Patent Application
20250051501
The present invention relates to a resist composition and a resist pattern formation method.
Priority is claimed on Japanese Patent Application No. 2021-205205, filed Dec. 17, 2021, the content of which is incorporated herein by reference.
In recent years, in the production of semiconductor elements and liquid crystal display elements, advances in lithography techniques have led to rapid progress in the field of pattern fining. Typically, these pattern fining techniques involve shortening the wavelength (increasing the energy) of the light source for exposure.
Resist materials for use with these types of light sources for exposure require lithography characteristics such as a high resolution capable of reproducing a fine-sized pattern, and a high level of sensitivity to these types of light sources for exposure.
As a resist material that satisfies these requirements, a chemical amplification-type resist composition that contains a base material component that exhibits changed solubility in a developing solution under action of an acid, and an acid generator component that generates an acid upon exposure has been used in the related art.
As one of techniques for improving resolution, a lithography method, which is so-called liquid immersion lithography is known, where a liquid (liquid immersion medium) having a higher refractive index than that of air is interposed between an objective lens of an exposure device and a sample to carry out exposure (liquid immersion lithography). According to liquid immersion lithography, even in a case of using a light source with the same exposure wavelength, the same high resolution as in a case of using a light source with a shorter wavelength or a high NA lens can be achieved, and the depth of focus is not even degraded. In addition, liquid immersion lithography can be carried out using the exposure apparatus of the related art. Therefore, liquid immersion lithography has been used in recent years because liquid immersion lithography can realize the formation of a resist pattern that is low in cost and has a high resolution and an excellent depth of focus. Liquid immersion lithography is considered to be effective in forming any pattern shape and to be combined with a super-resolution technique such as a phase shift method or a deformed illumination method. At the present time, a technique using an ArF excimer laser as a light source is being actively researched as a liquid immersion lithography technique. As the liquid immersion medium, water is mainly examined.
In the above-describe liquid immersion lithography, a resist material having characteristics corresponding to the liquid immersion lithography technique in addition to the typical lithography characteristics (the sensitivity, the resolution, the etching resistance, and the like) is required. For example, in liquid immersion lithography, in a case where a resist film is brought into contact with a liquid immersion solvent, elution of a substance in the resist film into the liquid immersion solvent (substance elution) occurs. The substance elution causes phenomena such as deterioration of the resist layer and a change in the refractive index of the liquid immersion solvent and degrades the lithography characteristics. Since the amount of the substance elution is affected by the characteristics (such as the hydrophilicity and the hydrophobicity) of the surface of the resist film, the substance elution is reduced by, for example, increasing the hydrophobicity of the surface of the resist film, and thus the lithography characteristics are improved.
Adding a compound having a fluorine atom to a resist composition used for such liquid immersion lithography has been proposed. For example, Patent Document 1 discloses, as a compound having a fluorine atom which is added to a resist composition, a fluorine-containing polymeric compound having a constitutional unit having a fluorine atom.
A resist composition in the related art has poor followability (dynamic contact angle) to water in a case where liquid immersion lithography is carried out using water as a liquid immersion medium. Therefore, water droplets tend to remain on the wafer surface after the liquid immersion lithography. In addition, it has not been possible to suppress the elution of components of a resist material into water. These factors have made it impossible to suppress the occurrence of water mark defects (WMDs) in the resist composition in the related art.
The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a resist composition that makes it possible to form a resist pattern having reduced occurrence of water mark defects, and a resist pattern formation method using the resist composition.
In order to achieve the above-described object, the present invention employs the following configurations.
A first aspect of the present invention is a resist composition that generates an acid upon exposure and exhibits changed solubility in a developing solution under action of the acid, the resist composition containing a resin component (A1) that exhibits changed solubility in a developing solution under action of the acid, a photodecomposable base (DO); and a fluorine additive component (F), in which the fluorine additive component (F) is a polymeric compound having a constitutional unit (f01) represented by General Formula (f01-1) and a constitutional unit (f02) represented by General Formula (f02-1).
[In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Vf01 represents an alkylene group having 1 to 10 carbon atoms or a halogenated alkylene group having 1 to 5 carbon atoms, and Yf01 represents —CO—O— or —O—CO—. Rf01 represents an organic group containing a fluorine atom, and nf01 represents an integer in a range of 0 to 5.]
[In the formulae, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Vf02 represents a divalent hydrocarbon group which may have a substituent. nf02 represents an integer in a range of 0 to 2. Rf02 represents an acid dissociable group represented by General Formula (f02-r1-1). Rf021 and Rf022 each independently represent a hydrocarbon group which may have a substituent. Rf021 and Rf022 may be bonded to each other to form a ring structure. Yf02 represents a quaternary carbon atom. Rf023, Rf024, and Rf025 each independently represent a hydrocarbon group which may have a substituent. * represents a bonding site for bonding to an oxygen atom to which Rf02 in General Formula (f02-1) is bonded.]
The second aspect according to the present invention is a resist pattern formation method, including a step of forming a resist film on a support using the resist composition according to the first aspect, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.
According to the present invention, it is possible to provide a resist composition that makes it possible to form a resist pattern having reduced occurrence of water mark defects, and a resist pattern formation method using the resist composition.
In the present specification and the scope of the present claims, the term “aliphatic” is a relative concept used with respect to the term “aromatic” and defines a group or compound that has no aromaticity.
The term “alkyl group” includes a monovalent saturated hydrocarbon group that is linear, branched, or cyclic unless otherwise specified. The same applies to the alkyl group of an alkoxy group.
The term “alkylene group” includes a divalent saturated hydrocarbon group that is linear, branched, or cyclic unless otherwise specified.
Examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The term “constitutional unit” means a monomer unit (a monomeric unit) that contributes to the formation of a polymeric compound (a resin, a polymer, or a copolymer).
The expression “may have a substituent” includes both a case where a hydrogen atom (—H) is substituted with a monovalent group and a case where a methylene group (—CH2—) is substituted with a divalent group.
The term “exposure” is used as a general concept that includes irradiation with any form of radiation.
The term “acid decomposable group” is a group having acid decomposability, in which at least part of bonds in the structure of the acid decomposable group can be cleaved under action of an acid.
Examples of the acid decomposable group having a polarity that is increased under action of an acid include groups that are decomposed under action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (—SO3H).
More specific examples of the acid decomposable group include a group obtained by protecting the above-described polar group with an acid dissociable group (for example, a group obtained by protecting a hydrogen atom of the OH-containing polar group with an acid dissociable group).
The term “acid dissociable group” refers to any one of (i) a group having acid dissociability, in which a bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved under action of an acid; and (ii) a group in which part of bonds are cleaved under action of an acid, and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid dissociable group and the atom adjacent to the acid dissociable group.
It is necessary that the acid dissociable group that constitutes the acid decomposable group be a group that exhibits a lower polarity than the polar group generated by the dissociation of the acid dissociable group. Thus, in a case where the acid dissociable group is dissociated under action of an acid, a polar group that exhibits a higher polarity than the acid dissociable group is generated, thereby increasing the polarity. As a result of the above, the polarity of the total component (A1) is increased. With the increase in the polarity, the solubility in a developing solution relatively changes. The solubility in a developing solution is increased in a case where the developing solution is an alkali developing solution, whereas the solubility in a developing solution is decreased in a case where the developing solution is an organic developing solution.
The term “base material component” is an organic compound having a film-forming ability. The organic compounds used as the base material component are roughly classified into a non-polymer and a polymer. As the non-polymer, those having a molecular weight of 500 or more and less than 4,000 are generally used. Hereinafter, “low molecular weight compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4,000. As the polymer, those having a molecular weight of 1,000 or more are generally used. Hereinafter, “resin”, “polymeric compound”, or “polymer” refers to a polymer having a molecular weight of 1,000 or more. As the molecular weight of the polymer, a weight average molecular weight in terms of the polystyrene equivalent value determined by gel permeation chromatography (GPC) is used.
The term “constitutional unit derived from” means a constitutional unit that is formed by the cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond.
In the “acrylic acid ester”, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (Rαx) that is substituted for a hydrogen atom bonded to the carbon atom at the α-position is an atom or a group other than the hydrogen atom. In addition, the acrylic acid ester includes itaconic acid diester in which the substituent (Rαx) has been substituted with a substituent having an ester bond and α-hydroxyacryl ester in which the substituent (Rαx) has been substituted with a hydroxyalkyl group or a group obtained by modifying a hydroxyl group thereof. It is noted that a carbon atom at the α-position of an acrylic acid ester indicates the carbon atom bonded to the carbonyl group of acrylic acid unless otherwise specified.
Hereinafter, an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent is also referred to as an α-substituted acrylic acid ester.
The term “derivative” includes a compound in which the hydrogen atom at the α-position of the object compound has been substituted with another substituent such as an alkyl group or a halogenated alkyl group; and derivatives thereof. Examples of the derivatives thereof include a derivative in which the hydrogen atom of the hydroxyl group of the object compound in which the hydrogen atom at the α-position may be substituted with a substituent is substituted with an organic group; and a derivative in which a substituent other than a hydroxyl group is bonded to the object compound in which the hydrogen atom at the α-position may be substituted with a substituent. It is noted that the α-position refers to the first carbon atom adjacent to the functional group unless otherwise specified.
Examples of the substituent that is substituted for a hydrogen atom at the α-position of hydroxystyrene include the same ones as those for Rαx.
In the present specification and the present claims, asymmetric carbons may be present and enantiomers or diastereomers may be present depending on the structures of the chemical formulae. In that case, these isomers are represented by one chemical formula. These isomers may be used alone or in the form of a mixture.
The resist composition according to the present embodiment is a resist composition that generates an acid upon exposure and exhibits changed solubility in a developing solution under action of the acid.
Such a resist composition contains a base material component (A) (hereinafter, also referred to as a “component (A)”) that exhibits changed solubility in a developing solution under action of an acid, an acid diffusion controlling agent component (D) (hereinafter, also referred to as a “component (D)”), and a fluorine additive component (F).
In a case where a resist film is formed using the resist composition according to the present embodiment and the formed resist film is subjected to selective exposure, an acid is generated at exposed portions of the resist film, and the generated acid acts on the component (A) to change the solubility of the component (A) in a developing solution. On the other hand, the solubility of the component (A) in a developing solution is not changed at unexposed portions of the resist film, which generates the difference in solubility in the developing solution between exposed portions and unexposed portions of the resist film. As a result, in a case where the resist film is subjected to development, exposed portions of the resist film are dissolved and removed to form a positive-tone resist pattern in a case where the resist composition is a positive-tone type, whereas unexposed portions of the resist film are dissolved and removed to form a negative-tone resist pattern in a case where the resist composition is a negative-tone type. In the present specification, a resist composition which forms a positive-tone resist pattern by dissolving and removing exposed portions of the resist film is called a positive-tone resist composition, and a resist composition which forms a negative-tone resist pattern by dissolving and removing unexposed portions of the resist film is called a negative-tone resist composition.
The resist composition according to the present embodiment may be a positive-tone resist composition or a negative-tone resist composition.
In addition, in the formation of a resist pattern, the resist composition according to the present embodiment can be applied to an alkali developing process using an alkali developing solution in the developing treatment, or a solvent developing process using an organic developing solution in the developing treatment.
The resist composition according to the present embodiment has a function of generating an acid upon light exposure, the component (A) may generate an acid upon light exposure, and an additive component that is separately blended from the component (A) may generate an acid upon light exposure.
Specifically, the resist composition according to the present embodiment may be (1) a resist composition containing an acid generator component (B) (hereinafter referred to as a “component (B)”) that generates an acid upon exposure, may be (2) a resist composition in which the component (A) is a component that generates an acid upon exposure, or may be (3) a resist composition in which the component (A) is a component that generates an acid upon exposure and which further contains the component (B).
That is, in the cases of (2) and (3) described above, the component (A) becomes a “base material component that generates an acid upon exposure and exhibits changed solubility in a developing solution under action of the acid”. In a case where the component (A) is a base material component that generates an acid upon exposure and exhibits changed solubility in a developing solution under action of the acid, it is preferable that the component (A1) that will be described later be a polymeric compound that generates an acid upon exposure and exhibits changed solubility in a developing solution under action of the acid. As such a polymeric compound, a resin having a constitutional unit that generates an acid upon exposure can be used. As the constitutional unit that generates an acid upon exposure, a known constitutional unit can be used.
In the resist composition according to the present embodiment, the component (A) preferably contains a resin component (A1) (hereinafter, also referred to as a “component (A1)”) that exhibits changed solubility in a developing solution under action of an acid. In the alkali developing process and the solvent developing process, since the polarity of the base material component before and after the exposure is changed by using the component (A1), an excellent development contrast can be obtained.
As the component (A), at least the component (A1) is used, and another polymeric compound and/or a low molecular weight compound may be used in combination, together with the component (A1).
In the case of applying an alkali developing process, a base material component containing the component (A1) is insoluble in an alkali developing solution prior to exposure, and, for example, in a case where an acid is generated from the component (B) upon exposure, the action of this acid causes an increase in the polarity of the base material component, thereby increasing the solubility of the base material component in an alkali developing solution. Therefore, in the resist pattern formation, in the case of carrying out selective exposure of a resist film formed by applying the resist composition onto a support, exposed portions of the resist film change from an insoluble state to a soluble state in an alkali developing solution, whereas unexposed portions of the resist film remain insoluble in an alkali developing solution, and thus a positive-tone resist pattern is formed by alkali developing.
On the other hand, in the case of a solvent developing process, the base material component containing the component (A1) exhibits high solubility in an organic developing solution prior to exposure, and, for example, in a case where an acid is generated from the component (B) upon exposure, polarity is increased by the action of the generated acid, thereby decreasing the solubility in an organic developing solution. Therefore, in the resist pattern formation, by carrying out selective exposure of a resist film formed by applying the resist composition onto a support, exposed portions of the resist film change from a soluble state to an insoluble state in an organic developing solution, whereas unexposed portions of the resist film remain soluble and do not change, thereby a contrast between exposed portions and unexposed portions can be obtained, and thus a negative-tone resist pattern is formed by developing in the organic developing solution.
In the resist composition according to the present embodiment, the component (A) may be used alone or in a combination of two or more kinds thereof.
The component (A1) is a resin component that exhibits changed solubility in a developing solution under action of an acid.
The component (A1) preferably has a constitutional unit (a1) that includes an acid decomposable group having a polarity that is increased under action of an acid.
The component (A1) may have other constitutional units as necessary in addition to the constitutional unit (a1).
<<Constitutional Unit (a1)>>
The constitutional unit (a1) is a constitutional unit that contains an acid decomposable group having a polarity that is increased under action of an acid.
Examples of the acid dissociable group include those which have been proposed so far as acid dissociable groups for the base resin for a chemical amplification-type resist composition.
Specific examples of the acid dissociable group of the base resin proposed for a chemical amplification-type resist composition include an “acetal-type acid dissociable group”, a “tertiary alkyl ester-type acid dissociable group”, and a “tertiary alkyloxycarbonyl acid dissociable group” described below.
Examples of the acid dissociable group for protecting a carboxy group or a hydroxyl group as a polar group include the acid dissociable group represented by General Formula (a1-r-1) shown below (hereinafter, also referred to as an “acetal-type acid dissociable group”).
[In the formula, Ra′1 and Ra′2 represent a hydrogen atom or an alkyl group. Ra′3 represents a hydrocarbon group, and Ra′3 may be bonded to any of Ra′1 and Ra′2 to form a ring.]
In General Formula (a1-r-1), it is preferable that at least one of Ra′1 or Ra′2 represent a hydrogen atom and more preferable that both Ra′1 and Ra′2 represent a hydrogen atom.
In a case where Ra′1 or Ra′2 represents an alkyl group, examples of the alkyl group include the same one as the alkyl group described for the substituent which may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylic acid ester. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Specific examples thereof preferably include a linear or branched alkyl group. More specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
In General Formula (a1-r-1), examples of the hydrocarbon group as Ra′3 include a linear or branched alkyl group and a cyclic hydrocarbon group.
The linear alkyl group has preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
The branched alkyl group has preferably 3 to 10 carbon atoms and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group. Among these, an isopropyl group is preferable.
