9,000, and the dispersity (Mw / Mn) is 1.70. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0693] A1-10: The polymer represented by the chemical formula A1-10 below. The weight-average molecular weight (Mw) calculated using GPC based on standard polystyrene is 8,100, and the dispersity (Mw / Mn) is 1.63. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 40 / 20.

[0694] A1-11: The polymer represented by the chemical formula A1-11 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,500, and its dispersity (Mw / Mn) is 1.65. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 40 / 20.

[0695] A2-1: The polymer represented by the chemical formula A2-1 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 8,000, and its dispersity (Mw / Mn) is 1.80. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0696] A2-2: The following chemical formula A2-2 represents a polymer compound. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 7,300, and its dispersity (Mw / Mn) is 1.62. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40 / 50 / 10.

[0697] A2-3: The polymer represented by the chemical formula A2-3 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 8,000, and its dispersity (Mw / Mn) is 1.83. (Using...)13 The copolymer composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m = 60 / 40.

[0698] A2-4: The polymer represented by the chemical formula A2-4 below. Its weight-average molecular weight (Mw), calculated using GPC and converted to standard polystyrene, is 8.000, and its dispersity (Mw / Mn) is 2.60. (Using...) 13 The copolymer composition ratio (the proportion of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n / o / p / q=26 / 34 / 12 / 18 / 7 / 3.

[0699] [Chemical Formula 46]

[0700]

[0701] [Chemical Formula 47]

[0702]

[0703] [Chemical Formula 48]

[0704]

[0705] [Chemical Formula 49]

[0706]

[0707] B-1: An acid-producing agent composed of compounds represented by the following chemical formula B-1.

[0708] B-2: An acid-producing agent composed of compounds represented by the following chemical formula B-2.

[0709] B-3: An acid-producing agent composed of compounds represented by the following chemical formula B-3.

[0710] [Chemical Formula 50]

[0711]

[0712] D-1: Nitrogen-containing organic compounds composed of compounds represented by the following chemical formula D-1.

[0713] D-2: Nitrogen-containing organic compounds composed of compounds represented by the following chemical formula D-2.

[0714] D-3: An ionic compound consisting of compounds represented by the chemical formula D-3.

[0715] [Chemical Formula 51]

[0716]

[0717] Z-1~Z-4: The aforementioned polymers Z-1~Z-4.

[0718] [Evaluation 1 (Photolithography Evaluation)]

[0719] <Formation of resist pattern>

[0720] On a 12-inch silicon wafer, an organic antireflective film composition “ARC29A” (manufactured by Brewer Science, Inc.) is applied using a spin coater and then fired at 205°C for 60 seconds on a hot plate to dry it, thereby forming an organic antireflective film with a thickness of 85 nm.

[0721] The resist composition prepared in <Preparation of Resist Composition 1> is applied to the antireflective film using a spin coater. The film is then pre-baked (PAB) at 110°C for 60 seconds on a hot plate and dried to form a resist film with a thickness of 500 nm.

[0722] Using an ArF exposure apparatus NSR-S308F [Nikon; NA (aperture number) = 0.75, Conventional, Sigma 0.6], selective irradiation was performed with an ArF excimer laser (193 nm) through a photomask (6% halftone). Then, a PEB treatment was performed at 100°C for 60 seconds.

[0723] Next, alkaline development was performed at 23°C for 15 seconds using a 2.38% by mass TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.), followed by rinsing with pure water for 15 seconds and spin drying. As a result, in all examples, independent spaced patterns with a space size of 140 nm and a spacing of 1650 nm (mask size of 150 nm) were formed.

[0724] <Evaluation of resist patterns>

[0725] [Sensitivity (Optimal Exposure)]

[0726] Determine the optimal exposure (mJ / cm) for forming the aforementioned independent interval pattern. 2 The sensitivity values ​​are recorded in Tables 2-4.

[0727] [Resolution Evaluation]

[0728] In the independent spaced patterns formed in the aforementioned <Formation of Resist Patterns>, the spaced width was measured using a length-measuring SEM (scanning electron microscope, accelerating voltage 500V, trade name: CG4100, manufactured by Hitachi High-Technologies Corporation) when the mask size was reduced. The spaced width before the spaced pattern became indistinguishable is shown in Tables 2-4 as the resolution (limiting resolution). The smaller the value, the higher the resolution.

[0729] [Evaluation 2 (Crack and Porosity Evaluation)]

[0730] <Formation of resist pattern>

[0731] On a 12-inch silicon wafer that has been treated with hexamethyldisilazane (HMDS) at 90°C for 36 seconds, the resist composition prepared in <Preparation of Resist Composition 2> above is applied using a spin coater. The wafer is then pre-baked (PAB) at 110°C for 60 seconds on a hot plate and dried to form a resist film with a thickness of 1200 nm.

