Patent Application
20250130492
The present invention relates to a resist composition, a method for forming a resist pattern, and a compound.
Priority is claimed on Japanese Patent Application No. 2022-007875, filed Jan. 21, 2022, the content of which is incorporated herein by reference.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, advances in lithography technologies have led to rapid progress in the field of pattern miniaturization. These pattern miniaturization techniques typically involve shortening the wavelength (increasing the energy) of the exposure light source.
Resist materials are required to have lithography characteristics such as sensitivity to these kinds of exposure light sources and resolution that enables reproduction of patterns with minute dimensions.
As a resist material that satisfies these requirements, a chemically amplified resist composition containing a base material component whose solubility in a developing solution is changed due to an action of an acid and an acid generator component that generates an acid upon light exposure has been used in the related art.
In the chemically amplified resist composition, a resin having a plurality of constitutional units is typically used in order to improve lithography characteristics and the like.
For example, Patent Document 1 discloses a resist composition containing a resin component (A1) that has a constitutional unit (a01) containing a specific acid dissociable group, a constitutional unit (a02) containing a cyclic group (here, a cyclic group forming a crosslinked structure is excluded) in which —O—C(═O)— forms a part of a ring skeleton, and a specific constitutional unit (a03) containing a hydroxy group. Patent Document 1 discloses that this resist composition controls diffusion of an acid, improves the affinity for a developing solution, and is also excellent in sensitivity, a roughness reducing property, and resolution.
With further advances in lithography technologies, rapid progress in the field of pattern fining is being achieved together with the expansion of application fields. In association with this, in a case of manufacturing a semiconductor element or the like, there is a demand for a technology that enables formation of a fine pattern in a satisfactory shape.
However, in response to such a demand, in the resist composition of the related art described in Patent Document 1, both the sensitivity and the roughness reducing property in the resist pattern formation are not necessarily and sufficiently achieved. Therefore, both the sensitivity and the roughness reducing property are required to be achieved at a higher level.
The present invention has been made in consideration of the above-described circumstances, and an object thereof is to provide a resist composition capable of forming a resist pattern that can achieve high sensitivity and has a satisfactory roughness reducing property, a method for forming a resist pattern using the resist composition, and a compound capable of preparing a resin contained in the resist composition.
In order to achieve the above-described object, the present invention employs the following configurations.
That is, according to a first aspect of the present invention, there is provided a resist composition which generates an acid upon light exposure and whose solubility in a developing solution is changed due to an action of the acid, the resist composition including: a resin component (A1) having a constitutional unit (a01) derived from a compound represented by General Formula (a0-1).
[In the formula, R01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. L01 represents a divalent linking group. Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
According to a second aspect of the present invention, there is provided a method for forming a resist pattern, 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 to light; and a step of developing the resist film exposed to light to form a resist pattern.
According to a third aspect of the present invention, there is provided a compound represented by General Formula (a0-1).
According to the present invention, it is possible to provide a resist composition capable of forming a resist pattern that can achieve high sensitivity and has a satisfactory roughness reducing property, a method for forming a resist pattern using the resist composition, and a compound capable of preparing a resin contained in the resist composition.
In the present specification and the scope of the present patent claims, the term “aliphatic” is a relative concept used in relation to the term “aromatic”, and defines a group or compound that has no aromaticity.
The term “alkyl group” includes a linear, branched, or cyclic monovalent saturated hydrocarbon group unless otherwise specified. The same applies to the alkyl group in an alkoxy group.
The term “alkylene group” includes a linear, branched, or cyclic divalent saturated hydrocarbon group unless otherwise specified.
Examples of “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The term “constitutional unit” indicates a monomer unit constituting a polymer 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 (—CH2—) group is substituted with a divalent group.
The term “light exposure” is a general concept for irradiation with radiation.
The term “acid decomposable group” indicates a group having acid decomposability in which at least a part of a bond in the structure of the acid decomposable group can be cleaved due to the action of an acid.
Examples of the acid decomposable group whose polarity is increased due to the action of an acid include groups which are decomposed due to the 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 in which the above-described polar group has been protected by an acid dissociable group (such as a group in which a hydrogen atom of the OH-containing polar group has been protected by an acid dissociable group).
Here, the term “acid dissociable group” indicates both a group (i) having an acid dissociation property in which a bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved due to the action of an acid and a group (ii) in which some bonds are cleaved due to the action of an acid, a decarboxylation reaction occurs, and thus the bond between the acid dissociable group and the atom adjacent to the acid dissociable group can be cleaved.
It is necessary that the acid dissociable group that constitutes the acid decomposable group is a group which exhibits a lower polarity than that of the polar group generated by the dissociation of the acid dissociable group. In this manner, in a case where the acid dissociable group is dissociated due to the action of an acid, a polar group exhibiting a higher polarity than that of the acid dissociable group is generated so that the polarity is increased. As a result, the polarity of an entire component (A1) is increased. Due to the increase in the polarity, relatively, the solubility in a developing solution is changed such that the solubility is increased in a case where the developing solution is an alkali developing solution and the solubility is decreased in a case where the developing solution is an organic developing solution.
The term “base material component” denotes an organic compound having a film-forming ability. Organic compounds used as the base material component are classified into non-polymers and polymers. As the non-polymers, those having a molecular weight of 500 or greater and less than 4000 are typically used. Hereinafter, the term “low-molecular-weight compound” denotes a non-polymer having a molecular weight of 500 or greater and less than 4000. As the polymer, those having a molecular weight of 1000 or greater are typically used. Hereinafter, “resin”, “polymer compound”, or “polymer” indicates a polymer having a molecular weight of 1000 or greater. As the molecular weight of the polymer, the weight-average molecular weight in terms of polystyrene according to gel permeation chromatography (GPC) is used.
The expression “constitutional unit to be derived” denotes a constitutional unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond.
In “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 substitutes the hydrogen atom bonded to the carbon atom at the α-position is an atom other than the hydrogen atom or a group. Further, 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. Further, the carbon atom at the α-position of acrylic acid ester indicates the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified, Hereinafter, acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position has been substituted with a substituent is also referred to as α-substituted acrylic acid ester.
The concept “derivative” includes those obtained by substituting a hydrogen atom at the α-position of a target compound with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. Examples of the derivatives thereof include those obtained by substituting a hydrogen atom of a hydroxyl group of a target compound, in which the hydrogen atom at the α-position may be substituted with a substituent, with an organic group, and those obtained by bonding a substituent other than a hydroxyl group to a target compound in which the hydrogen atom at the α-position may be substituted with a substituent. Further, the α-position denotes the first carbon atom adjacent to a functional group unless otherwise specified.
Examples of the substituent that substitutes the hydrogen atom at the α-position of hydroxystyrene include those for Rαx.
In the present specification and the scope of the present patent claims, asymmetric carbons may be present and enantiomers or diastereomers may be present depending on the structures of the chemical formulae. In this 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 which generates an acid upon light exposure and whose solubility in a developing solution is changed by the action of the acid.
The resist composition contains a base material component (A) (hereinafter, also referred to as “component (A)”) whose solubility in a developing solution is changed due to the action of the acid.
In the resist composition according to the present embodiment, the component (A) may generate an acid upon light exposure, or an additive component that is blended separately from the component (A) may generate an acid upon light exposure.
Specifically, the resist composition according to the present embodiment may (1) further contain an acid generator component (B) (hereinafter, referred to as “component (B)”) that generates an acid upon light exposure; (2) have a component (A) that generates an acid upon light exposure; and (3) have a component (A) that generates an acid upon light exposure and further contains component (B).