In a case where Ra′3 represents a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group and may be a polycyclic group or a monocyclic group.
The aliphatic hydrocarbon group which is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
In a case where the cyclic hydrocarbon group as Ra′3 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and the aromatic ring may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably has 5 to 20 carbon atoms, still more preferably has 6 to 15 carbon atoms, and particularly preferably has 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting the above-described aromatic hydrocarbon ring with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group as Ra′3 include a group in which one hydrogen atom has been removed from the above-described aromatic hydrocarbon ring or aromatic heterocyclic ring (such as an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound having two or more aromatic rings (such as biphenyl or fluorene); and a group in which one hydrogen atom of the above-described aromatic hydrocarbon ring or aromatic heterocyclic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring preferably has 1 to 4 carbon atoms, more preferably has 1 or 2 carbon atoms, and particularly preferably has 1 carbon atom.
The cyclic hydrocarbon group as Ra′3 may include a substituent. Examples of the substituent include —RP1, —RP2—O—RP1, —RP2—CO—RP1, —RP2—CO—ORP1, —RP2—O—CO—RP1, —RP2—OH, —RP2—CN, and —RP2—COOH (hereinafter, these substituents will also be collectively referred to as “Rax5”).
Here, RP1 represents a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. In addition, RP2 represents a single bond, a chain-like divalent saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, part or all of hydrogen atoms in the chain-like saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group, and the aromatic hydrocarbon group as RP1 and RP2 may be substituted with a fluorine atom. In the aliphatic cyclic hydrocarbon group, one or more of the above-described substituents may be included as a single kind, or one or more of the above-described substituents may be included as a plurality of kinds.
Examples of the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, or phenanthrene.
In a case where Ra′3 is bonded to any of Ra′1 and Ra′2 to form a ring, the cyclic group is preferably a 4- to 7-membered ring and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.
Among the above polar groups, examples of the acid dissociable group for protecting the carboxy group include the acid dissociable group represented by General Formula (a1-r-2) shown below.
It is noted that among the acid dissociable groups represented by General Formula (a1-r-2), for convenience, a group which is constituted of alkyl groups is referred to as a “tertiary alkyl ester-type acid dissociable group”.
[In the formula, Ra′4 to Ra′6 each represent a hydrocarbon group, and Ra′5 and Ra′6 may be bonded to each other to form a ring.]
Examples of the hydrocarbon group as Ra′4 include a linear or branched alkyl group, a chain-like or cyclic alkenyl group, and a cyclic hydrocarbon group.
Examples of the linear or branched alkyl group and the cyclic hydrocarbon group (an aliphatic hydrocarbon group which is a monocyclic group, an aliphatic hydrocarbon group which is a polycyclic group, or an aromatic hydrocarbon group) as Ra′4 include the same ones as Ra′3.
As the chain-like or cyclic alkenyl group as Ra′4, an alkenyl group having 2 to 10 carbon atoms is preferable.
Examples of the hydrocarbon group as Ra′5 or Ra′6 include the same ones as Ra′3.
In a case where Ra′5 and Ra′6 are bonded to each other to form a ring, suitable examples thereof include a group represented by General Formula (a1-r2-1), a group represented by General Formula (a1-r2-2), and a group represented by General Formula (a1-r2-3).
Meanwhile, in a case where Ra′4 to Ra′6 independently represent a hydrocarbon group without being bonded to each other, suitable examples thereof include a group represented by General Formula (a1-r2-4).
[In General Formula (a1-r2-1), Ra′10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which a part thereof may be substituted with a halogen atom or a hetero atom-containing group. Ra′11 represents a group that forms an aliphatic cyclic group together with the carbon atom to which Ra′10 has been bonded. In General Formula (a1-r2-2), Ya represents a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Part or all of hydrogen atoms contained in the cyclic hydrocarbon group may be substituted. Ra101 to Ra103 each independently represent a hydrogen atom, a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Part or all of hydrogen atoms contained in the chain-like saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra101 to Ra103 may be bonded to each other to form a cyclic structure. In General Formula (a1-r2-3), Yaa represents a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra104 represents an aromatic hydrocarbon group which may have a substituent. In General Formula (a1-r2-4), Ra′12 and Ra′13 each independently represent a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Part or all of hydrogen atoms contained in the chain-like saturated hydrocarbon group may be substituted. Ra′14 represents a hydrocarbon group which may have a substituent. * represents a bonding site.]
In General Formula (a1-r2-1), Ra′10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which a part thereof may be substituted with a halogen atom or a hetero atom-containing group.
The linear alkyl group as Ra′10 has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Examples of the branched alkyl group as Ra′10 include those for Ra′3 described above.
The alkyl group in Ra′10 may be partially substituted with a halogen atom or a hetero atom-containing group. For example, a part of hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a hetero atom-containing group. In addition, a part of carbon atoms (those in the methylene group or the like) constituting the alkyl group may be substituted with a hetero atom-containing group.
Examples of the hetero atom mentioned here include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom-containing group include (—O—), —C(═O)—O—, —O—C(═O)—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH—, —S—, —S(═O)2—, and —S(═O)2—O—.
In General Formula (a1-r2-1), preferred examples of Ra′11 (a group that forms an aliphatic cyclic group together with the carbon atom to which Ra′10 has been bonded) include the groups described as the examples of the aliphatic hydrocarbon group (alicyclic hydrocarbon group) which is a monocyclic group or a polycyclic group as Ra′3 in General Formula (a1-r-1). Among the above, a monocyclic alicyclic hydrocarbon group is preferable, specifically, a cyclopentyl group or a cyclohexyl group is more preferable, and a cyclopentyl group is still more preferable.
In General Formula (a1-r2-2), examples of the cyclic hydrocarbon group that is formed by Xa together with Ya include a group in which one or more hydrogen atoms have been further removed from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) as Ra′3 in General Formula (a1-r-1).
The cyclic hydrocarbon group that is formed by Xa together with Ya may have a substituent. Examples of the substituent include those described as the examples of the substituents which may be contained in the cyclic hydrocarbon group as Ra′3.
In General Formula (a1-r2-2), examples of the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms as Ra101 to Ra103 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms as Ra101 to Ra103 include a monocyclic aliphatic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, or a cyclododecyl group; and a polycyclic aliphatic saturated hydrocarbon group such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, or an adamantyl group.
From the viewpoint of ease of synthesis, Ra101 to Ra103 are preferably a hydrogen atom or a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.
Examples of the substituent included in the chain-like saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by Ra101 to Ra103 include the same substituents as those for Rax5.
Examples of the group having a carbon-carbon double bond generated by two or more of Ra101 to Ra103 being bonded to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylideneethenyl group, and a cyclohexylideneethenyl group. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferable from the viewpoint of ease of synthesis.
In General Formula (a1-r2-3), as the aliphatic cyclic group that is formed by Xaa together with Yaa, the group described as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group as Ra′3 in General Formula (a1-r-1) is preferable.
In General Formula (a1-r2-3), examples of the aromatic hydrocarbon group as Ra104 include a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among the examples, Ra104 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene or naphthalene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.
Examples of the substituent which may be contained in Ra104 in General Formula (a1-r2-3) include a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like), and an alkyloxycarbonyl group.
In General Formula (a1-r2-4), Ra′12 and Ra′13 each independently represent a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms as Ra′12 and Ra′13 include those described as the examples of the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms as Ra10 to Ra′103. Part or all of hydrogen atoms contained in the chain-like saturated hydrocarbon group may be substituted.
Among them, Ra′12 and Ra′13 are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
In a case where the chain-like saturated hydrocarbon group represented by Ra′12 and Ra′13 is substituted, examples of the substituent thereof include the same substituents as those for Rax5.
In General Formula (a1-r2-4), Ra′14 represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group as Ra′14 include a linear or branched alkyl group and a cyclic hydrocarbon group.
The linear alkyl group as Ra′14 has preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
The branched alkyl group as Ra′14 has preferably 3 to 10 carbon atoms and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group. Among these, an isopropyl group is preferable.
In a case where Ra′14 represents a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group and may be a polycyclic group or a monocyclic group.
The aliphatic hydrocarbon group which is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
Examples of the aromatic hydrocarbon group as Ra′14 include the same ones as the aromatic hydrocarbon group as Ra104. Among these, Ra′14 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene.
Examples of the substituent which may be contained in Ra′14 include the same one as the substituent which may be contained in Ra104.
In a case where Ra′14 in General Formula (a1-r2-4) represents a naphthyl group, the position bonded to the tertiary carbon atom in General Formula (a1-r2-4) may be the 1-position or the 2-position of the naphthyl group.
In a case where Ra′14 in General Formula (a1-r2-4) represents an anthryl group, the position bonded to the tertiary carbon atom in General Formula (a1-r2-4) may be the 1-position, the 2-position, or the 9-position of the anthryl group.
Specific examples of the group represented by General Formula (a1-r2-1) are shown below.
Specific examples of the group represented by General Formula (a1-r2-2) are shown below.
Specific examples of the group represented by General Formula (a1-r2-3) are shown below.
Specific examples of the group represented by General Formula (a1-r2-4) are shown below.
Among the polar groups, examples of the acid dissociable group for protecting a hydroxyl group include an acid dissociable group (hereinafter, for convenience, also referred to as a “tertiary alkyloxycarbonyl acid dissociable group”) represented by General Formula (a1-r-3) shown below.
[In the formula, Ra′7 to Ra′9 each represent an alkyl group.]
In General Formula (a1-r-3), Ra′7 to Ra′9 are each preferably an alkyl group having 1 to 5 carbon atoms and more preferably an alkyl group having 1 to 3 carbon atoms.
In addition, the total number of carbon atoms in each of the alkyl groups is preferably in a range of 3 to 7, more preferably in a range of 3 to 5, and most preferably 3 or 4.
Examples of the constitutional unit (a1) include a constitutional unit derived from an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent; a constitutional unit derived from acrylamide; a constitutional unit in which at least a part of hydrogen atoms in a hydroxyl group of a constitutional unit derived from hydroxystyrene or a hydroxystyrene derivative are protected by a substituent including the above-described acid decomposable group; and a constitutional unit in which at least a part of hydrogen atoms in —C(═O)—OH of a constitutional unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative are protected by a substituent including the above-described acid decomposable group.
Among the above, the constitutional unit (a1) is preferably a constitutional unit derived from an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
Preferred specific examples of such a constitutional unit (a1) include constitutional units represented by General Formula (a1-1) or (a1-2).
[In the formulae, R represents a hydrogen atom. an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va1 represents a divalent hydrocarbon group which may have an ether bond. na1 represents an integer in a range of 0 to 2. Ra1 represents an acid dissociable group represented by General Formula (a1-r-1) or (a1-r-2). Wa1 represents a (na2+1)-valent hydrocarbon group, na2 represents an integer in a range of 1 to 3, and Ra2 represents an acid dissociable group represented by General Formula (a1-r-1) or (a1-r-3).]
In General Formula (a1-1), the alkyl group having 1 to 5 carbon atoms as R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which part or all of hydrogen atoms in the alkyl group having 1 to 5 carbon atoms have been substituted with a halogen atom. The halogen atom is particularly preferably a fluorine atom.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable in terms of industrial availability.
In General Formula (a1-1), the divalent hydrocarbon group as Va1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group as the divalent hydrocarbon group represented by Va1 may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group be saturated.
Specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group containing a ring in the structure thereof.
The linear aliphatic hydrocarbon group described above preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 4 carbon atoms, and most preferably has 1 to 3 carbon atoms.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [—CH2—], an ethylene group [—(CH2)2—], a trimethylene group [—(CH2)3—], a tetramethylene group [—(CH2)4—], and a pentamethylene group [—(CH2)5—].
The branched aliphatic hydrocarbon group described above preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, still more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkylalkylene groups, for example, 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—; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2CH(CH3)CH2—; and alkyltetramethylene groups such as —CH(CH3)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
Examples of the aliphatic hydrocarbon group containing a ring in the structure thereof include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the alicyclic hydrocarbon group is bonded to the terminal of the linear or branched aliphatic hydrocarbon group, and a group in which the alicyclic hydrocarbon group is interposed in the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as the above-described linear aliphatic hydrocarbon group or the above-described branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a group having 7 to 12 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The aromatic hydrocarbon group as the divalent hydrocarbon group represented by Va1 is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably has 5 to 30 carbon atoms, still more preferably has 5 to 20 carbon atoms, particularly preferably has 6 to 15 carbon atoms, and most preferably has 6 to 12 carbon atoms. Here, the number of carbon atoms in a substituent is not included in the number of carbon atoms.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting the above-described aromatic hydrocarbon ring with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the above-described aromatic hydrocarbon ring (an arylene group); and a group in which one hydrogen atom of a group (an aryl group) formed by removing one hydrogen atom from the aromatic hydrocarbon ring has been substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group (an alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably has 1 or 2 carbon atoms, and particularly preferably has 1 carbon atom.
In General Formula (a1-1), Ra1 represents an acid dissociable group represented by General Formula (a1-r-1) or (a1-r-2).
In General Formula (a1-2), the (na2+1)-valent hydrocarbon group as Wa1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group indicates a hydrocarbon group that has no aromaticity and may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group be saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure thereof, and a combination of the linear or branched aliphatic hydrocarbon group and the aliphatic hydrocarbon group containing a ring in the structure thereof.
The valency of na2+1 is preferably divalent to tetravalent and more preferably divalent or trivalent.
In General Formula (a1-2), Ra2 represents an acid dissociable group represented by General Formula (a1-r-1) or (a1-r-3).
Specific examples of the constitutional unit represented by General Formula (a1-1) are shown below. In the formulae shown below, Ra represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
The constitutional unit (a1) contained in the component (A1) may be one kind or may be two or more kinds.
The constitutional unit (a1) is more preferably a constitutional unit represented by General Formula (a1-1) since lithography characteristics (sensitivity, shape, and the like) depending on an electron beam or EUV can be more easily increased.
Among these, the constitutional unit (a1) particularly preferably includes a constitutional unit represented by General Formula (a1-1-1) shown below.
[In the formulae, Ra1″ represents an acid dissociable group represented by General Formula (a1-r2-1), (a1-r2-3), or (a1-r2-4).]
R, Va1, and na1 in General Formula (a1-1-1) are the same as R, Va1, and na1 in General Formula (a1-1).
The description for the acid dissociable group represented by General Formula (a1-r2-1), (a1-r2-3), or (a1-r2-4) is as described above.
In General Formula (a1-1-1), Ra1″ is preferably, among the above, an acid dissociable group represented by General Formula (a1-r2-1) or (a1-r2-4).
The proportion of the constitutional unit (a1) in the component (A1) is preferably in a range of 5% to 80% by mole, more preferably in a range of 10% to 75% by mole, still more preferably in a range of 30% to 70% by mole, and particularly preferably in a range of 40% to 70% by mole, with respect to the total (100% by mole) of all constitutional units constituting the component (A1).
In a case where the proportion of the constitutional unit (a1) is equal to or larger than the lower limit value of the above-described preferred range, lithography characteristics such as sensitivity, resolution, and roughness amelioration are improved. On the other hand, in a case where the proportion is equal to or smaller than the upper limit value of the above-described preferred range, balance with other constitutional units can be obtained, and various lithography characteristics are improved.
The component (A1) may have other constitutional units as necessary in addition to the constitutional unit (a1) described above.
Examples of the other constitutional units include a constitutional unit (a2) containing a lactone-containing cyclic group, a —SO2— containing cyclic group, or a carbonate-containing cyclic group; a constitutional unit (a3) containing a polar group-containing aliphatic hydrocarbon group; a constitutional unit (a4) containing an acid non-dissociable aliphatic cyclic group; a constitutional unit (st) derived from styrene or a styrene derivative; and a constitutional unit derived from hydroxystyrene or a hydroxystyrene derivative.
The component (A1) may further have a constitutional unit (a2) (however, those corresponding to the constitutional unit (a1) are excluded) containing a lactone-containing cyclic group, a —SO2— containing cyclic group, or a carbonate-containing cyclic group, in addition to the constitutional unit (a1).