[0732] Using an ArF exposure apparatus NSR-S308F [Nikon; NA (aperture number) = 0.75, Conventional, Sigma 0.6], selective irradiation was performed with an ArF excimer laser (193 nm) through a photomask (6% halftone). Then, a PEB treatment was performed at 100°C for 60 seconds.

[0733] Next, alkaline development was performed at 23°C for 15 seconds using a 2.38% by mass TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.), followed by rinsing with pure water for 15 seconds and spin drying. As a result, in all examples, contact hole patterns (hereinafter referred to as CH patterns) with a hole size of 400 nm and a spacing of 800 nm (mask size of 420 nm) were formed.

[0734] <Evaluation of resist patterns>

[0735] [Evaluation of the crack]

[0736] Using a length-measuring SEM (scanning electron microscope, accelerating voltage 500V, trade name: CG4100, manufactured by Hitachi High-Technologies Corporation), the corners of the large area surrounding the pattern formed in the aforementioned <formation of resist pattern> were observed, and the presence or absence of cracks was counted and shown in Tables 2 to 4.

[0737] Evaluation Criteria

[0738] ◎: There are 0 cracks.

[0739] 〇: 1 to 5 cracks

[0740] △: There are 6 to 20 cracks.

[0741] ×: There are 21 or more cracks.

[0742] [Evaluation of the gap]

[0743] Using a length-measuring SEM (scanning electron microscope, 8kV, trade name: SU-8000, manufactured by Hitachi High-Technologies Corporation), the cross-sectional shape of the CH pattern formed in the aforementioned <Formation of Resist Pattern> was observed, and the number of voids (pores) generated in the resist portion of the pattern was counted and shown in Tables 2 to 4.

[0744] Evaluation Criteria

[0745] ◎: There are 0 gaps

[0746] 〇: The number of gaps is 1 to 5

[0747] △: The number of gaps is 6 to 20.

[0748] ×: There are 21 or more gaps

[0749] The results shown in Tables 2-4 confirm that the resist compositions of Examples 1-24 have good resolution, suppress crack formation, and suppress void formation.

[0750] Industrial availability

[0751] According to the present invention, a resist composition with excellent resolution and that is not prone to cracking or voids, and a method for forming a resist pattern using the resist composition, can be provided.

[0752] The invention has been described in detail and with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0753] This application is based on Japanese Patent Application No. 2023-078151, filed on May 10, 2023, the contents of which are incorporated herein by reference.

Claims

1. A photoresist composition capable of generating acid upon exposure and whose solubility in a developer is altered by the action of the acid, said photoresist composition comprising: The solubility of the substrate component in the developer solution can be changed by the action of acid (A), the acid-generating agent component that can generate acid through exposure (B), and Plasticizer component (Z), The substrate component (A) comprises a resin component (A1) having structural units (a1) and (a2) and free of aromatic rings. The structural unit (a1) is a structural unit represented by the following general formula (a1-1) containing an acid-degrading group whose polarity can increase through the action of an acid. The structural unit (a2) comprises any one of a cyclic group containing a lactone, a cyclic group containing -SO2-, or a cyclic group containing a carbonate. The plasticizer component (Z) has a structural unit (z1) represented by the following general formula (z1-1). The content of the plasticizer component (Z) is 20 parts by weight or less relative to 100 parts by weight of the resin component (A1). [Chemical Formula 1] In general formula (a1-1), R1 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms; Va01 is a divalent linking group; na01 is an integer from 0 to 2; Ra01 is a chain-like alkyl group; Ya01 is a carbon atom; and Xa01 is a group that forms a monocyclic alicyclic hydrocarbon group together with Ya01, wherein some or all of the hydrogen atoms in the monocyclic alicyclic hydrocarbon group can be substituted. [Chemical Formula 2] In general 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, and Vz 0 Rz is a single bond or a divalent hydrocarbon group that may contain heteroatoms. 0 It is a hydrogen atom or a group represented by the following general formula (z1-r-1). [Chemical Formula 3] In the general formula (z1-r-1), Rz 01 Rz is a hydrocarbon group that can have substituents. 02 Rz is a hydrogen atom or a hydrocarbon group that may have substituents. 01 With Rz 02 They can bond together to form a ring structure, with * being the connecting bond.

2. The resist composition according to claim 1, wherein, The plasticizer component (Z) does not contain acid-dissociable groups.

3. The resist composition according to claim 1 or 2, wherein, The acid-producing agent component (B) contains an ionic compound.

4. The resist composition of claim 1 or 2, further comprising an alkaline component (D) for controlling the diffusion of acid generated by the acid-generating component (B) upon exposure.

5. The resist composition according to claim 1 or 2, wherein, The resin component (A1) also has a structural unit (a3) ​​containing an aliphatic hydrocarbon group with a polar group.

6. A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using the resist composition according to claim 1 or 2; exposing the resist film; and developing the resist film to form a resist pattern.

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