That is, in the cases of (2) and (3) described above, the component (A) is “base material component which generates an acid upon light exposure and whose solubility in a developing solution is changed due to the action of the acid”. In a case where the component (A) is a base material component which generates an acid upon light exposure and whose solubility in a developing solution is changed due to the action of the acid, it is preferable that the component (A1) described below is a resin which generates an acid upon light exposure and whose solubility in a developing solution is changed due to the action of the acid. As such a resin, a polymer compound having a constitutional unit that generates an acid upon light exposure can be used. As the constitutional unit that generates an acid upon light exposure, those which have been known can be used.
Among the examples, it is preferable that the resist composition according to the present embodiment corresponds to the case (1). That is, it is preferable that the resist composition according to the present embodiment contains the component (A) and the component (B).
In a case where a resist film is formed of the resist composition according to the present embodiment and the resist film is selectively exposed, since an acid is generated from the component (B) in an exposed portion of the resist film and the solubility of the component (A) in a developing solution is changed due to the action of the acid while the solubility of the component (A) in a developing solution is not changed in an unexposed portion of the resist film, a difference in solubility in the developing solution occurs between the exposed portion and the unexposed portion. Therefore, in a case where the resist film is developed, the exposed portion of the resist film is dissolved and removed to form a positive-tone resist pattern in a case where the resist composition is of a positive tone, whereas the unexposed portion of the resist film is dissolved and removed to form a negative tone resist pattern in a case where the resist composition is of a negative tone.
The resist composition of the present embodiment may be a positive tone resist composition or a negative tone resist composition. Further, the resist composition of the present embodiment may be used in an alkali developing process using an alkali developing solution in the developing treatment in a case of forming a resist pattern or may be used in a solvent developing process using a developing solution containing an organic solvent (organic developing solution) in the developing treatment.
In the resist composition according to the present embodiment, the component (A) contains a resin component (A1) (hereinafter, also referred to as “component (A1)”) whose solubility in a developing solution is changed due to the action of an acid.
Since the polarity of the base material component before and after the light exposure is changed by using the component (A1), a satisfactory development contrast can be obtained not only in an alkali developing process but also in a solvent developing process.
As the component (A), another polymer compound and/or a low-molecular-weight compound may be used in combination with the component (A1).
In the resist composition according to the present embodiment, the component (A) may be used alone or a combination of two or more kinds thereof may be used.
In regard to component (A1)
The component (A1) is a resin component whose solubility in a developing solution is changed by the action of an acid.
The component (A1) has a constitutional unit (a01) derived from a compound represented by General Formula (a0-1).
The component (A1) may have other constitutional units as necessary in addition to the constitutional unit (a01).
[in the formula, R01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. L01 represents a divalent linking group. Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms]
In General Formula (a0-1), R01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms.
As the alkyl group having 1 to 10 carbon atoms as R01, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable. 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 10 carbon atoms is a group in which some or all hydrogen atoms in the alkyl group having 1 to 10 carbon atoms have been substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
R01 represents 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 more preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.
In General Formula (a0-1), L01 represents a divalent linking group such as a divalent hydrocarbon group which may have a substituent or a divalent linking group having a heteroatom.
Divalent Hydrocarbon Group which May have Substituent:
In a case where L01 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 L01
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 is saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group having 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, alkylniethylene groups such as —CH(CH3)—, —CH(CH2CH3)—, —C(CH3)2—, —C(CH3)(CH2CH3)—, —C(CH3)(CH2CH2CH3)—, and —C(CH2CH3)—; alkylethylene groups such as —CH(CH3)CH2—, —CH(CH3)CH(CH3)—, —C(CH2)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)CH2—CH2CH2— and —CH2CH(CH)CH2CH2—. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.
The linear or branched aliphatic hydrocarbon group may 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 having a ring in the structure thereof include a cyclic aliphatic hydrocarbon group which may have a substituent having a heteroatom in the ring structure thereof (a group in which two hydrogen atoms have been removed 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 the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as those described above.
The cyclic aliphatic hydrocarbon group has preferably 3 to 20 carbon atoms and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane has preferably 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a polycycloalkane is preferable. As the polycycloalkane, a group having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The cyclic aliphatic hydrocarbon group may 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.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group is more preferable, and a methoxy group or an ethoxy group is still more preferable.
As the halogen atom as the substituent, a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which some or all hydrogen atoms in the above-described alkyl groups have been substituted with the above-described halogen atoms.
In the cyclic aliphatic hydrocarbon group, some carbon atoms constituting the ring structure thereof may be substituted with a substituent having a heteroatom. As the substituent having a heteroatom, —O—, —C(═O)—O—, —S—, —S(═O)2—, or —S(═O)2—O— is preferable.
Further, the cyclic aliphatic hydrocarbon group may be a lactone-containing cyclic group such as a group represented by any of General Formulae (L-r-1) to (L-r-7).
[In the formulae, Ra′021's each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR0″, —OC(═O)R0″, a hydroxyalkyl group, or a cyano group, R0″ represents a hydrogen atom, an alkyl group, or a lactone-containing cyclic group, A0″ represents an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom (—O—) or a sulfur atom (—S—), an oxygen atom, or a sulfur atom, n0′ represents an integer of 0 to 2, and m0′ represents 0 or 1. * represents a bonding site with respect to the carbon atom to which R01 in General Formula (a0-1) is bonded. ** represents a bonding site with respect to the carbon atom of the carbonyl group in General Formula (a0-1).]
In General Formulae (L-r-1) to (L-r-7), it is preferable that the alkyl group as Ra′021 is an alkyl group having 1 to 6 carbon atoms. It is preferable that the alkyl group is linear or branched.
It is preferable that the alkoxy group as Ra′021 is an alkoxy group having 1 to 6 carbon atoms. It is preferable that the alkoxy group is linear or branched. Specific examples of the alkoxy groups include a group formed by linking the above-described alkyl group described as the alkyl group represented by Ra′021 to an oxygen atom (—O—).
As the halogen atom as Ra′021, a fluorine atom is preferable,
Examples of the halogenated alkyl group as Ra′021 include groups in which some or all hydrogen atoms in the alkyl group as Ra′021 have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
In —COOR0″ and —OC(═O)R0″ as Ra′021, each R0″ represents a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
The alkyl group as R0″ may be linear, branched, or cyclic and has preferably 1 to 15 carbon atoms.
In a case where R0″ represents a linear or branched alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.
In a case where R0″ represents a cyclic alkyl group, the number of carbon atoms thereof is preferably in a range of 3 to 15, more preferably in a range of 4 to 12, and most preferably in a range of 5 to 10.
Examples of the lactone-containing cyclic group as R0″ include the same groups as the groups each represented by General Formulae (L-r-1) to (L-r-7).
As the hydroxyalkyl group as Ra′021, 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′021 has been substituted with a hydroxyl group.
In General Formulae (L-r-2), (L-r-3), and (L-r-5), as the alkylene group having 1 to 5 carbon atoms as A0″, 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 in the terminal of the alkylene group or between the carbon atoms of the alkylene group. Further, examples thereof include —O—CH2—, —CH2—O—CH2—, —S—CH2—, and —CH2—S—CH2—. It is preferable that A0″ represents an alkylene group having 1 to 5 carbon atoms or —O—.