In a case where the component (A1) is used for forming a resist film, the lactone-containing cyclic group, the —SO2— containing cyclic group, or the carbonate-containing cyclic group in the constitutional unit (a2) is effective for improving the adhesiveness of the resist film to the substrate. In addition, due to having the constitutional unit (a2), lithography characteristics and the like can be improved, for example, by the effects obtained by appropriately adjusting the acid diffusion length, increasing the adhesiveness of the resist film to the substrate, and appropriately adjusting the solubility during development.
The term “lactone-containing cyclic group” indicates a cyclic group that contains a ring (lactone ring) containing a —O—C(═O)— in the ring skeleton. In a case where the lactone ring is counted as the first ring and the group contains only the lactone ring, the group is referred to as a monocyclic group. Further, in a case where the group has other ring structures, the group is referred to as a polycyclic group regardless of the structures. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group for the constitutional unit (a2) is not particularly limited, and any lactone-containing cyclic group may be used. Specific examples thereof include a group represented by each of General Formulae (a2-r-1) to (a2-r-7) shown below.
[In the formulae, each Ra′21 independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ represents a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO2—-containing cyclic group; A″ represents an oxygen atom, a sulfur atom, or an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom (—O—) or a sulfur atom (—S—); and n′ represents an integer in a range of 0 to 2, and m′ is 0 or 1. * represents a bonding site.]
In General Formulae (a2-r-1) to (a2-r-7), it is preferable that the alkyl group as Ra′21 be an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a linear alkyl group or a branched alkyl group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Among these, a methyl group or ethyl group is preferable, and a methyl group is particularly preferable.
It is preferable that the alkoxy group as Ra′21 be an alkoxy group having 1 to 6 carbon atoms. Further, the alkoxy group is preferably a linear or branched alkoxy group. Specific examples of the alkoxy groups include a group formed by linking the above-described alkyl group described as the examples of the alkyl group represented by Ra′21 to an oxygen atom (—O—).
The halogen atom as Ra′21 is preferably a fluorine atom.
Examples of the halogenated alkyl group as Ra′21 include groups in which some or all hydrogen atoms in the alkyl group as Ra′21 have been substituted with halogen atoms. The halogenated alkyl group is preferably a fluorinated alkyl group and particularly preferably a perfluoroalkyl group.
In —COOR″ and —OC(═O)R″ as Ra′21, each R″ represents a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO2—-containing cyclic group.
The alkyl group as R″ may be linear, branched, or cyclic and has preferably 1 to 15 carbon atoms.
In a case where R″ represents a linear or branched alkyl group, it is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group.
In a case where R″ represents a cyclic alkyl group, the cyclic alkyl group preferably has 3 to 15 carbon atoms, more preferably has 4 to 12 carbon atoms, and most preferably has 5 to 10 carbon atoms. Specific examples thereof include a group obtained by removing one or more hydrogen atoms from a monocycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as bicycloalkane, tricycloalkane, or tetracycloalkane. More specific examples thereof include a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane; and a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.
Examples of the lactone-containing cyclic group as R″ include the same ones as the group represented by each of General Formulae (a2-r-1) to (a2-r-7).
The carbonate-containing cyclic group as R″ is the same as the carbonate-containing cyclic group that will be described later. Specific examples thereof include groups represented by General Formulae (ax3-r-1) to (ax3-r-3).
The —SO2— containing cyclic group as R″ is the same as the —SO2— containing cyclic group that will be described later, and specific examples thereof include groups represented by each of General Formulae (a5-r-1) to (a5-r-4).
As the hydroxyalkyl group as Ra′21, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable, and specific examples thereof include a group in which at least one hydrogen atom in the alkyl group as Ra′2′ has been substituted with a hydroxyl group.
Among the examples, it is preferable that each Ra′21 independently represent a hydrogen atom or a cyano group.
In General Formulae (a2-r-2), (a2-r-3), and (a2-r-5), as the alkylene group having 1 to 5 carbon atoms as A″, a linear or branched alkylene group is preferable, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. In a case where the alkylene group has an oxygen atom or a sulfur atom, specific examples thereof include groups in which —O— or —S— is interposed between the terminals or carbon atoms of the alkylene group. Further, examples thereof include —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 a methylene group.
Specific examples of the group represented by each of General Formulae (a2-r-1) to (a2-r-7) are shown below.
The term “—SO2— containing cyclic group” denotes a cyclic group having a ring containing —SO2— in the ring skeleton thereof. Specifically, the —SO2— containing cyclic group is a cyclic group in which the sulfur atom (S) in —SO2— forms a part of the ring skeleton of the cyclic group. In a case where the ring containing —SO2— in the ring skeleton thereof is counted as the first ring and the group has only the ring, the group is referred to as a monocyclic group. In a case where the group further has other ring structures, the group is referred to as a polycyclic group regardless of the structures. The —SO2—-containing cyclic group may be a monocyclic group or a polycyclic group.
The —SO2—-containing cyclic group is particularly preferably a cyclic group containing —O—SO2— in the ring skeleton thereof, that is, a cyclic group containing a sultone ring in which —O—S— in —O—SO2— forms a part of the ring skeleton thereof. More specific examples of the —SO2— containing cyclic group include groups represented by each of General Formulae (a5-r-1) to (a5-r-4).
[In the formulae, each Ra′51 independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ represents a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO2—-containing cyclic group; A″ represents an oxygen atom, a sulfur atom, or an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom; and n′ represents an integer in a range of 0 to 2. * represents a bonding site.]
In General Formulae (a5-r-1) and (a5-r-2), A″ is the same as A″ in General Formulae (a2-r-2), (a2-r-3), and (a2-r-5).
Examples of the alkyl group, the alkoxy group, the halogen atom, the halogenated alkyl group, —COOR″, —OC(═O)R″, and the hydroxyalkyl group as Ra′51 include the same ones as those described for Ra′21 in General Formulae (a2-r-1) to (a2-r-7).
Specific examples of the group represented by each of General Formulae (a5-r-1) to (a5-r-4) are shown below. In the formulae shown below, “Ac” represents an acetyl group.
The term “carbonate-containing cyclic group” indicates a cyclic group having a ring (a carbonate ring) containing —O—C(═O)—O— in the ring skeleton thereof. In a case where the carbonate ring is counted as the first ring and the group contains only the carbonate ring, the group is referred to as a monocyclic group. Further, in a case where the group has other ring structures, the group is referred to as a polycyclic group regardless of the structures. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.
The carbonate-containing cyclic group is not particularly limited, and any carbonate-containing cyclic group may be used. Specific examples thereof include groups represented by each of General Formulae (ax3-r-1) to (ax3-r-3) shown below.
[In the formulae, each Ra′x31 independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ represents a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO2— containing cyclic group; A″ represents an oxygen atom, a sulfur atom, or an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom; and p′ represents an integer in a range of 0 to 3, and q′ is 0 or 1. * represents a bonding site.]
In General Formulae (ax3-r-2) and (ax3-r-3), A″ is the same as A″ in General Formulae (a2-r-2), (a2-r-3), and (a2-r-5).
Examples of the alkyl group, the alkoxy group, the halogen atom, the halogenated alkyl group, —COOR″, —OC(═O)R″, and the hydroxyalkyl group as Ra′31 include the same ones as those described for Ra′21 in General Formulae (a2-r-1) to (a2-r-7).
Specific examples of the group represented by each of General Formulae (ax3-r-1) to (ax3-r-3) are shown below.
Among them, the constitutional unit (a2) is preferably a constitutional unit derived from an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
The constitutional unit (a2) is preferably a constitutional unit represented by General Formula (a2-1).
[In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya21 represents a single bond or a divalent linking group. La21 represents —O—, —COO—, —CON(R′)—, —OCO—, —CONHCO—, or —CONHCS—, and R′ represents a hydrogen atom or a methyl group. In a case where La21 represents —O—, Ya21 does not represent —CO—. Ra21 represents a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO2—-containing cyclic group.]
In General Formula (a2-1), R has the same definition as described above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group in terms of industrial availability.
In General Formula (a2-1), the divalent linking group as Ya21 is not particularly limited, and suitable examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group having a hetero atom.
Divalent Hydrocarbon Group which May have Substituent:
In a case where Ya21 represents a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
Aliphatic hydrocarbon group as Ya21
The aliphatic hydrocarbon group indicates a hydrocarbon group that has no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group be saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group containing a ring in the structure thereof.
The linear aliphatic hydrocarbon group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [—CH2—], an ethylene group [—(CH2)2—], a trimethylene group [—(CH2)3—], a tetramethylene group [—(CH2)4—], and a pentamethylene group [—(CH2)5—].
The branched aliphatic hydrocarbon group has preferably 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkylalkylene groups, for example, 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—; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2CH(CH3)CH2—; and alkyltetramethylene groups such as —CH(CH3)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The linear or branched aliphatic hydrocarbon group may have a substituent or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, which has been substituted with a fluorine atom, and a carbonyl group.
Examples of the aliphatic hydrocarbon group containing a ring in the structure thereof include a cyclic aliphatic hydrocarbon group which may have a substituent containing a hetero atom in the ring structure thereof (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms and more preferably has 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The cyclic aliphatic hydrocarbon group may have or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and still more preferably a methoxy group or an ethoxy group.
The halogen atom as the substituent is preferably a fluorine atom.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of hydrogen atoms in the above-described alkyl groups have been substituted with the above-described halogen atom.
In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure thereof may be substituted with a substituent having a hetero atom. As the substituent having a hetero atom, —O—, —C(═O)—O—, —S—, —S(═O)2—, or —S(═O)2—O— is preferable.
Aromatic hydrocarbon group as Ya21
The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2)π electrons, and the aromatic ring may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably has 5 to 20 carbon atoms, still more preferably has 6 to 15 carbon atoms, and particularly preferably has 6 to 12 carbon atoms. Here, the number of carbon atoms in a substituent is not included in the number of carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting the above-described aromatic hydrocarbon ring with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the above-described aromatic hydrocarbon ring or aromatic heterocyclic ring (an arylene group or a heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound having two or more aromatic rings (for example, biphenyl or fluorene); and a group in which one hydrogen atom of a group (an aryl group or a heteroaryl group) obtained by removing one hydrogen atom from the above-described aromatic hydrocarbon ring or aromatic heterocyclic ring has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from an aryl group in arylalkyl groups such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably has 1 or 2 carbon atoms, and particularly preferably has 1 carbon atom.
In the aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable.
Examples of the alkoxy group, the halogen atom, and the halogenated alkyl group, as the substituent, include those described as the examples of the substituent that is substituted for a hydrogen atom contained in the cyclic aliphatic hydrocarbon group.
In a case where Ya21 represents a divalent linking group having a hetero atom, preferred examples of the linking group include —O—, —C(═O)—O—, —O—C(═O)—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH—, —NH—C(═NH)— (H may be substituted with a substituent such as an alkyl group or an acyl group), —S—, —S(═O)2—, —S(═O)2—O—, and a group represented by General Formula: —Y21—O—Y22—, —Y21—O—, —Y21—C(═O)—O—, —C(═O)—O—Y21—, —[Y21—C(═O)—O]m″—Y22—, —Y21—O—C(═O)—Y22—, or —Y21—S(═O)2—O—Y22— [in the formulae, Y21 and Y22 each independently represent a divalent hydrocarbon group which may have a substituent, 0 represents an oxygen atom, and m″ represents an integer in a range of 0 to 3].
When the divalent linking group including a hetero atom is —C(═O)—NH—, —C(═O)—NH—C(═O)—, —NH—, or —NH—C(═NH)—, H may be substituted with a substituent such as an alkyl group or an acyl group. The substituent (an alkyl group, an acyl group, or the like) preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and particularly preferably has 1 to 5 carbon atoms.
In General Formula —Y21—O—Y22—, —Y21—O—, —Y21—C(═O)—O—, —C(═O)—O—Y21—, —[Y21—C(═O)—O]m″—Y22, —Y21—O—C(═O)—Y22—, or —Y21—S(═O)2—O—Y22—, Y21 and Y22 each independently represent a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include those described as the divalent linking group (the divalent hydrocarbon group which may have a substituent) as Ya21.
Y21 represents preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.
Y22 represents preferably a linear or branched aliphatic hydrocarbon group and more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by Formula —[Y21—C(═O)—O]m″—Y22—, m″ represents an integer in a range of 0 to 3, preferably an integer in a range of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, a group represented by Formula —Y21—C(═O)—O—Y22— is particularly preferable as the group represented by Formula —[Y21—C(═O)—O]m″—Y22—. Among these, a group represented by Formula —(CH2)a′—C(═O)—O—(CH2)b′— is preferable. In the formula, a′ represents an integer in a range of 1 to 10, preferably an integer in a range of 1 to 8, more preferably an integer in a range of 1 to 5, still more preferably 1 or 2, and most preferably 1. b′ represents an integer in a range of 1 to 10, preferably an integer in a range of 1 to 8, more preferably an integer in a range of 1 to 5, still more preferably 1 or 2, and most preferably 1.
Among the examples, it is preferable that Ya21 represent a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof.
In General Formula (a2-1), Ra21 represents a lactone-containing cyclic group, a —SO2—-containing cyclic group, or a carbonate-containing cyclic group.
Suitable examples of the lactone-containing cyclic group, the —SO2— containing cyclic group, and the carbonate-containing cyclic group as Ra21 include the above-described group represented by each of General Formulae (a2-r-1) to (a2-r-7), a group represented by each of General Formulae (a5-r-1) to (a5-r-4), and a group represented by each of General Formulae (ax3-r-1) to (ax3-r-3).
Among the examples, the lactone-containing cyclic group or the —SO2— containing cyclic group is preferable, a group represented by each of General Formulae (a2-r-1), (a2-r-2), (a2-r-6), and (a5-r-1) is more preferable, and a group represented by each of General Formulae (a2-r-2) and (a5-r-1) is still more preferable. Specifically, any group represented by each of Chemical Formulae (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r-lc-6-1), (r-sl-1-1), or (r-sl-1-18), is preferable, any group represented by each of Chemical Formulae (r-lc-2-1) to (r-lc-2-18), or (r-sl-1-1) is more preferable, and any group represented by each of Chemical Formula (r-lc-2-1), (r-lc-2-12), or (r-sl-1-1) is still more preferable.
The constitutional unit (a2) contained in the component (A1) may be one kind or may be two or more kinds.
In a case where the component (A1) has the constitutional unit (a2), the proportion of the constitutional unit (a2) is preferably in a range of 5% to 60% by mole, more preferably in a range of 10% to 60% by mole, still more preferably in a range of 20% to 60% by mole, and particularly preferably in a range of 30% to 60% by mole with respect to the total (100% by mole) of all constitutional units constituting the component (A1).
In a case where the proportion of the constitutional unit (a2) is equal to or larger than the lower limit value of the above-described preferred range, the effect obtained by allowing the constitutional unit (a2) to be contained can be sufficiently achieved by the effect described above. In a case where the proportion of the constitutional unit (a2) is equal to or smaller than the upper limit value of the above-described preferred range, balance with other constitutional units can be obtained, and various lithography characteristics are improved.
The component (A1) may further have, as necessary, a constitutional unit (a3) (however, a constitutional unit corresponding to the constitutional unit (a1) or the constitutional unit (a2) is excluded) containing a polar group-containing aliphatic hydrocarbon group, in addition to the constitutional unit (a1). In a case where the component (A1) has the constitutional unit (a3), the hydrophilicity of the component (A) is increased, which contributes to an improvement in resolution. In addition, acid diffusion length can be appropriately adjusted.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group have been substituted with a fluorine atom, and the polar group is particularly preferably a hydroxyl group.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group (preferably an alkylene group) having 1 to 10 carbon atoms, and a cyclic aliphatic hydrocarbon group (a cyclic group). The cyclic group may be a monocyclic group or a polycyclic group. For example, these cyclic groups can be appropriately selected from a large number of groups that have been proposed in resins for a resist composition for an ArF excimer laser.