The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as the aromatic ring is a cyclic conjugated system having (4n+2) π electrons and may be monocyclic or polycyclic. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 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 aromatic heterocyclic rings in which some of the carbon atoms constituting the above-described aromatic hydrocarbon rings have been substituted with heteroatoms. Examples of the heteroatom 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 in which two hydrogen atoms have been removed from the above-described aromatic hydrocarbon ring or aromatic heterocyclic ring (an arylene group or a heteroarylene group); a group in which two hydrogen atoms have 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 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 obtained by further removing one hydrogen atom from an aryl group in 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 number of carbon atoms in the alkylene group bonded to the aryl group or the heteroaryl group is preferably in a range of 1 to 4, more preferably 1 or 2, and particularly preferably 1.
In the aromatic hydrocarbon group, the hydrogen atom 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.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable.
As the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituents, the groups described as the substituents that substitute a hydrogen atom in the cyclic aliphatic hydrocarbon group are exemplary examples.
In a case where L01 represents a divalent linking group having a heteroatom, 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]m2—Y22—, —Y21—O—C(═O)—Y22—, or —Y22—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 of 0 to 3].
In a case where the divalent linking group containing a heteroatom 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, an acyl group, or the like. The substituent (an alkyl group, an acyl group, or the like) has preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
In General Formula
—Y21—O—Y22—, —Y21—O—, —Y21C(═O)—O—, —C(═O)—O—Y21—, —[Y21—C(═O)—O]m—Y22—, —Y21—O—C(═O)—Y22—,
or
—Y22(═O)2—Y21—, Y22
and Y21 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 L01.
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 of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, a group represented by Formula
—Y21—C(═)—O—Y22—
is particularly preferable as the group represented by Formula
—[Y21—C(═)—O]m,—Y22.
Among these, a group represented by Formula
—(CH2)—C(═O)—O—(CH2)—
is preferable In the formula, a′ represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1, b′ represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.
Among the examples, it is preferable that L01 represents an ester bond [—C(═O)— O— or —O—C(═O)—], an aromatic hydrocarbon group, a lactone-containing cyclic group, or a divalent linking group containing a group consisting of a combination of these groups.
More specifically, it is preferable that L01 represents a group consisting of an ester bond and an alkylene group, an aromatic hydrocarbon group, or a group consisting of an ester bond and a lactone-containing cyclic group.
As the alkylene group in the group consisting of an ester bond and an alkylene group, a linear or branched alkylene group having 1 to 5 carbon atoms is preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group or an ethylene group is still more preferable.
Further, the alkylene group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl 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 the aromatic ring is a cyclic conjugated system having (4n+2) z electrons and may be monocyclic or polycyclic. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 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 aromatic heterocyclic rings in which some of the carbon atoms constituting the above-described aromatic hydrocarbon rings have been substituted with heteroatoms. Examples of the heteroatom 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 in which two hydrogen atoms have been removed from the above-described aromatic hydrocarbon ring or aromatic heterocyclic ring (an arylene group or a heteroarylene group); a group in which two hydrogen atoms have 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 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 obtained by further removing one hydrogen atom from an aryl group in 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 number of carbon atoms in the alkylene group bonded to the aryl group or the heteroaryl group is preferably in a range of 1 to 4, more preferably 1 or 2, and particularly preferably 1.
Further, the aromatic hydrocarbon group may have a substituent. Examples of substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
Among the examples, as the aromatic hydrocarbon group, an arylene group which may have a substituent is preferable, an arylene group having a substituent is more preferable, an arylene group having a hydroxyl group is still more preferable, and a phenylene group having a hydroxyl group is particularly preferable.
As the lactone-containing cyclic group in the group consisting of an ester bond and a lactone-containing cyclic group, a group represented by any of General Formulae (L-r-1) to (L-r-7) is preferable, and a group represented by General Formula (L-r-2) is more preferable.
Among the examples, it is preferable that L01 represents a group represented by any of General Formulae (L0-r-1) to (L0-r-5).
[in the formulae, Rx00's each independently represent an alkylene group. Ar00 represents an arylene group which may have a substituent. Lc00 represents a lactone-containing cyclic group represented by any one of General Formulae (L-r-1) to (L-r-7). * represents a bonding site with respect to the carbon atom to which R01 in General Formula (a0-1) is bonded. ** represents a bonding site with respect to the carbon atom of the carbonyl group in General Formula (a10-1)]
It is preferable that Rx00 represents an alkylene group having 1 to 5 carbon atoms.
Ar00 represents preferably an arylene group which may have a substituent, more preferably an arylene group having a hydroxyl group, and still more preferably a phenylene group having a hydroxyl group.
Lc00 represents a lactone-containing cyclic group represented by any of General Formulae (L-r-1) to (L-r-7) and preferably a lactone-containing cyclic group represented by (General Formula (L-r-2).
Among the examples, LP represents preferably a group represented by any one of General Formulae (L0-r-3) to (L0-r-5) and more preferably a group represented by General Formula (L0-r-3).
Examples of the hydrocarbon groups as Ra01 and Ra02 in General Formula (a0-1) include a linear or branched hydrocarbon group and a cyclic hydrocarbon group.
Examples of the linear or branched hydrocarbon group include a linear or branched saturated hydrocarbon group (alkyl group) and a linear or branched unsaturated hydrocarbon group.
Specific examples of the linear or branched alkyl group 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.
More specific examples of the linear or branched unsaturated hydrocarbon group include an unsaturated hydrocarbon group having a double bond, such as an alkenyl group, an alkadienyl group, or an alkatrienyl group; and an unsaturated hydrocarbon group having a triple bond, such as an alkynyl group, a group obtained by removing one hydrogen atom from a dialkyne, or a group obtained by removing one hydrogen atom from a trialkylene.
Specific examples of the linear or branched alkenyl group include a linear alkenyl group such as a vinyl group, a propenyl group (an allyl group), or a 2-butenyl group; and a branched alkenyl group such as a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, or 2-methylpropenyl group.
Specific examples of the alkadienyl group include a propadienyl group and a butadienyl group.
Specific examples of the alkatrienyl group include a butatrienyl group.
Specific examples of the linear or branched alkynyl group include a linear alkynyl group such as an ethynyl group, a propargyl group, or a 3-pentynyl group; and a branched alkynyl group such as a 1-methylpropargyl group.
Specific examples of the group obtained by removing one hydrogen atom from the dialkyne include a group obtained by removing one hydrogen atom from diacetylene.
Specific examples of the group obtained by removing one hydrogen atom from the trialkyne include a group obtained by removing one hydrogen atom from hexa-1,3,5-triyne.
The cyclic hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferable. The monocycloalkane has preferably 3 to 6 carbon atoms, and specific examples thereof include cyclopropane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferable. As the polycycloalkane, a group having 7 to 12 carbon atoms is preferable, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
Examples of the aromatic hydrocarbon group include an aryl group and a heteroaryl group, and specific examples thereof include a phenyl group and a naphthyl group.
Examples of the substituent that the hydrocarbon group as Ra01 and Ra02 may have include —ReP1, —RP2—O—, —RP1, —RP2—CO—RP1, —RP2—CO—ORP1, —RP2—O—CO—RP1, —RP2—OH, —RP2—CN, and —RP—COOH (hereinafter, these substituents will also be collectively referred to as “Rax5″”.
Here, RP1 represents a chain-like monovalent 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. Further, 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. Here, some or all 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 fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of a single kind of substituents or one or more of each of plural kinds of the substituents.
Examples of the chain-like monovalent 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 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.
Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a group formed by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, or phenanthrene.
In General Formula (a0-1), among the examples, Ra01 and Ra02 each independently represent preferably a linear or branched saturated hydrocarbon group or a linear or branched unsaturated hydrocarbon group, more preferably a linear or branched saturated hydrocarbon group having 1 to 5 carbon atoms or a linear or branched unsaturated hydrocarbon group having 1 to 5 carbon atoms, still more preferably a linear saturated hydrocarbon group having 1 to 5 carbon atoms or a linear unsaturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a methyl group, an ethyl group, an ethynyl group, or a vinyl group.
More specifically, it is preferable that both Ra01 and Ra02 represent a methyl group or an ethyl group, or Ra01 represents a methyl group or an ethyl group and Ra02 represents an ethynyl group or a vinyl group.
In General Formula (a0-1), Ar1 represents an aryl group in which some or all hydrogen atoms have been substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms have been substituted with iodine atoms.
Examples of the aryl group as Ar01 include a group obtained by removing one hydrogen atom from an aromatic ring. Examples of the aromatic ring include benzene, naphthalene, anthracene, and phenanthrene.
Specifically, a phenyl group is preferable as the aryl group represented by Ar01
Examples of the heteroaryl group as Ar01 include a group in which one hydrogen atom has been removed from an aromatic heterocyclic ring. Examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
Specifically, a thiophenyl group is preferable as the heteroaryl group represented by Ar01.
Some or all hydrogen atoms in the aryl group and the heteroaryl group as Ar01 are substituted with iodine atoms.
The number of the iodine atoms is preferably in a range of 1 to 5, more preferably in a range of 1 to 3, still more preferably 2 or 3, and particularly preferably 3.
The aryl group and the heteroaryl group as Ar01 may have a substituent other than the iodine atom Examples of substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
In General Formula (a0-1), among the examples, Ar01 represents preferably an aryl group having 1 to 3 iodine atoms or a heteroaryl group having 1 to 3 iodine atoms, more preferably an aryl group having 1 to 3 iodine atoms, and still more preferably a phenyl group having 1 to 3 iodine atoms.
Among the examples, it is preferable that the constitutional unit (a01) is a constitutional unit (a011) derived from a compound represented by General Formula (a0-1-1).
[In the formula, RW01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. L001 represents an ester bond, an aromatic hydrocarbon group, a lactone-containing cyclic group, or a divalent linking group having a group consisting of a combination of these groups. Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
R01, Ra01, Ra02, and Ar01 in General Formula (a0-1-1) each have the same definition as that for R01, Ra01, Ra02, and Ar01 in General Formula (a0-1).
In General Formula (a0-1-1), L001 represents an ester bond, an aromatic hydrocarbon group, a lactone-containing cyclic group, or a divalent linking group having a group consisting of a combination of these groups. Examples of the divalent linking group include the same groups as those for the ester bond, the aromatic hydrocarbon group, the lactone-containing cyclic group, or the divalent linking group having a group consisting of a combination of these groups as L01 in General Formula (a0-1),
in General Formula (a0-1-1), L001 represents preferably a group represented by any of General Formulae (L0-r-1) to (L0-r-5), more preferably a group represented by any of General Formulae (L0-r-3) to (L0-r-5), and still more preferably a group represented by General Formula (L0-r-3).
Specific examples of the compound represented by General Formula (a0-1) are shown below,
Among the examples, as the constitutional unit. (a01) in the resist composition according to the present embodiment, a constitutional unit derived from a compound by any of Chemical Formulae (a01-01-1) to (a01-01-17) is preferable, a constitutional unit derived from a compound represented by any one of Chemical Formulae (a01-01-2) to (a01-01-9) is more preferable, a constitutional unit derived from a compound represented by Chemical Formula (a01-01-6), (a01-01-8), or (a01-01-9) is still more preferable, and a constitutional unit derived from a compound represented by Chemical Formula (a01-01-8) or (a01-01-9) is particularly preferable.
The proportion of the constitutional unit (a01) in the component (A1) is preferably in a range of 20% to 80% by mole, more preferably in a range of 30% to 70% by mole, and still more preferably in a range of 40% to 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the component (A1). In a case where the proportion of the constitutional unit (a01) is greater than or equal to the lower limits of the above-described preferable ranges, the sensitivity and the roughness reducing property are further improved. Meanwhile, in a case where the proportion thereof is equal to or less than the upper limits of the above-described preferable ranges, that is, in a case where the component (A1) has other constitutional units in addition to the constitutional unit (a01), the lithography characteristics can be further improved depending on the balance between the constitutional unit (a01) and the other constitutional units described below.
The component (A1) may have other constitutional units as necessary in addition to the constitutional unit (a01) described above.
Examples of the other constitutional units include a constitutional unit (a1) containing an acid decomposable group whose polarity is increased due to the action of an acid; a constitutional unit (a10) represented by General Formula (a10-1); a constitutional unit (a2) containing a lactone-containing cyclic group; and a constitutional unit (a8) derived from a compound represented by General Formula (a8-1).
Further, constitutional units corresponding to the above-described constitutional unit (a01) are excluded as the other constitutional units.
«Constitutional unit (a1)»
The constitutional unit (a1) is a constitutional unit that contains an acid decomposable group whose polarity is increased due to the action of an acid.
Here, constitutional units corresponding to the above-described constitutional unit (a01) are excluded.
Examples of the acid dissociable group are the same as those which have been suggested as the acid dissociable groups of the base resin for a chemically amplified resist composition.
Specific examples of those which have been suggested as the acid dissociable groups of the base resin for a chemically amplified resist composition include “acetal type acid dissociable group”, “tertiary alkyl ester type acid dissociable group”, “tertiary alkyloxycarbonyl acid dissociable group”, and “secondary alkyl ester type acid dissociable group” described below.
Acetal type acid dissociable group:
Examples of the acid dissociable group that protects a carboxy group or a hydroxyl group in the polar groups include an acid dissociable group represented by General Formula (a1-r-1) (hereinafter, also referred to as “acetal type acid dissociable group”).
[In the formula, R′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 Formula (a1-r-1), it is preferable that at least one of Ra′1 or Ra′2 represents 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 alkyl groups exemplified as 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 preferred examples thereof include linear or branched alkyl groups. 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 more preferable, and a methyl group is particularly preferable.
In 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.
As the aliphatic hydrocarbon group which is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferable. The monocycloalkane has preferably 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferable. As the polycycloalkane, a group having 7 to 12 carbon atoms is preferable, 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 the aromatic ring is a cyclic conjugated system having (4n+2) π electrons and may be monocyclic or polycyclic. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the above-described aromatic hydrocarbon rings have been substituted with heteroatoms. Examples of the heteroatom 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 number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably in a range of 1 to 4, more preferably 1 or 2, and particularly preferably 1.
The cyclic hydrocarbon group as Ra′3 may include a substituent. Examples of the substituent include Ra′5 described above,
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.
Tertiary alkyl ester type acid dissociable group:
Examples of the acid dissociable group that protects a carboxy group among the polar groups include an acid dissociable group represented by General Formula (a1-r-2).
Among examples of the acid dissociable group represented by Formula (a1-r-2), a group formed of an alkyl group is referred to as “tertiary alkyl ester type acid dissociable group” for convenience.
[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 groups as those for 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 groups as those for 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 (a1-2-1), 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 one another, suitable examples thereof include a group represented by General Formula (a1-r2-4).
[In 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 heteroatom-containing group. Ra′11 represents a group that forms an aliphatic cyclic group with the carbon atom to which Ra′10 has been bonded. In Formula (a1-r2-2), Ya represents a carbon atom. Xa represents a group that forms a cyclic hydrocarbon group with Ya. Some or all hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra101 to Ra103 each independently represent a hydrogen atom, a chain-like monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all hydrogen atoms 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 Formula (a1-r2-3), Yaa represents a carbon atom. Xaa represents a group that forms an aliphatic cyclic group with Yaa. Ra104 represents an aromatic hydrocarbon group which may have a substituent. In Formula (a1-r2-4), Ra′12 and Ra′13 each independently represent a chain-like monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra′14 represents a hydrocarbon group which may have a substituent. * represents a bonding site (the same applies hereinafter).]