In a case where the cyclic group is a monocyclic group, the monocyclic group preferably has 3 to 10 carbon atoms. Among them, a constitutional unit derived from an acrylic acid ester that contains an aliphatic monocyclic group containing a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group have been substituted with a fluorine atom is particularly preferable. Examples of the monocyclic group include a group obtained by removing two or more hydrogen atoms from a monocycloalkane. Specific examples of the monocyclic group include a group obtained by removing two or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, or cyclooctane. Among these monocyclic groups, a group obtained by removing two or more hydrogen atoms from cyclopentane or a group obtained by removing two or more hydrogen atoms from cyclohexane are industrially preferable.
In a case where the cyclic group is a polycyclic group, the polycyclic group preferably has 7 to 30 carbon atoms. Among them, a constitutional unit derived from an acrylic acid ester that contains an aliphatic polycyclic group containing a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group have been substituted with a fluorine atom is particularly preferable. Examples of the polycyclic group include groups obtained by removing two or more hydrogen atoms from a bicycloalkane, tricycloalkane, tetracycloalkane, or the like. Specific examples thereof include a group obtained by removing two or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, or a group obtained by removing two or more hydrogen atoms from tetracyclododecane are industrially preferable.
The constitutional unit (a3) is not particularly limited, and any constitutional unit may be used as long as the constitutional unit contains a polar group-containing aliphatic hydrocarbon group.
The constitutional unit (a3) is a constitutional unit derived from an acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and a constitutional unit containing a polar group-containing aliphatic hydrocarbon group is preferable.
In a case where the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the constitutional unit (a3) is preferably a constitutional unit derived from a hydroxyethyl ester of acrylic acid.
In addition, as the constitutional unit (a3), in a case where the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, a constitutional unit represented by General Formula (a3-1), a constitutional unit represented by General Formula (a3-2), and a constitutional unit represented by General Formula (a3-3) are preferable, and in a case where the hydrocarbon group is a monocyclic group, a constitutional unit represented by General Formula (a3-4) is preferable.
[In the formulae, R has the same definition as described above, j represents an integer in a range of 1 to 3, k represents an integer in a range of 1 to 3, t′ represents an integer in a range of 1 to 3, 1 represents an integer in a range of 0 to 5, and s represents an integer in a range of 1 to 3.]
In General Formula (a3-1), j is preferably 1 or 2 and more preferably 1. In a case where j represents 2, it is preferable that the hydroxyl groups be bonded to the 3- and 5- positions of the adamantyl group. In a case where j represents 1, it is preferable that the hydroxyl group be bonded to the 3-position of the adamantyl group.
It is preferable that j represent 1, and it is particularly preferable that the hydroxyl group be bonded to the 3-position of the adamantyl group.
In General Formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5- or 6-position of the norbornyl group.
In General Formula (a3-3), it is preferable that t′ represent 1. It is preferable that l represent 1. It is preferable that s represent 1. Further, it is preferable that a 2-norbornyl group or 3-norbornyl group be bonded to the terminal of the carboxy group of the acrylic acid. It is preferable that the fluorinated alkyl alcohol be bonded to the 5-position or 6-position of the norbornyl group.
In General Formula (a3-4), it is preferable that t′ represent 1 or 2. It is preferable that l represent 0 or 1. It is preferable that s represent 1. It is preferable that the fluorinated alkyl alcohol be bonded to the 3- or 5-position of the cyclohexyl group.
The constitutional unit (a3) contained in the component (A1) may be one kind or may be two or more kinds.
In a case where the component (A1) has the constitutional unit (a3), the proportion of the constitutional unit (a3) is preferably in a range of 1% to 30% by mole, more preferably in a range of 2% to 25% by mole, and still more preferably in a range of 5% to 20% by mole, with respect to the total (100% by mole) of all constitutional units constituting the component (A1).
In a case where the proportion of the constitutional unit (a3) is equal to or larger than the lower limit value of the preferred range, the effect obtained by allowing the constitutional unit (a3) to be contained can be sufficiently achieved by the effect described above. In a case where the proportion of the constitutional unit (a3) is equal to or smaller than the upper limit value of the preferred range, balance with other constitutional units can be obtained, and various lithography characteristics are improved.
The component (A1) may further have, in addition to the constitutional unit (a1), a constitutional unit (a4) containing an acid non-dissociable aliphatic cyclic group.
In a case where the component (A1) has the constitutional unit (a4), the dry etching resistance of the formed resist pattern is improved. In addition, the hydrophobicity of the component (A) increases. The improvement in hydrophobicity contributes to the improvement in resolution, a resist pattern shape, and the like, particularly in the case of a solvent developing process.
The term “acid non-dissociable cyclic group” in the constitutional unit (a4) is a cyclic group that remains in the constitutional unit without being dissociated even when an acid acts in a case where an acid is generated in the resist composition by exposure (for example, in a case where an acid is generated from the constitutional unit that generates the acid upon exposure, or the component (B)).
Examples of the constitutional unit (a4) preferably include a constitutional unit derived from an acrylic acid ester including an acid non-dissociable aliphatic cyclic group. As the cyclic group, a large number of cyclic groups known in the related art as cyclic groups used as a resin component of a resist composition for an ArF excimer laser, KrF excimer laser (preferably an ArF excimer laser), or the like can be used.
The cyclic group is particularly preferably at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group, from the viewpoint of industrial availability. These polycyclic groups may have, as a substituent, a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples of the constitutional unit (a4) include constitutional units represented by General Formulae (a4-1) to (a4-7).
[In the formulae, R″ has the same definition as described above.]
The constitutional unit (a4) contained in the component (A1) may be one kind or may be two or more kinds.
In a case where the component (A1) has the constitutional unit (a4), the proportion of the constitutional unit (a4) is preferably in a range of 1% to 40% by mole and more preferably in a range of 5% to 20% by mole, with respect to the total (100% by mole) of all constitutional units constituting the component (A1).
In a case where the proportion of the constitutional unit (a4) is equal to or larger than the lower limit value of the preferred range, the effect that is obtained by allowing the constitutional unit (a4) to be contained can be sufficiently achieved. In a case where the proportion of the constitutional unit (a4) is equal to or smaller than the upper limit value of the preferred range, the balance with other constitutional units is obtained easily.
The constitutional unit (st) is a constitutional unit derived from styrene or a styrene derivative. “Constitutional unit derived from styrene” means a constitutional unit that is formed by the cleavage of an ethylenic double bond of styrene. “Constitutional unit derived from a styrene derivative” means a constitutional unit (provided that a constitutional unit corresponding to the constitutional unit (a10) is excluded) formed by the cleavage of an ethylenic double bond of a styrene derivative.
The term “styrene derivative” means a compound in which at least a part of hydrogen atoms of styrene are substituted with a substituent. Examples of the styrene derivative include a derivative in which the hydrogen atom at the α-position of styrene is substituted with a substituent, a derivative in which one or more hydrogen atoms of the benzene ring of styrene are substituted with a substituent, and a derivative in which the hydrogen atom at the α-position of styrene and one or more hydrogen atoms of the benzene ring are substituted with a substituent.
Examples of the substituent that is substituted for the hydrogen atom at the α-position of styrene include an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The halogenated alkyl group having 1 to 5 carbon atoms is a group obtained by substituting part or all of hydrogen atoms in the alkyl group having 1 to 5 carbon atoms with a halogen atom. The halogen atom is particularly preferably a fluorine atom.
The substituent that is substituted for the hydrogen atom at the α-position of styrene is preferably an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group from the viewpoint of industrial availability.
Examples of the substituent that is substituted for the hydrogen atom of the benzene ring of styrene include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and still more preferably a methoxy group or an ethoxy group.
The halogen atom as the substituent is preferably a fluorine atom.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of hydrogen atoms in the above-described alkyl groups have been substituted with the above-described halogen atom.
The substituent that is substituted for the hydrogen atom of the benzene ring of styrene is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
The constitutional unit (st) is preferably a constitutional unit derived from styrene or a constitutional unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a constitutional unit derived from styrene, or a constitutional unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with a methyl group, and still more preferably a constitutional unit derived from styrene.
The constitutional unit (st) contained in the component (A1) may be one kind or may be two or more kinds.
In a case where the component (A1) has the constitutional unit (st), the proportion of the constitutional unit (st) is preferably in a range of 1% to 30% by mole and more preferably in a range of 3% to 20% by mole with respect to the total (100% by mole) of all constitutional units constituting the component (A1).
The component (A1) contained in the resist composition may be used alone or in a combination of two or more kinds thereof.
In the resist composition according to the present embodiment, examples of the component (A1) include a polymeric compound having a repeating structure of the constitutional unit (a1), and preferred examples thereof include a polymeric compound having a repeating structure of the constitutional unit (a1) and the constitutional unit (a2).
Among them, suitable examples of the component (A1) include a polymeric compound consisting of a repeating structure of a constitutional unit (a1) and a constitutional unit (a2); and a polymeric compound consisting of a repeating structure of a constitutional unit (at), a constitutional unit (a2), and a constitutional unit (a3).
In the polymeric compound having a repeating structure of the constitutional unit (a1) and the constitutional unit (a2), the proportion of the constitutional unit (a1) is preferably in a range of 10% to 90% by mole, more preferably in a range of 20% to 80% by mole, still more preferably in a range of 30% to 70% by mole, and particularly preferably in a range of 40% to 70% by mole with respect to the total (100% by mole) of all constitutional units constituting the polymeric compound.
In addition, the proportion of the constitutional unit (a2) in each of the polymeric compounds described above is preferably in a range of 10% to 90% by mole, more preferably in a range of 20% to 80% by mole, still more preferably in a range of 30% to 70% by mole, and particularly preferably in a range of 30% to 60% by mole, with respect to the total (100% by mole) of all constitutional units constituting the polymeric compound.
In the polymeric compound having a repeating structure of the constitutional unit (a1), the constitutional unit (a2), and the constitutional unit (a3), the proportion of the constitutional unit (a1) is preferably in a range of 20% to 80% by mole, more preferably in a range of 30% to 70% by mole, still more preferably in a range of 40% to 60% by mole, and particularly preferably in a range of 45% to 55% by mole with respect to the total (100% by mole) of all constitutional units constituting the polymeric compound.
In addition, the proportion of the constitutional unit (a2) in each of the polymeric compounds described above is preferably in a range of 10% to 70% by mole, more preferably in a range of 20% to 60% by mole, still more preferably in a range of 30% to 50% by mole, and particularly preferably in a range of 35% to 45% by mole, with respect to the total (100% by mole) of all constitutional units constituting the polymeric compound.
In addition, the proportion of the constitutional unit (a3) in the polymeric compound described above is preferably in a range of 1% to 30% by mole, more preferably in a range of 5% to 25% by mole, still more preferably in a range of 5% to 20% by mole, and particularly preferably in a range of 5% to 15% by mole, with respect to the total (100% by mole) of all constitutional units constituting the polymeric compound.
The molar ratio of the constitutional unit (a1) to the constitutional unit (a2) in the polymeric compound (the constitutional unit (a1): the constitutional unit (a2)) is preferably in a range of 2:8 to 8:2, more preferably in a range of 3:7 to 7:3, and still more preferably in a range of 4:6 to 6:4.
The component (A1) can be produced by dissolving, in a polymerization solvent, each monomer from which the constitutional unit is derived, and adding thereto a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (for example, V-601) to carry out polymerization.
Alternatively, the component (A1) can be produced by dissolving, in a polymerization solvent, a monomer from which the constitutional unit (a1) is derived and, as necessary, a monomer from which a constitutional unit (for example, the constitutional unit (a2)) other than the constitutional unit (a1) is derived, and adding thereto such a radical polymerization initiator as described above to carry out polymerization.
It is noted that a —C(CF3)2—OH group may be introduced into the terminal during the polymerization by using, in combination, a chain transfer agent such as HS—CH2—CH2—CH2—C(CF3)2—OH. As described above, a copolymer into which a hydroxyalkyl group, formed by substitution of a part of hydrogen atoms in the alkyl group with fluorine atoms, has been introduced is effective for reducing development defects and reducing line edge roughness (LER: uneven irregularities of a line side wall).
The weight average molecular weight (Mw) (in terms of the polystyrene equivalent value determined by gel permeation chromatography (GPC)) of the component (A1), which is not particularly limited, is preferably in a range of 1,000 to 50,000, more preferably in a range of 2,000 to 30,000, and still more preferably in a range of 3,000 to 20,000.
In a case where Mw of the component (A1) is equal to or smaller than the upper limit value of this preferred range, the resist composition exhibits sufficient solubility in a resist solvent such that the resist composition can be used as a resist. On the other hand, in a case where Mw thereof is equal to or larger than the lower limit value of this preferred range, dry etching resistance and the cross-sectional shape of the resist pattern become excellent.
Further, the polydispersity (Mw/Mn) of the component (A1) is not particularly limited; however, it is preferably in a range of 1.0 to 4.0, more preferably in a range of 1.0 to 3.0, and particularly preferably in a range of 1.0 to 2.0. It is noted that Mn represents the number average molecular weight.
In the resist composition according to the present embodiment, a base material component (hereinafter, referred to as a “component (A2)”) that exhibits changed solubility in a developing solution under action of an acid, which does not correspond to the component (A1), may be used in combination as the component (A).
The component (A2) is not particularly limited and may be freely selected from a large number of base material components for the chemical amplification-type resist composition known in the related art and used.
As the component (A2), a polymeric compound or a low molecular weight compound may be used alone or in a combination of two or more kinds thereof.
The proportion of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, and still more preferably 75% by mass or more, and it may be 100% by mass with respect to the total mass of the component (A). In a case where the proportion is 25% by mass or more, a resist pattern having various excellent lithography characteristics such as high sensitivity, resolution, and roughness amelioration can be easily formed.
The content of the component (A) in the resist composition according to the present embodiment may be adjusted depending on the resist film thickness to be formed.
The resist composition according to the present embodiment contains an acid diffusion controlling agent component (hereinafter, referred to as a component (D)). The component (D) acts as a quencher (an acid diffusion controlling agent) which traps the acid generated in the resist composition upon exposure. The resist composition according to the present embodiment contains a photodecomposable base (D0) (hereinafter, referred to as a “component (D0)”) as the component (D).
The component (D0) is a compound that decomposes upon exposure and loses acid diffusion controllability. In exposed portions, the component (D0) decomposes and loses acid diffusion controllability; however, in unexposed portions, it traps an acid generated in the exposed portions. This makes it possible to improve the contrast between the exposed portions and the unexposed portions in the resist film. The component (D0) can reduce the occurrence of WMDs by being used in combination with the component (F0) that will be described later.
The component (D0) is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability. The component (D0) is preferably one or more compounds selected from the group consisting of a compound represented by General Formula (d0-1) (hereinafter, referred to as a “component (d0-1)”), a compound represented by General Formula (d0-2) (hereinafter, referred to as a “component (d0-2)”), a compound represented by General Formula (d0-3) (hereinafter, referred to as a “component (d0-3)”), a compound represented by General Formula (d0-4) (hereinafter, referred to as a “component (d0-4)”), a compound represented by General Formula (d0-5) (hereinafter, referred to as a “component (d0-5)”), and a compound represented by General Formula (d0-6) (hereinafter, referred to as a “component (d0-6)”).
[In the formulae, Rd01, Rd02, Rd031, Rd032, and Rd041 to Rd043 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. However, no fluorine atom is bonded to the carbon atom adjacent to a sulfur atom in Rd02 of General Formula (d0-2). Rd031 and Rd032 may be bonded to each other to form a ring structure. Yd03 represents a single bond or a divalent linking group. Rd051, Rd052, and Rd061 to Rd063 each independently represent an aromatic hydrocarbon group which may have a substituent. m represents an integer of 1 or more, and Mm+'s each independently represent an m-valent organic cation].
{Component (d0-1)}
[In General Formula (d01-1), Rd01 represents a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.
Cyclic Group which May have Substituent:
The cyclic group as Rd01 is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group indicates a hydrocarbon group that has no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group be saturated.