In Formula (a1-r2-1), Ra′1 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 heteroatom-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 heteroatom-containing group. For example, some hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Further, some carbon atoms (methylene group or the like) constituting the alkyl group may be substituted with a heteroatom-containing group.
Examples of the heteroatoms here include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the heteroatom-containing group include (—O—), —C(═O)—O—, —O—C(═O)—, —C(═)—, —O—C(═O)—O—, —C(═O)—NHN—, —NH—, —S—, —S(═O)2—, and —S(═O)2—O—.
In Formula (a1-r2-1), preferred examples of Ra′11 (an aliphatic cyclic group that is formed together with a carbon atom to which Ra′10 is bonded) include the groups exemplified as the aliphatic hydrocarbon group (alicyclic hydrocarbon group) which is a monocyclic group or a polycyclic group as Ra′3 in Formula (a1-r-1). Among them it is preferably a monocyclic alicyclic hydrocarbon group, and specifically, it is more preferably a cyclopentyl group or a cyclohexyl group.
In 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 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 exemplified as the substituents that the cyclic hydrocarbon group as Ra′ may have.
In Formula (a1-r2-2), examples of the chain-like monovalent 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[22.2]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 represent preferably a hydrogen atom or a chain-like monovalent 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 cyclopentylidenethenyl group, and a cyclohexylidenethenyl group. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, or a cyclopentylidenethenyl group is preferable.
In Formula (a1-r2-3), as the aliphatic cyclic group that is formed by Xaa together with Yaa, the group exemplified as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group as Ra′021 in Formula (a1-r-1) is preferable.
In 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 represents 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 that Ra104 in Formula (a1-r2-3) may have include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group), and an alkyloxycarbonyl group.
in Formula (a1-r2-4), Ra′12 and Ra′13 each independently represent a chain-like monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of the chain-like monovalent saturated hydrocarbon group having 1 to 10 carbon atoms as Ra′12 and Ra′13 include those exemplified as the chain-like monovalent saturated hydrocarbon group having 1 to 10 carbon atoms as Ra101 to Ra103. Some or all hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted.
Ra′12 and Ra′13 represent preferably 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 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‘-’ 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-dinmethylbutyl 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.
As the aliphatic hydrocarbon group which is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferable. The monocycloalkane has preferably 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferable. As the polycycloalkane, a group having 7 to 12 carbon atoms is preferable, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
Examples of the aromatic hydrocarbon group as Ra′14 include the same groups as those for the aromatic hydrocarbon group as Ra104. Among these, Ra′14 represents 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 that Ra′14 may have include the same groups as those for the substituent that Ra104 may have.
In a case where Ra′14 in Formula (a1-r2-4) represents a naphthyl group, the position bonded to the tertiary carbon atom in Formula (a1-r2-4) may be the 1-position or the 2-position of the naphthyl group.
In a case where Ra′14 in Formula (a1-r2-4) represents an anthryl group, the position bonded to the tertiary carbon atom in 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 Formula (a1-r2-1) are shown below.
Specific examples of the group represented by Formula (a1-r2-2) are shown below.
Specific examples of the group represented by Formula (a1-r2-3) are shown below.
Specific examples of the group represented by Formula (a1-r2-4) are shown below.
Examples of the acid dissociable group that protects a hydroxyl group among the polar groups include an acid dissociable group (hereinafter, also referred to as “tertiary alkyloxycarbonyl acid dissociable group” for convenience) represented by General Formula (a1-r-3).
[In the formula, Ra′7 to Ra′9 each represent an alkyl group.]
In Formula (a1-r-3), Ra′7 to Ra′9 each represent preferably an alkyl group having 1 to 5 carbon atoms and more preferably an alkyl group having 1 to 3 carbon atoms.
Further, the total number of carbon atoms in each alkyl group 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 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 some hydrogen atoms in a hydroxyl group of a constitutional unit derived from hydroxystyrene or a hydroxystyrene derivative are protected by a substituent containing the acid decomposable group; and a constitutional unit in which at least some hydrogen atoms in —C(═)—OH of a constitutional unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative are protected by a substituent containing the acid decomposable group.
Examples of the acid dissociable group that protects a carboxy group among the polar groups include an acid dissociable group represented by General Formula (a1-r-4).
[In the formula, Ra′10 represents a hydrocarbon group. Ra′11 a and Ra′11 each independently represent a hydrogen atom, a halogen atom, or an alkyl group. Ra′12 represents a hydrogen atom or a hydrocarbon group. Ra′10 and Ra′11a, or Ra′11b may be bonded to each other to form a ring. Ra′11a or Ra′11b and Ra′12 may be bonded to each other to form a ring.]
Examples of the hydrocarbon group as Ra′10 or Ra′12 in the formula include the same groups as those for Ra′3.
Examples of the alkyl group as Ra′11a and Ra′11b in the formula include the same groups as those for the alkyl group as Ra′1.
In the formula, the hydrocarbon group as Ra′10 or Ra′12 and the alkyl group as Ra′11 and Ra′11b nay have a substituent. Examples of the substituent include Rax5 described above.
Ra′10 and Ra′11a or Ra′11b may be bonded to each other to form a ring. The ring may be a polycyclic ring or a monocyclic ring, and may be an alicyclic ring or an aromatic ring.
The alicyclic ring and the aromatic ring may have a heteroatom-.
Among the examples described above, as the ring formed by Ra′10 and Ra′11a or Ra′11b being bonded to each other, monocycloalkene, a ring in which some carbon atoms of monocycloalkene have been substituted with heteroatoms (such as an oxygen atom and a sulfur atom), or monocycloalkadiene is preferable, cycloalkene having 3 to 6 carbon atoms is preferable, and cyclopentene or cyclohexene is preferable.
The ring formed by Ra′10 and Ra′11a or Ra′11b being bonded to each other may be a condensed ring. Specific examples of the condensed ring include indane.
The ring formed by Ra′10 and Ra′11a or Ra′11b being bonded to each other may have a substituent. Examples of the substituent include Ra75 described above.
Ra′11a or Ra′11b and Ra′12 may be bonded to each other to form a ring, and examples of the ring include the rings formed by Ra′10 and Ra′11a or Ra′11b being bonded to each other.
Specific examples of the group represented by Formula (a1-r-4) are shown below.
Specific examples of the constitutional unit (a1) are shown below. In the formulae shown below, R0″ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
The constitutional unit (a1) of th component (A1) may be used alone or two or more kinds thereof.
The proportion of the constitutional unit (a1) in the component (A1) is preferably 50% by mole or less and more preferably in a range of 0% to 30% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the component (A1),
In regard to constitutional unit (a10):
The constitutional unit (a10) is a constitutional unit represented by General Formula (a10-1).
Here, constitutional units corresponding to the above-described constitutional unit (a01) are excluded.
[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. Yax1 represents a single bond or a divalent linking group. Wax1 represents an aromatic hydrocarbon group which may have a substituent. nax1 represents an integer of 1 or greater.]
In the Formula (a10-1), R01 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
R represents 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 from the viewpoint of industrial availability, more preferably a hydrogen atom, a methyl group, or trifluoromethyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom,
In Formula (a10-1), Yax1 represents a single bond or a divalent linking group.
In the chemical formula, the divalent linking group as Yax1 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 heteroatom.
Yax1 represents preferably a single bond, an ester bond [—C(═O)—O—or —O— C(═O)—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof and more preferably a single bond or an ester bond [—C(═O)—O— or —O—C(═O)—]
In Formula (a10-1), Wax1 represents an aromatic hydrocarbon group which may have a substituent.
Examples of the aromatic hydrocarbon group as Wax include a group in which (nax1+1) hydrogen atoms have been removed from an aromatic ring which may have a substituent. The aromatic ring is not particularly limited as long as the aromatic ring is a cyclic conjugated system having 4n+2) π electrons. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 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 some carbon atoms constituting the above-described aromatic hydrocarbon ring with a heteroatom. Examples of the heteroatom 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. Further, examples of the aromatic hydrocarbon group as Wax also include a group in which (nax1+1) hydrogen atoms have been removed from an aromatic compound having an aromatic ring (for example, biphenyl or fluorene) which may have two or more substituents.
Among the examples, Wax1 represents preferably a group in which (nax1+1) hydrogen atoms have been removed from benzene., naphthalene, anthracene, or biphenyl, more preferably a group in which (nax1+1) hydrogen atoms have been removed from benzene or naphthalene, and still more preferably a group in which (nax1+1) hydrogen atoms have been removed from benzene.
The aromatic hydrocarbon group as Wax1 may or may not have a substituent. Examples of substituents include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent include those described as the substituent of the cyclic aliphatic hydrocarbon group as Yax1. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, still more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. It is preferable that the aromatic hydrocarbon group as Wax1 has no substituent.
In Formula (a10-1), nax1 represents an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2, or 3, and particularly preferably 1 or 2.
Specific examples of the constitutional unit (a10) represented by Formula (a10-1) are described below.
In the formulae shown below, R01 represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
The constitutional unit (a10l) of the component (A1) may be used alone or two or more kinds thereof,
In a case where the component (A1) has the constitutional unit (a10)), the proportion of the constitutional unit (a10) in the component (A1)I is preferably in a range of 20% to 80% by mole, more preferably in a range of 30% to 70% v by mole, and still more preferably in a range of 30% to 60% by mole with respect to the total amount
In a case where the proportion of the constitutional unit (a10) is set to be greater than or equal to the above-described lower limits, the sensitivity is likely to be enhanced. Meanwhile, in a case where the proportion thereof is set to be less than or equal to the above-described upper limits, the constitutional unit (a10) and other constitutional units are likely to be balanced.
The component (A1) may further have a constitutional unit (a2) (here, constitutional units corresponding to the constitutional units (a01) and (a1) are excluded) containing a lactone-containing cyclic group.
In a case where the component (A1) is used to form a resist film, the lactone-containing cyclic group of the constitutional unit (a2) is effective for increasing the adhesiveness of the resist film to the substrate. Further, in a case where the component (A1) has the constitutional unit (a2), the lithography characteristics and the like are enhanced due to the effects of appropriately adjusting the acid diffusion length, increasing the adhesiveness of the resist film to the substrate, and appropriately adjusting the solubility during the development.
The term “lactone-containing cyclic group” indicates a cyclic group that has a ring (lactone ring) containing —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 in the constitutional unit (a2) is not particularly limited, and an optional constitutional unit can be used. Specific examples thereof include groups each represented by General Formulae (a2-r-1) to (a2-r-7).
[in the formulae, Ra′21's each independently represent 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, or a lactone-containing cyclic group. A″ represents an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom (—O—) or a sulfur atom (—S—), an oxygen atom, or a sulfur atom, n′ represents an integer of 0 to 2, and m′ is 0 or 1. * represents a bonding site (the same applies hereinafter).]
In General Formulae (a2-r-1) to (a2-r-7), it is preferable that the alkyl group as Ra′21 is an alkyl group having 1 to 6 carbon atoms. It is preferable that the alkyl group is linear or branched. 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 is an alkoxy group having 1 to 6 carbon atoms. It is preferable that the alkoxy group is linear or branched. Specific examples of the alkoxy groups include a group formed by linking the above-described alkyl group exemplified as the alkyl group represented by Ra′21 to an oxygen atom (—O—).
As the halogen atom as Ra′21, a fluorine atom is preferable.
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 the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable,
In —COOR″ and —OC(═O)R″ as Ra′21, any R″ represents a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
The alkyl group as R″ may be linear, branched, or cyclic, and it preferably has 1 to 15 carbon atoms.
In a case where R″ represents a linear or branched alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable. In a case where R″ represents a cyclic alkyl group, the number of carbon atoms thereof is preferably in a range of 3 to 15, more preferably in a range of 4 to 12, and most preferably in a range of 5 to 10. Specific examples thereof include groups in which one or more hydrogen atoms have been removed from a monocycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, or tetracycloalkane. More specific examples thereof include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.
Examples of the lactone-containing cyclic group as R″ include the same groups as those for the groups each represented by General Formulae (a2-r-F) to (a2-r-7). 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′21 has been substituted with a hydroxyl group.
Among the examples, it is preferable that Ra′21's each 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 in the terminal of the alkylene group or between the carbon atoms of the alkylene group. Further, examples thereof include —O—CH2—, —CH)—O—CH2—, —S—CH2—, and —CH2—S—CH2—. A″ represents 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 groups each represented by General Formulae (a2-r-1) to (a2-r-7) are shown below.
As the constitutional unit (a2), a constitutional unit derived from acrylic acid ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent is preferable.
It is preferable that such a constitutional unit (a2) is a constitutional unit represented by General Formula (a2-1).
[In the formula, R01 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.]
In Formula (a2-1), R has the same definition as described above. R represents 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 from the viewpoint of the industrial availability.
In 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 heteroatom.
It is preferable that Ya21 represents a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof.
In Formula (a2-1), it is preferable that Ya2′ represents a single bond and La21 represents —COO— or —OCO—.
In Formula (a2-1), Ra21 represents a lactone-containing cyclic group.
Suitable examples of the lactone-containing cyclic group as Ra2 include groups each represented by General Formulae (a2-r-1) to (a2-r-7).
Among these, a group represented by General Formula (a2-r-1), (A2-r-2), or (a2-r-6) is preferable, and a group represented by General Formula (a2-r-1) or (a2-r-2) is more preferable. Specifically, any one of groups each represented by Chemical Formulae (r-1c-1-1) to (r-1e-1-7), (r-1c-2-1) to (r-1c-2-18), and (r-1c-6-1) is more preferable, and any one of groups each represented by Chemical Formulae (r-1e-1-1), (r-1c-2-1), and (r-1c-2-7) is still more preferable.
The constitutional unit (a2) of the component (A1) may be used alone or two or more kinds thereof.
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 80% by mole, more preferably in a range of 5% to 70% by mole, and still more preferably in a range of 5% to 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the component (A1),
In a case where the proportion of the constitutional unit (a2) is set to be greater than or equal to the lower limits of the above-described preferable ranges, the effect to be obtained by allowing the component (A1) to have the constitutional unit (a2) is sufficiently obtained by the above-described effects. Further, in a case where the proportion thereof is set to be less than or equal to the upper limits of the above-described preferable ranges, the constitutional unit (a2) and other constitutional units can be balanced, and the lithography characteristics are enhanced.
In regard to constitutional unit (a8):
The constitutional unit (a8) is a constitutional unit derived from a compound represented by General Formula (a8-1).
Here, constitutional units corresponding to the constitutional unit (a0) are excluded.
[In the formula, W2 represents a polymerizable group-containing group. Yax2 represents a single bond or an (nax2+1)-valent linking group. Yax2 and W2 may form a condensed ring. R1 represents a fluorinated alkyl group having 1 to 12 carbon atoms. R2 represents an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom. R2 and Yax2 may be bonded to each other to form a ring structure. nax2 represents an integer of 1 to 3.]