The aromatic hydrocarbon group as Rd01 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably has 5 to 30 carbon atoms, still more preferably has 5 to 20 carbon atoms, particularly preferably has 6 to 15 carbon atoms, and most preferably has 6 to 10 carbon atoms. Here, the number of carbon atoms in a substituent is not included in the number of carbon atoms.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group as Rd01 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting any of these aromatic rings with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group as Rd01 include a group in which one hydrogen atom has been removed from the aromatic ring (an aryl group such as a phenyl group or a naphthyl group), and a group in which one hydrogen atom in the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group (an alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably has 1 or 2 carbon atoms, and particularly preferably has 1 carbon atom.
Examples of the cyclic aliphatic hydrocarbon group as Rd01 include an aliphatic hydrocarbon group having a ring in the structure thereof.
Examples of the aliphatic hydrocarbon group containing a ring in the structure thereof include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which the alicyclic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the alicyclic hydrocarbon group is interposed in a linear or branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among the above, the polycycloalkane is more preferably a polycycloalkane having a bridged ring-based polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a condensed ring-based polycyclic skeleton, such as a cyclic group having a steroid skeleton.
Among these examples, as the cyclic aliphatic hydrocarbon group as Rd01, a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane is preferable, a group in which one hydrogen atom has been removed from a polycycloalkane is more preferable, an adamantyl group or a norbornyl group is particularly preferable, and an adamantyl group is most preferable.
The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 4 carbon atoms, and particularly preferably has 1 to 3 carbon atoms.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [—CH2—], an ethylene group [—(CH2)2—], a trimethylene group [—(CH2)3—], a tetramethylene group [—(CH2)4—], and a pentamethylene group [—(CH2)5—].
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkylalkylene groups, for example, 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—; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2CH(CH3)CH2—; and alkyltetramethylene groups such as —CH(CH3)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
In addition, the cyclic hydrocarbon group as Rd01 may have a hetero atom such as a heterocyclic ring. Specific examples thereof include the lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7), the —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4), and another heterocyclic group represented by each of Chemical Formulae (r-hr-1) to (r-hr-16). In the formulae, * represents a bonding site for bonding to a carbon atom in General Formula (d01-1).
The cyclic hydrocarbon group as Rd01 may include a substituent. Examples of the above substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
The halogen atom as the substituent is preferably a fluorine atom.
Examples of the above-described halogenated alkyl group as the substituent include a group in which part or all of hydrogen atoms in an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group have been substituted with the above-described halogen atom.
The carbonyl group as the substituent is a group that substitutes a methylene group (—CH2—) constituting the cyclic hydrocarbon group.
Chain-Like Alkyl Group which May have Substituent:
The chain-like alkyl group as Rd01 may be linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples thereof include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
Chain-Like Alkenyl Group which May have Substituent:
The chain-like alkenyl group as Rd01 may be linear or branched.
The linear alkenyl group preferably has 2 to 10 carbon atoms, more preferably has 2 to 5 carbon atoms, still more preferably has 2 to 4 carbon atoms, and particularly preferably has 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (an allyl group), and a butynyl group.
The branched alkenyl group preferably has 3 to 10 carbon atoms, more preferably has 3 to 5 carbon atoms, still more preferably has 3 or 4 carbon atoms, and particularly preferably has 3 carbon atoms. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group.
Among the above, the chain-like alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.
The chain-like alkyl group or alkenyl group as Rd01 may have a substituent. Examples of the substituent of the cyclic group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group as Rd01.
Rd01 may be the same ones as those described as Ra′4 in General Formula (a1-r-2) described above.
Among the above, Rd01 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specific preferred examples thereof include a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7), and a —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4).
Among these, it is preferable that Rd01 represents an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent. Examples of the substituent that may be included in these groups include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, the lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7), an ether bond, an ester bond, and a combination thereof. In a case where the substituent contains an ether bond and/or an ester bond, these bonds may be bonded to an alkylene group. For example, the substituent may include a linking group represented by any one of Formulae (y-a1-1) to (y-a1-5).
[In the formulae, V′101 represents a single bond or an alkylene group having 1 to 5 carbon atoms, and V′102 represents a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]
As the divalent saturated hydrocarbon group as V′102, an alkylene group having 1 to 30 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 5 carbon atoms is still more preferable.
The alkylene group as V′101 and V′102 may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferable.
Specific examples of the alkylene group as V′101 and V′102 include a methylene group [—CH2—]; an alkylmethylene group such as —CH(CH3)—, —CH(CH2CH3)—, —C(CH3)2—, —C(CH3)(CH2CH3)—, —C(CH3)(CH2CH2CH3)—, or —C(CH2CH3)2—; an ethylene group [—CH2CH2—]; an alkylethylene group such as —CH(CH3)CH2—, —CH(CH3)CH(CH3)—, —C(CH3)2CH2—, or —CH(CH2CH3)CH2—; a trimethylene group (n-propylene group) [—CH2CH2CH2—]; an alkyltrimethylene group such as —CH(CH3)CH2CH2— or —CH2CH(CH3)CH2—; a tetramethylene group [—CH2CH2CH2CH2—]; an alkyltetramethylene group such as —CH(CH3)CH2CH2CH2— or —CH2CH(CH3)CH2CH2—; and a pentamethylene group [—CH2CH2CH2CH2CH2—].
In addition, a part of methylene groups in the alkylene group as V′101 and V′102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. As the aliphatic cyclic group, a divalent group in which one hydrogen atom has been further removed from the cyclic aliphatic hydrocarbon group (a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group) as Ra′3 in General Formula (a1-r-1) is preferable, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferable.
Suitable examples of the aromatic hydrocarbon group as Rd01 include a phenyl group, a naphthyl group, and a polycyclic structure (a polycyclic structure including a bicyclooctane skeleton and a ring structure other than the bicyclooctane skeleton) including a bicyclooctane skeleton. The aromatic hydrocarbon group preferably has a hydroxyl group as a substituent.
The aliphatic cyclic group as Rd01 is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The chain-like alkyl group preferably as Rd01 has 1 to 10 carbon atoms, and specific examples thereof include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group, and a branched alkyl group such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, or a 4-methylpentyl group.
In a case where the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the fluorinated alkyl group preferably has 1 to 11 carbon atoms, more preferably has 1 to 8 carbon atoms, and still more preferably has 1 to 4 carbon atoms. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of the atom other than a fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the anion moiety of the component (d01-1) are shown below; however, the specific examples thereof are not limited thereto.
In General Formula (d01-1), Mm+ represents an m-valent organic cation. Mm+ is preferably a sulfonium cation or an iodonium cation. m represents an integer of 1 or more.
Preferred examples of the cation moiety ((Mm+)1/m) include an organic cation represented by each of General Formulae (ca-1) to (ca-5).
[In the formulae, R201 to R207, R211, and R212 each independently represent an aryl group, an alkyl group, or an alkenyl group which may have a substituent. R201 to R203, R206 and R207, and R211 and R212 may be bonded to each other to form a ring with the sulfur atom in the formulae. R208 and R209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R210 represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an SO2— containing cyclic group which may have a substituent. L201 represents —C(═O)— or —C(═O)—O—. Y201's each independently represent an arylene group, an alkylene group, or an alkenylene group. x represents 1 or 2. W201 represents an (x+1)-valent linking group.]
In General Formulae (ca-1) to (ca-5), examples of the aryl group as R201 to R207, R211, and R212 include an unsubstituted aryl group having 6 to 20 carbon atoms. Among these, a phenyl group or a naphthyl group is preferable.
The alkyl group as R201 to R207, R211, and R212 is a chain-like or cyclic alkyl group, and the number of carbon atoms thereof is preferably in a range of 1 to 30.
It is preferable that the alkenyl group as R201 to R207, R211, and R212 have 2 to 10 carbon atoms.
Examples of the substituent which may be contained in R201 to R207 and R210 to R212 include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by General Formulae (ca-r-1) to (ca-r-7).
[In the formulae, R′201's each independently represent a hydrogen atom, a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.]
Cyclic Group which May have Substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group indicates a hydrocarbon group that has no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group be saturated.
The aromatic hydrocarbon group as R′201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably has 5 to 30 carbon atoms, still more preferably has 5 to 20 carbon atoms, particularly preferably has 6 to 15 carbon atoms, and most preferably has 6 to 10 carbon atoms. Here, the number of carbon atoms in a substituent is not included in the number of carbon atoms.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group as R′201 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring obtained by substituting a part carbon atoms constituting any of these aromatic rings with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group as R′201 include a group in which one hydrogen atom has been removed from the aromatic ring (an aryl group such as a phenyl group or a naphthyl group), and a group in which one hydrogen atom in the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group (an alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably has 1 or 2 carbon atoms, and particularly preferably has 1 carbon atom.
Examples of the cyclic aliphatic hydrocarbon group as R′201 include an aliphatic hydrocarbon group having a ring in the structure thereof.
Examples of the aliphatic hydrocarbon group containing a ring in the structure thereof include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which the alicyclic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the alicyclic hydrocarbon group is interposed in a linear or branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among the above, the polycycloalkane is more preferably a polycycloalkane having a bridged ring-based polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a condensed ring-based polycyclic skeleton, such as a cyclic group having a steroid skeleton.
Among these examples, as the cyclic aliphatic hydrocarbon group as R′201, a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane is preferable, a group in which one hydrogen atom has been removed from a polycycloalkane is more preferable, an adamantyl group or a norbornyl group is particularly preferable, and an adamantyl group is most preferable.
The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 4 carbon atoms, and particularly preferably has 1 to 3 carbon atoms.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [—CH2—], an ethylene group [—(CH2)2—], a trimethylene group [—(CH2)3—], a tetramethylene group [—(CH2)4—], and a pentamethylene group [—(CH2)5—].
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkylalkylene groups, for example, 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—; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2CH(CH3)CH2—; and alkyltetramethylene groups such as —CH(CH3)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
In addition, the cyclic hydrocarbon group as R′201 may have a hetero atom such as a heterocyclic ring. Specific examples thereof include the lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7), the —SO2—-containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4), and other heterocyclic group represented by each of Chemical Formulae (r-hr-1) to (r-hr-16).
Examples of the substituent for the cyclic group as R′201 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
The halogen atom as the substituent is preferably a fluorine atom.
Examples of the above-described halogenated alkyl group as the substituent include a group in which part or all of hydrogen atoms in an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group have been substituted with the above-described halogen atom.
The carbonyl group as the substituent is a group that substitutes a methylene group (—CH2—) constituting the cyclic hydrocarbon group.
Chain-Like Alkyl Group which May have Substituent:
The chain-like alkyl group as R′201 may be linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples thereof include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
Chain-Like Alkenyl Group which May have Substituent:
The chain-like alkenyl group as R′201 may be linear or branched, and the number of carbon atoms thereof is preferably in a range of 2 to 10, more preferably in a range of 2 to 5, still more preferably in a range of 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (an allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group.
Among the above, the chain-like alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.
Examples of the substituent for the chain-like alkyl group or alkenyl group as R′201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a cyclic group as R′201.
Examples of the cyclic group which may have a substituent, the chain-like alkyl group which may have a substituent, and the chain-like alkenyl group which may have a substituent as R′201 include those for the acid dissociable group represented by General Formula (a1-r-2) which are the exemplary examples of the cyclic group which may have a substituent and the chain-like alkyl group which may have a substituent, in addition to those described above.
Among the examples, R′201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specific preferred examples thereof include a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7), and a —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4).
In General Formulae (ca-1) to (ca-5), in a case where R201 to R203, R206 and R207, and R211 and R212 are bonded to each other to form a ring with a sulfur atom in the formula, these groups may be bonded to each other via a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a functional group such as a carbonyl group, —SO—, —SO2—, —SO3—, —COO—, —CONH— or —N(RN)— (here, RN represents an alkyl group having 1 to 5 carbon atoms). Regarding the ring to be formed, it is preferable that a ring containing the sulfur atom in the formula in the ring skeleton thereof be a 3- to 10-membered ring and it is particularly preferable that it be a 5- to 7-membered ring, in a case where the sulfur atom is included. Specific examples of the ring to be formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.
R208 and R209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In a case where R208 and R209 represent an alkyl group, R208 and R209 may be bonded to each other to form a ring.
R210 represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a SO2—-containing cyclic group which may have a substituent.
Examples of the aryl group as R210 include an unsubstituted aryl group having 6 to 20 carbon atoms. Among these, a phenyl group or a naphthyl group is preferable.
The alkyl group as R210 is preferably a chain-like or cyclic alkyl group, which preferably has 1 to 30 carbon atoms.
It is preferable that the alkenyl group as R210 have 2 to 10 carbon atoms. As the —SO2— containing cyclic group as R210 which may have a substituent, “a —SO2— containing polycyclic group” is preferable, and a group represented by General Formula (a5-r-1) is more preferable.
Y201's each independently represent an arylene group, an alkylene group, or an alkenylene group.
Examples of the arylene group as Y201 include a group obtained by removing one hydrogen atom from the aryl group described as the example of the aromatic hydrocarbon group represented by R101 in General Formula (b-1) that will be described later.
Examples of the alkylene group and alkenylene group as Y201 include a group obtained by removing one hydrogen atom from the group described as the example of the chain-like alkyl group or the chain-like alkenyl group as R101 in General Formula (b-1) that will be described later.
In General Formula (ca-4), x represents 1 or 2.
W201 represents an (x+1)-valent linking group, that is, a divalent or trivalent linking group.
As the divalent linking group represented by W201, a divalent hydrocarbon group which may have a substituent is preferable, and examples thereof include the same divalent hydrocarbon groups which may have a substituent as those for Ya21 in General Formula (a2-1). The divalent linking group as W201 may be either linear, branched, or cyclic, and is preferably cyclic. Among these, a group in which two carbonyl groups are combined with both ends of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group. Among these, a phenylene group is particularly preferable.
Examples of the trivalent linking group as W201 include a group in which one hydrogen atom has been removed from the above-described divalent linking group as W201 and a group obtained by bonding the divalent linking group to another divalent linking group described above. As the trivalent linking group as W201, a group obtained by bonding two carbonyl groups to an arylene group is preferable.
Specific examples of the suitable cation represented by General Formula (ca-1) include a cation represented by each of Chemical Formulae (ca-1-1) to (ca-1-70) shown below.
[In the formulae, g1, g2, and g3 represent the numbers of repetitions, g1 is an integer in a range of 1 to 5, g2 is an integer in a range of 0 to 20, and g3 is an integer in a range of 0 to 20. ]
[In the formulae, R″201 represents a hydrogen atom or a substituent, and examples of the substituent include the same groups as those for the substituents which may be contained in R201 to R207 and R210 to R212.
Specific examples of the suitable cation represented by General Formula (ca-2) include a diphenyliodonium cation and a bis(4-tert-butylphenyl)iodonium cation.
Specific examples of the suitable cation represented by General Formula (ca-3) include a cation represented by each of General Formulae (ca-3-1) to (ca-3-6).
Specific examples of the suitable cation represented by General Formula (ca-4) include a cation represented by each of General Formulae (ca-4-1) and (ca-4-2) shown below.
Specific examples of the suitable cation represented by General Formula (ca-5) include a cation represented by each of General Formulae (ca-5-1) to (ca-5-3) shown below.
Among the above, the cation moiety ((Mm+)1/m) is preferably a cation represented by General Formula (ca-1), more preferably the cation represented by each of General Formula (ca-1-1) to (ca-1-70), and still more preferably the cation represented by each of General Formula (ca-1-1) to (ca-1-47).
{Component (d0-2)}
In General Formula (d0-2), Rd02 represents a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples thereof include the same ones as R′201.
However, no fluorine atom is bonded to the carbon atom adjacent to the S atom in Rd02 (the carbon atom is not substituted with fluorine). As a result, the anion of the component (d0-2) becomes an appropriately weak acid anion, thereby improving the quenching ability of the component (D).
It is preferable that Rd02 represent a chain-like alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent. The chain-like alkyl group preferably has 1 to 10 carbon atoms and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is more preferably a group (which may have a substituent) obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; and a group obtained by removing one or more hydrogen atoms from camphor or the like.
The hydrocarbon group as Rd02 may have a substituent, and examples of the substituent include the same ones as the substituent which may be contained in the hydrocarbon group (such as an aromatic hydrocarbon group, an aliphatic cyclic group, or a chain-like alkyl group) as Rd01 in General Formula (d0-1).