The term “polymerizable group” in the polymerizable group-containing group as W2 denotes a group that enables a compound containing a polymerizable group to be polymerized by radical polymerization or the like, which is, for example, a group having a multiple bond between carbon atoms, such as an ethylenic double bond.
The polymerizable group-containing group may be a group formed of only a polymerizable group or a group formed of a polymerizable group and a group other than the polymerizable group. Examples of the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent and a divalent linking group having a heteroatom.
Suitable examples of the polymerizable group-containing group include a group represented by Chemical Formula:
C(RX11)(RX12)═C(RX13)—Yax0
In the chemical formula, RX11, RX12, and RX13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Yax0 represents a single bond or a divalent linking group.
Examples of the condensed ring formed by Yax2 and W2 include a condensed ring formed by a polymerizable group of the W2 moiety with Yax2 and a condensed ring formed by a group other than the polymerizable group of the W2 moiety with Yax2.
The condensed ring formed by Yax2 and W2 may have a substituent.
Specific examples of the constitutional unit (a8) are shown below.
In the following formulae, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
Among the examples, the constitutional unit (a8) is preferably at least one selected from the group consisting of constitutional units each represented by Chemical Formulae (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10) and more preferably at least one selected from the group consisting of constitutional units each represented by Chemical Formulae (a8-1-01) to (a8-1-04) and (a8-1-09).
The constitutional unit (a8) of the component (A1) may be used alone or two or more kinds thereof,
The proportion of the constitutional unit (a8) in the component (A1) is preferably 50% by mole or less and more preferably in a range of 0% to 30% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the component (A1).
The component (A1) of the resist composition may be used alone or a combination of two or more kinds thereof may be used.
In the resist composition according to the present embodiment, examples of the component (A1) include a polymer compound having a repeating structure of the constitutional unit (a01).
Among the examples, suitable examples of the component (A1) include a polymer compound having a repeating structure of the constitutional unit (a01) and the constitutional unit (a10).
More specific suitable examples of the component (A1) include a polymer compound having a repeating structure of the constitutional unit (a01) and the constitutional unit (a10); a polymer compound having a repeating structure of the constitutional unit (a01) and the constitutional unit (a2); and a polymer compound having a repeating structure of the constitutional unit (a01), the constitutional unit (a10), and the constitutional unit (a2).
The proportion of the constitutional unit (a01) in the polymer compound having a repeating structure of the constitutional unit (a01) and the constitutional unit (a10) 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 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the polymer compound.
In addition, the proportion of the constitutional unit (a10) in the polymer compound 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 40% to 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the polymer compound.
The proportion of the constitutional unit (a01) in the polymer compound having a repeating structure of the constitutional unit (a01) and the constitutional unit (a2) 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 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the polymer compound.
In addition, the proportion of the constitutional unit (a2) in the polymer compound 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 40% to 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the polymer compound.
The proportion of the constitutional unit (a01) in the polymer compound having a repeating structure of the constitutional unit (a01), the constitutional unit (a10), and the constitutional unit (a2) is preferably in a range of 10% to 90% by mole, more preferably in a range of 2.0% 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 60% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the polymer compound.
Further, the proportion of the constitutional unit (a10) in the polymer compound is preferably in a range of 5% to 80% by mole, more preferably in a range of 10% to 70% by mole, still more preferably in a range of 20% to 60% by mole, and particularly preferably in a range of 30% to 50% by mole with respect to the total amount (100% by mole) of all constitutional units constituting the polymer compound.
Further, the proportion of the constitutional unit (a2) in the polymer compound is preferably in a range of 1% to 30% by mole, more preferably in a range of 3% to 20% 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 amount (100% by mole) of all constitutional units constituting the polymer compound.
Such a component (A1) can be produced by dissolving a monomer, from which each constitutional unit is derived, in a polymerization solvent and adding a radical polymerization initiator such as azobisisobutylonitrile (AIBN) or dimethyl azobisisobutyrate (for example, V-601) to the solution so that the polymerization is carried out.
Alternatively, the component (A1) can be produced by dissolving, in a polymerization solvent, a monomer from which the constitutional unit (a01) is derived and, as necessary, a monomer from which a constitutional unit (for example, the constitutional unit (a10)) other than the constitutional unit (a01) is derived, adding thereto a radical polymerization initiator as described above to carry out polymerization, and carrying out a deprotection reaction.
Further, a —C(CF3)2—OH group may be introduced to the terminal during the polymerization using a combination of chain transfer agents such as HS—CH2—CH2—CH2—C(CF3)2—OH. As described above, a copolymer into which a hydroxyalkyl group, formed by substitution of some 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 polystyrene according to gel permeation chromatography (GPC)) of the component (A1) is not particularly limited, but is preferably in a range of 1000 to 50000, more preferably in a range of 2000 to 30000, and still more preferably in a range of 3000 to 20000.
In a case where the Mw of the component (A1) is less than or equal to the upper limits of the above-described preferable ranges, the resist composition exhibits satisfactory solubility in a resist solvent for a resist enough to be used as a resist. Meanwhile. in a case where the Mw of the component (A1) is greater than or equal to the lower limits of the above-described preferable ranges, the dry etching resistance and the cross-sectional shape of the resist pattern are satisfactory.
Further, the dispersity (Mw/Mn) of the component (A1) is not particularly limited, but 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 10.0 to 2.0. Further, Mn represents the number average molecular weight.
In the resist composition of the present embodiment, a base material component (hereinafter, also referred to as “component (A2)”) which does not correspond to the component (A1) and whose solubility in a developing solution is changed due to the action of an acid may be used in combination as the component (A).
The component (A2) is not particularly limited and may be optionally selected from a plurality of components of the related art which have been known as base material components for a chemically amplified resist composition and used.
As the component (A2), a polymer compound or a low-molecular-weight compound may be used alone or a combination of two or more kinds thereof may be used.
The proportion of the component (A1) in the component (A) is preferably 25% by mass or greater, more preferably 50% by mass or greater, and still more preferably 75% by mass or greater, and may be 100% by mass with respect to the total mass of the component (A). In a case where the proportion thereof is 25% by mass or greater, a resist pattern having excellent various lithography characteristics such as high sensitivity, high resolution, and improved roughness is likely to be formed.
In the resist composition of the present embodiment, the amount of the component (A) may be adjusted according to the thickness of the resist film intended to be formed.
The resist composition according to the present embodiment may further contain other components in addition to the component (A) described above. Examples of the other components include a component (B), a component (D), a component (E), a component (F), and a component (S), which are described below.
It is preferable that the resist composition according to the present embodiment further contains an acid generator component (B) that generates an acid upon light exposure.
The component (B) is not particularly limited, and those which have been suggested so far as an acid generator for a chemically amplified resist composition in the related art can be used.
Examples of the acid generator include various acid generators, for example, 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)diazonethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.
Examples of the onium salt-based acid generators include a compound represented by General Formula (b-1) (hereinafter, also referred to as “component (b-1)”), a compound represented by General Formula (b-2) (hereinafter, also referred to as “component (b-2)”), and a compound represented by General Formula (b-3) (hereinafter, also referred to as “component (b-3)”).
Examples of the onium salt-based acid generators include a compound represented by General Formula (b-1) (hereinafter, also referred to as “component (b-1)”), a compound represented by General Formula (b-2) (hereinafter, also referred to as “component (b-2)”), and a compound represented by General Formula (b-3) (hereinafter, also referred to as “component (b-3)”).