Specific examples of the preferred anion moiety for the component (d0-2) are shown below.
In General Formula, (d0-2), Mm+ represents an m-valent organic cation and is the same as Mm+ in General Formula (d0-1).
{Component (d0-3)}
[In General Formula (d0-3), Rd031 and Rd032 each independently represents a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. Examples of Rd031 and Rd032 include the same ones as R′201.
Rd032 is preferably a cyclic group containing a fluorine atom, a chain-like alkyl group, or a chain-like alkenyl group. Among these, Rd031 is preferably a fluorinated alkyl group, and more preferably the same ones as the fluorinated alkyl group represented by Rd01.
Rd032 is preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a cyclic group which may have a substituent.
Rd031 and Rd032 may be bonded to each other to form a ring structure together with -Yd03-N—SO2—. The ring structure formed by the bonding of Rd031 and Rd032 together with -Yd03-N—SO2— is preferably an aliphatic ring. The aliphatic ring may be a saturated aliphatic ring or may contain an unsaturated bond; however, it is preferably a saturated aliphatic ring. The aliphatic ring preferably has 2 to 10 carbon atoms, more preferably has 3 to 8 carbon atoms, still more preferably has 3 to 6 carbon atoms, and particularly preferably has 3 or 4 carbon atoms.
In General Formula (d0-3), Yd03 represents a single bond or a divalent linking group.
The divalent linking group as Yd03 is not particularly limited, and examples thereof include a divalent hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group) which may have a substituent, and a divalent linking group having a hetero atom. These include the same ones as the divalent hydrocarbon group which may have a substituent and the divalent linking group having a hetero atom, which are described for the divalent linking group as Ya21 in General Formula (a2-1).
It is preferable that Yd03 represent a carbonyl group, an ester bond, an amide bond, an alkylene group, a sulfonyl group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and still more preferably a methylene group or an ethylene group.
The component (d0-3) is preferably a compound represented by General Formula (d0-3-1).
[In the formula, Rd031 and Rd032 are the same as those in General Formula (d0-3). m represents an integer of 1 or more, and Mm+'s each independently represent an m-valent organic cation].
In General Formula (d0-3), Rd031 and Rd032 are the same as those in General Formula (d0-3).
Rd031 and Rd032 are preferably a chain-like alkyl group which may have a substituent. The alkyl group preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, still more preferably has 1 to 6 carbon atoms, and particularly preferably has 1 to 4 carbon atoms.
Rd031 and Rd032 may be bonded to each other to form a ring structure together with SO2—N—SO2—.
Specific examples of the preferred anion moiety for the component (d0-3) are shown below.
In General Formula (d0-3), Mm+ represents an m-valent organic cation and is the same as Mm+ in General Formula (d0-1).
{Component (d0-4)}
[In General Formula (d0-4), Rd041 to Rd043 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. Examples of Rd041 to Rd043 include the same ones as R′201.
Rd041 to Rd043 are preferably a chain-like alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent. The chain-like alkyl group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 4 carbon atoms, and particularly preferably has 1 to 3 carbon atoms. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; and a group obtained by removing one or more hydrogen atoms from camphor or the like. The chain-like alkyl group or the aliphatic cyclic group, as Rd141 to Rd043, may have a substituent or may not have a substituent. Examples of the substituent include the same ones as the substituent in R′201.
A specific example of the preferred anion moiety for the component (d0-4) is shown below.
In General Formula (d0-4), Mm+ represents an m-valent organic cation and is the same as Mm+ in General Formula (d0-1).
{Component (d0-5)}
In General Formula (d0-5), Rd051 and Rd052 each independently represent an aromatic hydrocarbon group.
Rd051 represents a monovalent aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group as Rd051 include the same ones as the aromatic hydrocarbon group as R′201.
Rd052 represents a divalent aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group as Rd052 include a group obtained by removing two hydrogen atoms from the above-described aromatic ring (an arylene group); and a group in which one hydrogen atom of a group (an aryl group) formed by removing one hydrogen atom from the aromatic ring has been substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group (an alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably has 1 or 2 carbon atoms, and particularly preferably has 1 carbon atom.
Examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocyclic ring obtained by substituting a part of carbon atoms constituting the above-described aromatic hydrocarbon ring with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom.
A preferred specific example of the component (d0-5) is shown below.
{Component (d0-6)}
In General Formula (d0-6), Rd061 to Rd063 each independently represent an aromatic hydrocarbon group.
Rd061 and Rd062 each independently represent a monovalent aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group as Rd061 and Rd162 include the same ones as the aromatic hydrocarbon group as R′201.
Rd063 represents a divalent aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group as Rd063 include the same ones as Rd052.
A preferred specific example of the component (d0-6) is shown below.
The component (D0) is preferably a component having a highly hydrophobic anion moiety. For example, an interaction distance Ra between a Hansen solubility parameter of a compound in which the anion moiety of the component (D0) is protonated (a compound in which a proton is bonded to the anion moiety of the component (D0)) and a Hansen solubility parameter of water may be 20 or more. The interaction distance Ra between the Hansen solubility parameter of the component (D0) and the Hansen solubility parameter of water may be 25 or more, 26 or more, 27 or more, 28 or more, 29 or more, 30 or more, 31 or more, 32 or more, 33 or more, 34 or more, 35 or more, or 36 or more. The upper limit value of the interaction distance Ra is not particularly limited. The interaction distance Ra may be, for example, 45 or less, 42 or less, 40 or less, 39 or less, 38 or less, or 37 or less. The compound in which the anion moiety of the component (D0) is protonated is a compound in which a proton is bonded to the anion moiety of the component (D0).
The Hansen solubility parameter can be calculated from predetermined parameters based, for example, on solubility parameters and aggregation properties as described by Charles Hansen in Charles M. Hansen's “Hansen Solubility Parameters: A User's Handbook”, CRC Press (2007) and “The CRC Handbook and Solubility Parameters and Cohesion Parameters,” (1999) edited by Allan F. M. Barton (1999).
The Hansen solubility parameter is theoretically calculated as a numerical constant and is a useful tool for predicting the ability of a solvent material to dissolve a particular solute.
The Hansen solubility parameters can be a measure of the overall strength and selectivity of a material by combining the following three experimentally and theoretically derived Hansen solubility parameters (that is, δD, δP, and δH). The units for the Hansen solubility parameter are given in MPa 0.5 or (J/cc) 0.5.
These three parameters (that is, δD, δP, and δH) are plotted as coordinates for points in three dimensions, also known as the Hansen space.
Within this three-dimensional space (Hansen space), the closer two molecules are, the more likely the two molecules are to dissolve into each other. In order to evaluate whether two molecules (molecules (1) and (2)) come closer to each other in the Hansen space, the interaction distance (Ra) between the Hansen solubility parameters is determined. Ra is calculated by the following Formula.
[In the expression,
The Hansen solubility parameters of the compound in which the anion moiety of the component (D0) is protonated and the water can be calculated with “Molecular Modeling Pro” software, version 5.1.9 (ChemSW, Fairfield CA, www.chemsw.com), Hansen Solubility from Dynacomp Software, or the like.
Specific examples of the component (D01) are shown below; however, the specific examples thereof are not limited thereto. Ra indicates the interaction distance (Ra) between the Hansen solubility parameter of the compound in which the anion moiety is protonated and the Hansen solubility parameter of water.
Ra indicated for the compound (D0-9) was calculated from the following compound having a structure obtained after photodecomposition.
In the resist composition according to the present embodiment, the component (D0) may be used alone or in a combination of two or more kinds thereof.
The content of the component (D0) in the resist composition according to the present embodiment is preferably 0.5 to 20 parts by mass, more preferably in a range of 1 to 15 parts by mass, and still more preferably in a range of 2 to 10 parts by mass, with respect to 100 parts by mass of the component (A1).
In a case where the content of the component (D0) is equal to or larger than the lower limit value of the above-described preferred range, the resolution of the pattern is easily maintained. On the other hand, when it is equal to or smaller than the upper limit value of the above-described preferred range, the sensitivity of the resist composition is easily maintained favorably.
A method for producing the component (D0) described above is not particularly limited, and the component (D0) can be produced by a conventionally known method.
The resist composition according to the present embodiment contains a fluorine additive component (hereinafter, referred to as a “component (F)”). The component (F) is used to impart water repellency to the resist film, where it is used as a resin different from the component (A) to improve lithography characteristics. The resist composition according to the present embodiment contains the component (F0) as the component (F).
The component (F0) is a polymeric compound having a constitutional unit (f01) represented by General Formula (f01-1) and a constitutional unit (f02) represented by General Formula (f02-1).
[In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Vf01 represents an alkylene group having 1 to 10 carbon atoms or a halogenated alkylene group having 1 to 5 carbon atoms, and Yf01 represents —CO—O— or —O—CO—. Rf01 represents an organic group containing a fluorine atom, and nf01 represents an integer in a range of 0 to 5.]
[In the formulae, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Vf02 represents a divalent hydrocarbon group which may have a substituent. nf02 represents an integer in a range of 0 to 2. Rf02 represents an acid dissociable group represented by General Formula (f02-r1-1). Rf021 and Rf022 each independently represent a hydrocarbon group which may have a substituent. Rf021 and Rf022 may be bonded to each other to form a ring structure. Yf02 represents a quaternary carbon atom. Rf023, Rf024, and Rf025 each independently represent a hydrocarbon group which may have a substituent. * represents a bonding site for bonding to an oxygen atom to which Rf02 in General Formula (f02-1) is bonded.]
Constitutional Unit (f01)
In General Formula (f01-1), R is as described above. R is preferably a hydrogen atom or a methyl group.
In General Formula (f0-1), Vf01 represents an alkylene group having 1 to 10 carbon atoms or a halogenated alkylene group having 1 to 5 carbon atoms. The halogenated alkylene group is preferably a fluorinated alkylene group. As Vf01, the alkylene group having 1 to 10 carbon atoms or the halogenated alkylene group having 1 to 5 carbon atoms preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, and still more preferably has 1 to 3 carbon atoms. Examples of the halogenated alkylene group as Vf01 include a group obtained by substituting part or all of hydrogen atoms in the alkylene group having 1 to 10 carbon atoms with a halogen atom. The halogen atom is preferably a fluorine atom. Specific examples of Vf01 include a methylene group, an ethylene group, —CF2—, —CH2CF2—, —CH(CH3)CF2—, and —CH(CH2CH3)CF2—.
In General Formula (f0-1), Yf01 represents —CO—O— or —O—CO—.
In General Formula (f0-1), nf01 represents an integer in a range of 0 to 5. nf01 is preferably an integer in a range of 0 to 3 and more preferably 0, 1, or 2.
In General Formula (f0-1), Rf01 represents an organic group containing a fluorine atom. Rf01 is preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be linear, branched, or cyclic. The hydrocarbon group containing a fluorine atom preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and particularly preferably has 1 to 10 carbon atoms.
In the hydrocarbon group containing a fluorine atom, 25% or more of the hydrogen atoms in the hydrocarbon group are preferably fluorinated, more preferably 50% or more are fluorinated, and particularly preferably 60% or more are fluorinated since the hydrophobicity of the resist film during liquid immersion lithography increases.
Among the examples, Rf01 is preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a trifluoromethyl group, —CH2—CF3, —CH2—CF2—CF3, —CH(CF3)2, —CH2—CH2—CF3, —CH2—CH2—CF2—CF2—CF2—CF3, or —CH2—C(CH3)(CF3)2.
Specific examples of the constitutional unit (f01) are shown below: however, the specific examples thereof are not limited thereto. In the formulae, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
The constitutional unit (f01) contained in the component (F01) may be one kind or may be two or more kinds.
The proportion of the constitutional unit (f01) in the component (F01) is preferably in a range of 20% to 95% by mole, more preferably in a range of 30% to 90% by mole, still more preferably in a range of 40% to 85% by mole, and particularly preferably in a range of 40% to 80% by mole, in a range of 50% to 80% by mole, or in a range of 60% to 80% by mole, with respect to the total amount (100% by mole) of all the constitutional units constituting the component (F01).
In a case where the proportion of the constitutional unit (f01) is set within the above-described preferred range, the occurrence of WMDs is more easily reduced.
Constitutional Unit (tU2)
In General Formula (f02-1), R is as described above. R is preferably a hydrogen atom or a methyl group.
In General Formula (f02-1), Vf02 represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group as Vf02 include the same ones as the divalent hydrocarbon group as Va1 in General Formula (a1-1).
Vf02 is preferably a chain-like alkylene group, more preferably a chain-like alkylene group having 1 to 3 carbon atoms, and still more preferably an ethylene group or a methylene group.
In General Formula (f02-1), nf02 represents an integer in a range of 0 to 2. nf02 is preferably 0 or 1.
In General Formula (f02-1), Rf02 represents an acid dissociable group represented by General Formula (f02-r1-1).
In General Formula (f02-r1-1), R021 and Rf022 each independently represent a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group as Rf021 and Rf022 include the same ones as Ra′3 in General Formula (a1-r-1).
Rf021 and Rf022 are preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Rf021 and Rf022 preferably have 1 to 10 carbon atoms, more preferably have 1 to 6 carbon atoms, still more preferably have 1 to 3 carbon atoms, and particularly preferably have an ethyl group or a methyl group. Rf021 and Rf022 preferably do not have a substituent that increases hydrophilicity and more preferably do not have a substituent.
Rf021 and Rf022 may be bonded to each other to form a ring structure. Examples of the ring structure formed by Rf021 and Rf022 include an aliphatic cyclic group. Examples of the aliphatic cyclic group include the same ones as the aliphatic cyclic group formed by Ra′11 in General Formula (a1-r2-1). The ring structure formed by Rf021 and Rf022 may be a monocyclic group or a polycyclic group. In the case of a monocyclic group, the monocyclic group preferably has 4 or more carbon atoms and more preferably has 5 or more carbon atoms. Specific examples of the monocyclic group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic group include an adamantyl group and a norbornyl group.
In General Formula (f02-r1-1), Yf02 represents a quaternary carbon atom.
In General Formula (f02-r1-1), Rf023, R024, and Rf025 each independently represent a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group as Rf023, Rf024, and Rf025 include the same ones as Ra′3 in General Formula (a1-r-1).
Rf023, Rf024, and Rf025 are preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Rf023, Rf024, and Rf025 preferably have 1 to 10 carbon atoms, more preferably have 1 to 6 carbon atoms, still more preferably have 1 to 3 carbon atoms, and particularly preferably have an ethyl group or a methyl group. Rf023, Rf024, and Rf025 preferably do not have a substituent that increases hydrophilicity and more preferably do not have a substituent.
Specific examples of the acid dissociable group represented by General Formula (f02-r1-1) are shown below: however, the specific examples thereof are not limited thereto.
Specific examples of the constitutional unit (f02) are shown below: however, the specific examples thereof are not limited thereto. In the formulae, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
The constitutional unit (f02) contained in the component (F0) may be one kind or may be two or more kinds.
The proportion of the constitutional unit (f02) in the component (F0) is preferably in a range of 5% to 60% by mole, more preferably in a range of 5% to 50% by mole, still more preferably in a range of 10% to 40% by mole, and particularly preferably in a range of 20% to 30% by mole, with respect to the total amount (100% by mole) of all the constitutional units constituting the component (F0).
In a case where the proportion of the constitutional unit (f0) is within the above-described preferred range, the occurrence of WMDs is more easily reduced.
The component (F0) may be used alone or in a combination of two or more kinds thereof.
Examples of the component (F0) include a polymeric compound having a repeating structure of a constitutional unit (f01) and a constitutional unit (f02). In this case, the molar ratio of the constitutional unit (f01) to the constitutional unit (f02) in the polymeric compound (constitutional unit (f01):constitutional unit (f02)) is preferably in a range of 95:10 to 40:60, more preferably in a range of 90:10 to 40:60, still more preferably in a range of 90:10 to 50:50 or 80:20 to 50:50, and particularly preferably in a range of 80:20 to 60:40.
The component (F0) may have another constitutional unit, in addition to the constitutional unit (f01) and the constitutional unit (f02). Examples of such another constitutional unit include a constitutional unit derived from acrylic acid or methacrylic acid.
As the component (F0), a polymeric compound having a repeating structure of the constitutional unit (f01) and the constitutional unit (f02) is preferable.
The weight average molecular weight (Mw) (based on the polystyrene equivalent value determined by gel permeation chromatography) of the component (F0) is preferably in a range of 1,000 to 50,000, more preferably in a range of 5,000 to 40,000, and still more preferably in a range of 10,000 to 30,000. In a case where the Mw of the component (F0) is equal to or smaller than the upper limit value of this range, the solubility in the resist solvent is improved. In a case where the Mw of the component (F0) is equal to or larger than the lower limit value of this range, the water repellency of the resist film is improved.
Further, the polydispersity (Mw/Mn) of the component (F0) is preferably in a range of 1.0 to 5.0, more preferably in a range of 1.0 to 3.0, and still more preferably in a range of 1.0 to 2.5.
The content of the component (F0) in the resist composition is preferably in a range of 0.5 to 10 parts by mass, more preferably in a range of 1 to 10 parts by mass, still more preferably in a range of 4 to 10 parts by mass, particularly preferably in a range of 4 to 6 parts by mass, and most preferably in a range of 5 to 6 parts by mass, with respect to 100 parts by mass of the component (A).
Specific examples of the component (F0) are shown below; however, the specific examples thereof are not limited thereto. In the formulae, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
The resist composition according to the present embodiment may contain a component (F) (hereinafter, also referred to as a “component (F1)”) other than the component (F0) as long as the effects of the present invention are not impaired.
As the component (F1), a fluorine-containing polymeric compound described in Japanese Unexamined Patent Application, First Publication No. 2010-002870, Japanese Unexamined Patent Application, First Publication No. 2010-032994, Japanese Unexamined Patent Application, First Publication No. 2010-277043, Japanese Unexamined Patent Application, First Publication No. 2011-13569, and Japanese Unexamined Patent Application, First Publication No. 2011-128226 can be mentioned.
Specific examples of the component (F1) include a polymer that has the constitutional unit (f0) but does not have the constitutional unit (f02). Examples of this polymer include a polymer (a homopolymer) consisting of only the following constitutional unit (f0); a copolymer of the constitutional unit (f0) and the constitutional unit (a1) (however, a constitutional unit corresponding to the constitutional unit (f02) is excluded); and a copolymer of the constitutional unit (f0), a constitutional unit derived from acrylic acid or methacrylic acid, and the constitutional unit (a1).
The resist composition according to the present embodiment may further contain other components in addition to the component (A), the component (D), and the component (F) described above. Examples of the other components include a component (B), a component (E), and a component (S) that will be described below.
The resist composition according to the present embodiment may further contain, in addition to the components described above, an acid generator component (B) that generates an acid upon exposure.
The component (B) is not particularly limited, and those which have been proposed so far as an acid generator for a chemical amplification-type resist composition in the related art can be used.
Examples of these acid generators are numerous and include onium salt-based acid generators such as iodonium salts and sulfonium salts; oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyl diazomethanes and poly(bis-sulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators; iminosulfonate-based acid generators; and disulfonate-based acid generators.
Examples of the onium salt-based acid generator include a compound represented by General Formula (b-1) (hereinafter, also referred to as a “component (b-1)”), a compound represented by General Formula (b-2) (hereinafter, also referred to as a “component (b-2)”), and a compound represented by General Formula (b-3) (hereinafter, also referred to as a “component (b-3)”), which are described below.
[In the formulae, R101 and R104 to R108 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R104 and R105 may be bonded to each other to form a ring structure. R102 represents a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y101 represents a divalent linking group having an oxygen atom or a single bond. V101 to V103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group. L101 and L102 each independently represent a single bond or an oxygen atom. L103 to L105 each independently represent a single bond, —CO—, or —SO2—. m represents an integer of 1 or more, and Mm+ represents an m-valent onium cation.]
Anion in Component (b-1)
In General Formula (b-1), R101 represents a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.
Cyclic Group which May have Substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group indicates a hydrocarbon group that has no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group be saturated.
Examples of the cyclic group as Rd01, which may have a substituent, include the same ones as Rd01 in General Formula (d01-1).
The cyclic hydrocarbon group as R101 may be a condensed cyclic group having a condensed ring in which an aliphatic hydrocarbon ring is condensed with an aromatic ring. Examples of the condensed ring include a condensed ring in which one or more aromatic rings are condensed with a polycycloalkane having a bridged ring-based polycyclic skeleton. Specific examples of the bridged ring-based polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the condensed cyclic group, a group having a condensed ring in which two or three aromatic rings are condensed with a bicycloalkane is preferable, and a group having a condensed ring in which two or three aromatic rings are condensed with bicyclo[2.2.2]octane is more preferable. Specific examples of the condensed cyclic group as R101 include those represented by General Formulae (r-br-1) and (r-br-2). In the formulae, * represents a bonding site for bonding to Y101 in General Formula (b-1).
Examples of the substituent which may be contained in the condensed cyclic group as R101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
Examples of the alkyl group, the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent of the condensed cyclic group include the same ones as those described as the substituent of the cyclic group as R101.
Examples of the aromatic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from the above-described aromatic ring (an aryl group; for example, a phenyl group or a naphthyl group), a group in which one hydrogen atom in the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, 1-naphthylethyl group, or a 2-naphthylethyl group), and the heterocyclic group represented by each of General Formulae (r-hr-1) to (r-hr-6).
Examples of the alicyclic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane or cyclohexane; a group obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; the lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7); the —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4); and the heterocyclic group represented by each of Formulae (r-hr-7) to (r-hr-16).
Chain-Like Alkyl Group which May have Substituent:
The chain-like alkyl group as R101 may be linear or branched. Examples of the chain-like alkyl group as R101 include the same ones as Rd01 in General Formula (d01-1).
Chain-Like Alkenyl Group which May have Substituent:
The chain-like alkenyl group as R101 may be linear or branched, and the number of carbon atoms thereof is preferably in a range of 2 to 10, more preferably in a range of 2 to 5, still more preferably in a range of 2 to 4, and particularly preferably 3. Examples of the chain-like alkyl group as R101 include the same ones as Rd01 in General Formula (d01-1).
Among the above, R101 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, as the cyclic hydrocarbon group, a phenyl group, a naphthyl group, or a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a lactone-containing cyclic group represented by each of General Formulae (a2-r-1) to (a2-r-7), or a —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4) is preferable, a group obtained by removing one or more hydrogen atoms from a polycycloalkane or a —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4) is more preferable, and an adamantyl group or a —SO2—-containing cyclic group represented by General Formula (a5-r-1) is still more preferable.
In a case where the cyclic hydrocarbon group has a substituent, the substituent is preferably a hydroxyl group.
In General Formula (b-1), Y101 represents a single bond or a divalent linking group having an oxygen atom.
In a case where Y101 represents a divalent linking group containing an oxygen atom, Y101 may contain an atom other than the oxygen atom. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.
Examples of divalent linking groups containing an oxygen atom include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (an ether bond; —O—), an ester bond (—C(═O)—O—), an oxycarbonyl group (—O—C(═O)—), an amide bond (—C(═O)—NH—), a carbonyl group (—C(═O)—), or a carbonate bond (—O—C(═O)—O—); and combinations of the above-described non-hydrocarbon-based oxygen atom-containing linking groups with an alkylene group. Further, a sulfonyl group (—SO2—) may be further linked to the combination. Examples of such a divalent linking group containing an oxygen atom include the linking groups represented by General Formulae (y-a1-1) to (y-a1-7). It is noted that in General Formulae (y-a1-1) to (y-a1-7), V′101 in General Formulae (y-a1-1) to (y-a1-7) is bonded to R101 in General Formula (b-1).
In General Formula (b-1), Y101 is preferably a divalent linking group having an ester bond or a divalent linking group having an ether bond and more preferably a linking group represented by each of General Formulae (y-a1-1) to (y-a1-5).
In General Formula (b-1), V101 represents a single bond, an alkylene group, or a fluorinated alkylene group. It is preferable that the alkylene group and the fluorinated alkylene group as V101 have 1 to 4 carbon atoms. Examples of the fluorinated alkylene group as V101 include a group in which part or all of hydrogen atoms in the alkylene group as V101 have been substituted with a fluorine atom. Among these examples, it is preferable that V101 represent a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.
In General Formula (b-1), R102 represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms and more preferably a fluorine atom.
In a case where Y101 represents a single bond, specific examples of the anion moiety represented by General Formula (b-1) include a fluorinated alkylsulfonate anion such as a trifluoromethanesulfonate anion or a perfluorobutanesulfonate anion. Further, in a case where Y101 represents a divalent linking group having an oxygen atom, specific examples thereof include an anion represented by any one of Formulae (an-1) to (an-3).
[In the formulae, R″101 represents an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by each of Chemical Formulae (r-hr-1) to (r-hr-6), a condensed cyclic group represented by General Formula (r-br-1) or (r-br-2), a chain-like alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent. R″102 represents an aliphatic cyclic group which may have a substituent, the condensed cyclic group represented by General Formula (r-br-1) or (r-br-2), the lactone-containing cyclic group represented by each of General Formulae (a2-r-1) and (a2-r-3) to (a2-r-7), or the —SO2— containing cyclic group represented by each of General Formulae (a5-r-1) to (a5-r-4). R″103 represents an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkenyl group which may have a substituent. V″101 represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R102 represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Each v″ independently represents an integer in a range of 0 to 3, each q″ independently represents an integer in a range of 0 to 20, and n″ represents 0 or 1.]
The aliphatic cyclic group as R″101, R″102, and R″103, which may have a substituent, is preferably the group described as the example of the cyclic aliphatic hydrocarbon group as R′101 in General Formula (b-1). Examples of the substituent include the same ones as the substituent which may be substituted for the cyclic aliphatic hydrocarbon group as R101 in General Formula (b-1).
The aromatic cyclic group which may have a substituent, as R″101 and R″103, is preferably the group described as the example of the aromatic hydrocarbon group for the cyclic hydrocarbon group as R101 in General Formula (b-1). Examples of the substituent include the same ones as the substituent which may be substituted for the aromatic hydrocarbon group as R101 in General Formula (b-1).
The chain-like alkyl group as R″101, which may have a substituent, is preferably the group described as the example of the chain-like alkyl group as R101 in General Formula (b-1).
The chain-like alkenyl group as R″103, which may have a substituent, is preferably the group described as the example of the chain-like alkenyl group as R101 in General Formula (b-1).
Anion in Component (b-2)
In General Formula (b-2), R104 and R105 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples thereof include the same ones as R101 in General Formula (b-1). Here, R104 and R105 may be bonded to each other to form a ring.
R104 and R105 are preferably a chain-like alkyl group which may have a substituent, and more preferably a linear or branched alkyl group or a linear or branched fluorinated alkyl group.
The chain-like alkyl group preferably has 1 to 10 carbon atoms, more preferably has 1 to 7 carbon atoms, and still more preferably has 1 to 3 carbon atoms. It is preferable that the number of carbon atoms in the chain-like alkyl group as R104 and R′105 decrease within the range of the number of carbon atoms from the viewpoint that the solubility in a solvent for a resist is also satisfactory. In addition, in the chain-like alkyl group as R104 and R10, it is preferable that the number of hydrogen atoms substituted with fluorine atoms be as large as possible from the viewpoint that the acid strength increases and the transparency to high energy light or electron beams having a wavelength of 250 nm or less is improved. The proportion of fluorine atoms in the chain-like alkyl group, that is, the fluorination rate, is preferably in a range of 70% to 100% and more preferably in a range of 90% to 100%, and it is most preferable that the chain-like alkyl group be a perfluoroalkyl group in which all hydrogen atoms are substituted with a fluorine atom.
In General Formula (b-2), V102 and V103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and examples thereof include the same ones as V101 in General Formula (b-1).
In General Formula (b-2), L101 and L102 each independently represent a single bond or an oxygen atom.
Anion in Component (b-3)
In General Formula (b-3), R106 to R108 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples thereof include the same ones as R101 in General Formula (b-1).
In General Formula (b-3), L103 to L105 each independently represent a single bond, —CO—, or —SO2—.
Among the above, the anion moiety of the component (B) is preferably an anion of the component (b-1). Among these, an anion represented by any one of General Formulae (an-1) to (an-3) is more preferable, an anion represented by any one of General Formula (an-1) or (an-2) is still more preferable, and an anion represented by General Formula (an-2) is particularly preferable.
In General Formulae (b-1), (b-2), and (b-3), Mm+ represents an m-valent onium cation. Among these, a sulfonium cation and an iodonium cation are preferable.
m represents an integer of 1 or more.
Preferred examples of the cation moiety ((Mm+)1/m) include the organic cations represented by each of General Formulae (ca-1) to (ca-5). Among the examples, it is preferable that the cation moiety ((Mm+)1/m) be a cation represented by General Formula (ca-1). Among the above, the cation moiety ((Mm+)1/m) is preferably a cation represented by each of General Formulae (ca-1-1) to (ca-1-70), and is more preferably a cation represented by each of General Formulae (ca-1-1) to (ca-1-47).
In the resist composition according to the present embodiment, the component (B) may be used alone or in a combination of two or more kinds thereof.
The content of the component (B) in the resist composition according to the present embodiment is preferably less than 40 parts by mass, more preferably in a range of 1 to 30 parts by mass, and still more preferably in a range of 3 to 20 parts by mass, with respect to 100 parts by mass of the component (A).
In a case where the content of the component (B) is set to be in the preferred range described above, pattern formation can be sufficiently carried out. In addition, in a case where each component of the resist composition is dissolved in an organic solvent, the above range is preferable since a homogeneous solution is easily obtained and the storage stability of the resist composition is improved.
<<At Least One Compound (E) Selected from Group Consisting of Organic Carboxylic Acid, Phosphorus Oxo Acid, and Derivatives Thereof>>
For the purpose of preventing any deterioration in sensitivity and improving the resist pattern shape and the post-exposure temporal stability, the resist composition according to the present embodiment may contain, as an optional component, at least one compound (E) (hereinafter referred to as a “component (E)”) selected from the group consisting of an organic carboxylic acid, a phosphorus oxo acid, and derivatives thereof.
Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, and among them, salicylic acid is preferable.
Examples of the phosphorus oxo acid include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
Examples of the phosphorus oxo acid derivative include an ester obtained by substituting a hydrogen atom in the above-described oxo acid with a hydrocarbon group.
Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 15 carbon atoms.
Examples of the phosphoric acid derivative include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of the phosphonic acid derivative include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate.
Examples of the phosphinic acid derivative include phosphinic acid esters and phenylphosphinic acid.
In the resist composition according to the present embodiment, the component (E) may be used alone or in a combination of two or more kinds thereof.
In a case where the resist composition contains the component (E), the content of the component (E) is preferably in a range of 0.01 to 5 parts by mass and more preferably in a range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the component (A). In a case of being set within the above range, sensitivity, lithography characteristics, and the like are improved.
The resist composition according to the present embodiment may be produced by dissolving the resist materials in an organic solvent component (hereinafter, referred to as a “component (S)”).
The component (S) may be any organic solvent which can dissolve each of the components to be used to obtain a homogeneous solution, and an optional organic solvent can be appropriately selected from those which are conventionally known in the related art as solvents for a chemical amplification-type resist composition and then used.
Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; polyhydric alcohol derivatives including compounds having an ether bond, such as a monoalkyl ether (such as monomethyl ether, monoethyl ether, monopropyl ether or monobutyl ether) or monophenyl ether of any of these polyhydric alcohols or compounds having an ester bond [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable]; cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene and mesitylene; and dimethylsulfoxide (DMSO).
In the resist composition according to the present embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds thereof. Among these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferable.
In addition, a mixed solvent obtained by mixing PGMEA with a polar solvent is also preferable as the component (S). The blending ratio (mass ratio) of the mixed solvent can be appropriately determined, taking into consideration the compatibility of the PGMEA with the polar solvent, but is preferably in a range of 1:9 to 9:1 and more preferably in a range of 2:8 to 8:2.
More specifically, in a case where EL or cyclohexanone is blended as the polar solvent, the PGMEA:EL or cyclohexanone mass ratio is preferably in a range of 1:9 to 9:1 and more preferably in a range of 2:8 to 8:2. Alternatively, in a case where PGME is blended as the polar solvent, the PGMEA:PGME mass ratio is preferably in a range of 1:9 to 9:1 and more preferably in a range of 2:8 to 8:2. Furthermore, a mixed solvent of PGMEA, PGME, and cyclohexanone is also preferable.
In addition, the component (S) is also preferably a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably in a range of 70:30 to 95:5.
The amount of the component (S) to be used is not particularly limited and is appropriately set, depending on a thickness of a film to be coated, to a concentration at which the component (S) can be applied onto a substrate or the like. Generally, the component (S) is used such that the solid content concentration of the resist composition is in a range of 0.1% to 20% by mass and preferably in a range of 0.2% to 15% by mass.
As desired, other miscible additives can also be added to the resist composition according to the present embodiment. For example, for improving the performance of the resist film, an additive resin, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a halation prevention agent, and a dye can be appropriately contained therein.
After dissolving the resist material in the component (S), the resist composition according to the present embodiment may be subjected to the removal of impurities and the like by using a porous polyimide membrane, a porous polyamideimide membrane, or the like. For example, the resist composition may be filtered using a filter consisting of a porous polyimide membrane, a filter consisting of a porous polyamideimide membrane, or a filter consisting of a porous polyimide membrane and a porous polyamideimide membrane. Examples of the porous polyimide membrane and the porous polyamideimide membrane include those described in Japanese Unexamined Patent Application, First Publication No. 2016-155121.
The resist composition according to the present embodiment described above contains the component (D0) and the component (F0) in addition to the component (A).
Since it contains the component (D0) and the component (F0) in combination, the followability to water is improved in the liquid immersion lithography using water as a medium. As a result, the amount of residual water droplets in the resist film after liquid immersion lithography is reduced. In addition, it is possible to suppress the elution of resist components from the resist film into water. These actions make it possible to suppress the occurrence of WMDs.
As described above, according to the resist composition according to the present embodiment, it is possible to form a resist pattern in which the number of WMDs is reduced.
A resist pattern formation method according to the second aspect according to the present invention is a method including a step of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.
Examples of one embodiment of such a resist pattern formation method include a resist pattern formation method carried out as described below.
First, the resist composition of the above-described embodiment is applied onto a support with a spinner or the like, and a baking (post-apply baking (PAB)) treatment is carried out, for example, at a temperature condition in a range of 80° C. to 150° C. for 40 to 120 seconds, preferably for 60 to 90 seconds to form a resist film.
Following the selective exposure carried out on the resist film by, for example, exposure through a mask (mask pattern) having a predetermined pattern formed on the mask by using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus, or direct irradiation of the resist film for drawing with an electron beam without using a mask pattern, baking treatment (post-exposure baking (PEB)) is carried out, for example, under a temperature condition in a range of 80° C. to 150° C. for 40 to 120 seconds and preferably 60 to 90 seconds.
Next, the resist film is subjected to a developing treatment. The developing treatment is carried out using an alkali developing solution in the case of an alkali developing process, and a developing solution containing an organic solvent (organic developing solution) in the case of a solvent developing process.
After the developing treatment, it is preferable to conduct a rinse treatment. As the rinse treatment, water rinsing using pure water is preferable in the case of an alkali developing process, and rinsing using a rinse liquid containing an organic solvent is preferable in the case of a solvent developing process.
In the case of a solvent developing process, after the developing treatment or the rinse treatment, the developing solution or the rinse liquid remaining on the pattern can be removed by a treatment using a supercritical fluid.
After the developing treatment or the rinse treatment, drying is carried out. As desired, baking treatment (post-baking) can be carried out following the developing treatment.
In this manner, a resist pattern can be formed.
The support is not specifically limited and a known support in the related art can be used. For example, substrates for electronic components, and such substrates having a predetermined wiring pattern formed thereon can be used. Specific examples of the material of the substrate include metals such as a silicon wafer, copper, chromium, iron and aluminum; and glass. Suitable materials for the wiring pattern include copper, aluminum, nickel, and gold.
The wavelength to be used for exposure is not particularly limited and the exposure can be carried out using radiation such as an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, an extreme ultraviolet ray (EUV), a vacuum ultraviolet ray (VUV), an electron beam (EB), an X-ray, and a soft X-ray. The resist composition is highly useful for a KrF excimer laser, an ArF excimer laser, EB, or EUV, and is more useful for an ArF excimer laser.
The exposure method of the resist film can be general exposure (dry exposure) carried out in air or an inert gas such as nitrogen, or liquid immersion lithography; however, liquid immersion lithography is more preferable.
Liquid immersion lithography is an exposure method in which the region between the resist film and the lens at the lowermost position of the exposure apparatus is pre-filled with a solvent (liquid immersion medium) that has a refractive index larger than the refractive index of air, and the exposure (liquid immersion lithography) is carried out in this state.
The liquid immersion medium is preferably a solvent that exhibits a refractive index larger than the refractive index of air but smaller than the refractive index of the resist film to be exposed, and examples thereof include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
As the liquid immersion medium, water is preferably used.
Examples of the alkali developing solution used for a developing treatment in an alkali developing process include an aqueous solution of tetramethylammonium hydroxide (TMAH) of 0.1% to 10% by mass.
As the organic solvent contained in the organic developing solution, which is used for a developing treatment in a solvent developing process, any one of the conventionally known organic solvents capable of dissolving the component (A) (component (A) prior to exposure) can be appropriately selected from the conventionally known organic solvents. Specific examples of the organic solvent include polar solvents such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, a nitrile-based solvent, an amide-based solvent, an ether-based solvent, and a hydrocarbon-based solvent.
A ketone-based solvent is an organic solvent containing C—C(═O)—C in the structure thereof. An ester-based solvent is an organic solvent containing C—C(═O)—O—C in the structure thereof. An alcohol-based solvent is an organic solvent containing an alcoholic hydroxyl group in the structure thereof. The term “alcoholic hydroxyl group” indicates a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. A nitrile-based solvent is an organic solvent containing a nitrile group in the structure thereof. An amide-based solvent is an organic solvent containing an amide group in the structure thereof. An ether-based solvent is an organic solvent containing C—O—C in the structure thereof.
Some organic solvents have a plurality of the functional groups which characterize the above-described solvents in the structure thereof. In such a case, the organic solvent can be classified as any type of solvent having a functional group that characterizes a solvent. For example, diethylene glycol monomethyl ether can be classified as an alcohol-based solvent or an ether-based solvent.
A hydrocarbon-based solvent consists of a hydrocarbon which may be halogenated and does not have any substituent other than a halogen atom. The halogen atom is preferably a fluorine atom.
Among the above, the organic solvent contained in the organic developing solution is preferably a polar solvent and preferably a ketone-based solvent, an ester-based solvent, or a nitrile-based solvent.
Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methylamyl ketone (2-heptanone). Among these examples, the ketone-based solvent is preferably methylamyl ketone (2-heptanone).
Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Among these, the ester-based solvent is preferably butyl acetate.
Examples of the nitrile-based solvent include acetonitrile, propionitrile, valeronitrile, and butyronitrile.
As desired, the organic developing solution may have a conventionally known additive blended. Examples of the additive include surfactants. The surfactant is not particularly limited, and for example, an ionic or non-ionic fluorine-based and/or silicon-based surfactant can be used. As the surfactant, a non-ionic surfactant is preferable, and a non-ionic fluorine-based surfactant or a non-ionic silicon-based surfactant is more preferable.
In a case where a surfactant is blended, the blending amount thereof is typically in a range of 0.001% to 5% by mass, preferably in a range of 0.005% to 2% by mass, and more preferably in a range of 0.01% to 0.5% by mass with respect to the total amount of the organic developing solution.
The developing treatment can be carried out by a conventionally known developing method. Examples thereof include a method in which the support is immersed in the developing solution for a predetermined time (a dip method), a method in which the developing solution is cast upon the surface of the support by surface tension and maintained for a predetermined time (a puddle method), a method in which the developing solution is sprayed onto the surface of the support (spray method), and a method in which a developing solution is continuously ejected from a developing solution ejecting nozzle and applied onto a support, which is being rotated at a constant rate while being scanned at a constant rate (dynamic dispense method).
As the organic solvent contained in the rinse liquid used in the rinse treatment after the developing treatment in the case of a solvent developing process, it is possible to appropriately select and use, for example, an organic solvent that hardly dissolves the resist pattern, among the organic solvents described as the organic solvent that is used for the organic developing solution. In general, at least one kind of solvent selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, and an ether-based solvent is used. Among these, at least one kind of solvent selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, and an amide-based solvent is preferable, at least one kind of solvent selected from an alcohol-based solvent and an ester-based solvent is more preferable, and an alcohol-based solvent is particularly preferable.
The alcohol-based solvent used for the rinse liquid is preferably a monohydric alcohol of 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable.
These organic solvents may be used alone or in a combination of two or more kinds thereof. In addition, an organic solvent other than the above-described examples or water may be mixed therewith. However, in consideration of the development characteristics, the amount of water to be blended in the rinse liquid is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less with respect to the total amount of the rinse liquid.
A conventionally known additive can be blended with the rinse liquid as necessary. Examples of the additive include surfactants. Examples of the surfactant include the same ones as those described above, and the surfactant is preferably a non-ionic surfactant and more preferably a non-ionic fluorine-based surfactant or a non-ionic silicon-based surfactant.
In a case where a surfactant is blended, the blending amount thereof is typically in a range of 0.001% to 5% by mass, preferably in a range of 0.005% to 2% by mass, and more preferably in a range of 0.01% to 0.5% by mass with respect to the total amount of the rinse liquid.
The rinse treatment using a rinse liquid (washing treatment) can be carried out by a conventionally known rinse method. Examples of the rinse treatment method include a method in which the rinse liquid is continuously ejected and applied onto the support while rotating it at a constant rate (rotational coating method), a method in which the support is immersed in the rinse liquid for a predetermined time (dip method), and a method in which the rinse liquid is sprayed onto the surface of the support (spray method).
According to the resist pattern formation method according to the present embodiment described above, since the resist composition described above is used, it is possible to form a resist pattern in which WMDs are reduced.
Various materials that are used in the resist composition according to the above-described embodiment and the method for forming a pattern according to the above-described embodiment (for example, a resist solvent, a developing solution, a rinse liquid, a composition for forming an antireflection film, and a composition for forming a top coat) preferably do not contain impurities such as a metal, a metal salt containing a halogen, an acid, an alkali, and a component containing a sulfur atom or phosphorus atom. Here, examples of the impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. The content of the impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, still more preferably 100 parts per trillion (ppt) or less, and particularly preferably 10 ppt or less, where it is most preferable that the impurities are substantially free (below the detection limit of the measuring device).
Hereinafter, the present invention will be described in more detail based on Examples; however, the present invention is not limited to these Examples.
Each of the components shown in Tables 1 to 3 was mixed and dissolved to prepare a resist composition of each Example.
In Tables 1 to 3, each abbreviation has the following meaning. The numerical values in [ ] indicate blending amounts (in terms of parts by mass).
(A1)-1: Polymeric compound represented by General Formula (A-1). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 7,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=50/50.
(A1)-2: Polymeric compound represented by General Formula (A-2). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 7,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=40/60.
(A1)-3: Polymeric compound represented by General Formula (A-3). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 7,000 in terms of weight average molecular weight (Mw), and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=40/60.
(A1)-4: Polymeric compound represented by General Formula (A-4). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 7,000 in terms of weight average molecular weight (Mw), and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NNMR is 1/m=50/50.
(B)-1 to (B)-3: Acid generators consisting of compounds represented by each of Chemical Formulae (B-1) to (B-3).
(D0)-1 to (D0)-9: Acid diffusion controlling agents consisting of compounds represented by Chemical Formulae (D0-1) to (D0-9). Ra indicates the interaction distance (Ra) between the Hansen solubility parameter of the compound in which the anion moiety is protonated and the Hansen solubility parameter of water. Ra in the compound represented by General Formula (D0-9) was calculated from the compound protonated after photodecomposition.
(D1)-1 to (D1)-3: Acid diffusion controlling agents consisting of compounds represented by Chemical Formulae (D1-1) to (D1-3).
(F0)-1: Polymeric compound represented by Chemical Formula (F0-1). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-2: Polymeric compound represented by Chemical Formula (F0-2). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=90/10.
(F0)-3: Polymeric compound represented by Chemical Formula (F0-3). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR was 1/m=70/30.
(F0)-4: Polymeric compound represented by Chemical Formula (F0-4). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=50/50.
(F0)-5: Polymeric compound represented by Chemical Formula (F0-5). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-6: Polymeric compound represented by Chemical Formula (F0-6). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-7: Polymeric compound represented by Chemical Formula (F0-7). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-8: Polymeric compound represented by Chemical Formula (F0-8). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-9: Polymeric compound represented by Chemical Formula (F0-9). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-10: Polymeric compound represented by Chemical Formula (F0-10). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-11: Polymeric compound represented by Chemical Formula (F0-11). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-12: Polymeric compound represented by Chemical Formula (F0-12). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F0)-13: Polymeric compound represented by Chemical Formula (F0-13). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F1)-1: Polymeric compound represented by Chemical Formula (F1-1). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(F1)-2: Polymeric compound represented by Chemical Formula (F1-2). The weight average molecular weight (Mw) in terms of the standard polystyrene equivalent value, acquired by the GPC measurement, is 25,000, and molecular weight polydispersity (Mw/Mn) is 1.5. The copolymerization composition ratio (the ratio (the molar ratio) among constitutional units in the structural formula) determined by 13C-NMR is 1/m=80/20.
(S)-1: A mixed solvent of propylene glycol monomethyl ether acetate:propylene glycol monomethyl ether:cyclohexanone=55:20:25 (in terms of mass ratio).
An organic antireflection film composition “ARC29A”, (manufactured by Brewer Science Inc.) was applied onto a 12-inch silicon wafer using a spinner and baked and dried on a hot plate at 205° C. for 60 seconds to form an organic antireflection film having a thickness of 102 m.
The resist composition of each Example was applied onto the antireflection film using a spinner, and a pre-baking (PAB) treatment was carried out at 100° C. for 60 seconds on a hot plate, followed by drying to form a resist film having a film thickness of 100 nm.
Next, the resist film was selectively irradiated with an ArF excimer laser (193 nm) through a photomask (halftone: 6%) using an ArF exposure apparatus for liquid immersion XT-1900Gi [manufactured by ASML; numerical aperture (NA)=1.35, Dipole 35X, Sigma: 0.78/0.97, Y-deflection, liquid immersion medium: ultrapure water]. Then, PEB treatment was carried out at 100° C. for 60 seconds.
Next, alkali development was carried out with a 2.38% by mass TMAH aqueous solution (product name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C. for 15 seconds, and then water rinsing was carried out for 15 seconds using pure water, followed by shake-off drying. As a result, a line-and-space (LS) pattern with a line width of 55 nm and a pitch of 100 nm (mask size: 50 nm) was formed in any example.
For the LS pattern formed in <Resist pattern formation> described above, the total number of defects (the number of all the defects) in a wafer was measured using a surface defect observation device (product name: KLA2905, manufactured by KLA Corporation). Defects having a size of 1 μm or more were measured. The measurement was carried out 10 times for each sample, from which the average value thereof was determined. The results are shown in Tables 4 to 6 as “Number of WMDs”.
As shown in Tables 4 to 6, it has been confirmed that in the resist compositions of Examples, the number of WMDs is reduced as compared with the resist compositions of Comparative Examples.
The preferred Examples of the present invention have been described as above; however, the present invention is not limited to these Examples. Additions, omissions, substitutions, and other modifications of the configuration can be made without departing from the spirit of the present invention. Accordingly, the present invention is not to be considered as being limited by the foregoing description and is only limited by the scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-205205 | Dec 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/045673 | 12/12/2022 | WO |