[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 greater, and M+ represents an n-valent onium cation.]
Anions in Component (b-1)
In 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. Further, the aliphatic hydrocarbon group may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group is saturated.
The aromatic hydrocarbon group as Ra101 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group has preferably 3 to 30 carbon atoms., more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 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 of the aromatic hydrocarbon group as R101 include benzene., fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and an aromatic heterocyclic ring in which some carbon atoms constituting any of these aromatic rings have been substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic rings include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group as R101 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, I-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group (alkyl chain in the arylalkyl group) has preferably 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
Examples of the cyclic aliphatic hydrocarbon group as R101 include an aliphatic hydrocarbon group having a ring in the structure thereof.
Examples of the aliphatic hydrocarbon group having a ring in the structure thereof include an alicyclic hydrocarbon group (a group in which one hydrogen atom has been removed 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 the middle of a linear or branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group has preferably 3 to 20 carbon atoms and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane has preferably 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane is preferable, and the number of carbon atoms of the polycycloalkane is preferably in a range of 7 to 30. Among these, a polycycloalkane having a cross]inked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; and a polycycloalkane having a condensed ring polycyclic skeleton such as a cyclic group having a steroid skeleton are preferable as the polycycloalkane.
Among the examples, as the cyclic aliphatic hydrocarbon group as R101, 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 still more preferable, and an adamantyl group is particularly preferable.
The linear aliphatic hydrocarbon group which may be bonded to the alicyclic 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 pentanethylene group [—(CH2)3—].
The branched aliphatic hydrocarbon group which may be bonded to the alicyclic 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(CH2)—, —CH(CH2CH3)—, —C(CH3)2—, —C(CH3)(CH2CH3)—, —C(CH3)(CH2CH2CH3), and —C(CHCH3)2—; alkylethylene groups such as —CH(CH3)CH2—, —CH(CH3)CH(CH3)—, —C(CH3)2CH2—, —CH(CH2 CH3)CH2—, and —C(CH2CH3)2—CH—; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2—CHCH2)CH2—; and alkyltetramethylene groups such as —CH(CH3)CH2CH—CH2— and —CH2CH(CH3)CH2CH2—. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.
Further, the cyclic hydrocarbon group as R101 may have a heteroatom such as a heterocyclic ring. Specific examples thereof include lactone-containing cyclic groups each represented by General Formulae (a2-r-1) to (a2-r-7), —SO2—containing cyclic groups each represented by General Formulae (b5-r-1) to (b5-r-4), and other heterocyclic groups each represented by Chemical Formulae (r-hr-1) to (r-hr-16). In the formulae, * represents a bonding site with respect to Y101 in Formula (b-1).
[In the formulae, Rb′51 's each independently represent 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, or a —SO2—containing cyclic group, B″ represents an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and n′ represents an integer of 0 to 2. * represents a bonding site.]
In General Formulae (b5-r-1) and (b5-r-2), B″ represents an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom.
B″ represents preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably a methylene group.
In General Formulae (b5-r-1) to (b5-r-4), Rb′51's each independently represent 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. Among these, it is preferable that Rb′51's each independently represent a hydrogen atom or a cyano group.
Specific examples of the groups each represented by General Formulae (b5-r-1) to (b5-r-4) are shown below. In the formulae shown below, “Ac” represents an acetyl group.
Examples of the substituent for the cyclic group as R101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group is more preferable, and a methoxy group or an ethoxy group is most preferable.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable.
Example of the above-described halogenated alkyl group as the substituent include a group in which some or all 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 atoms. The carbonyl group as the substituent is a group that substitutes a methylene group (—CH2—) constituting the cyclic hydrocarbon group.
The cyclic hydrocarbon group as R may be a condensed cyclic group having a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the condensed ring include those obtained by fusing one or more aromatic rings with a polycycloalkane having a crosslinked ring polycyclic skeleton. Specific examples of the crosslinked ring polycycloalkane include a bicycloalkane 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 Formulae (r-br-1) and (r-br-2). In the formulae, * represents a bonding site with respect to Y101 in Formula (b-1).
Examples of the substituent that the condensed cyclic group as R101 may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
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 those exemplified 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 in which one hydrogen atom has been removed from the aromatic ring (an aryl group such as 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 a heterocyclic group represented by any of 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 in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane or cyclohexane, a group in which one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane, a lactone-containing cyclic group represented by any of General Formulae (a2-r-1) to (a2-r-7), a —SO2—containing cyclic group represented by any of General Formulae (b5-r-1) to (b5-r-4), and a heterocyclic group represented by any 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.
The linear alkyl group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
The branched alkyl group has preferably 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 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 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 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 examples, as the chain-like alkenyl group, a linear alkenyl group is preferable, a vinyl group or a propenyl group is more preferable, and a vinyl group is particularly preferable.
Examples of the substituent for the chain-like alkyl group or alkenyl group as R101 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 R101.
Among the examples, R101 represents 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 group in which one or more hydrogen atoms have been removed from a phenyl group, a naphthyl group, or a polycycloalkane; a lactone-containing cyclic group represented by any of General Formulae (a2-r-1) to (a2-r-7); or a —SO2—containing cyclic group represented by any of General Formulae (b5-r-1) to (b5-r-4) is preferable, a group in which one or more hydrogen atoms have been removed from a polycycloalkane is more preferable, and an adamantyl group is still more preferable.
in 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 atoms other than an oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.
Examples of the divalent linking group having an oxygen atom include a non-hydrocarbon oxygen atom-containing linking group 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 oxygen atom-containing linking groups with an alkylene group. Further, a sulfonyl group (—SO2) may be further linked to the combination. Examples of the divalent linking group having an oxygen atom include linking groups each represented by General Formulae (y-a1-1) to (y-a1-7). Further, 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 Formula (b-1).
[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(CH)(CH2CH3)—, —C(CH3)(CH2CH2CH3)—, or —C(CH2CH3)2—; an ethylene group [—CH2CH2—]; an alkylethylene group such as —CH(CH3)CH2—, —CH2(CH3)CH(CH3)—, C(CH3)2CH2—, or —CH(CH2CH3)CH2—; a trimethylene group (n-propylene group) L CH2CH2CH2—]; an alkyltrimethylene group such as —CH4(CH3)CH2CH2— or —CH2CH(CH3)CH2—; a tetramethylene group [—CH2CH2CHC2—]; an alkyltetrarnethylene group such as —CH(CH3)CH2CH2CH2— or —CH2CH(CH2)CH2CH2—; and a pentamethylene group [—CH2CHC2CH2CH2—].
Further, a part of methylene group 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 Formula (a1-r-1) is preferable, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is More preferable.
Y101 represents 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 any of Formulae (y-a1-1) to (y-a1-5).
In 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 some or all hydrogen atoms in the alkylene group as V101 have been substituted with fluorine atoms. Among the examples, V101 represents preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms and more preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.
In Formula (b-1), R102 represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R102 represents preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms and more preferably a fluorine atom.
In a ease where Y101 represents a single bond, specific example of the anion moiety represented by 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 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 any of Chemical Formulae (r-hr-1) to (r-hr-6), a condensed cyclic group represented by Formula (r-br-1) or (r-br-2), or a chain-like alkyl group which may have a substituent. R″102 represents an aliphatic cyclic group which may have a substituent, a condensed cyclic group represented by Formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by any of General Formulae (a2-r-1) and (a2-r-3) to (a2-r-7), or a —SO2—containing cyclic group represented by any of General Formulae (b5-r-1) to (b5-r-4). R″102 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. V101 represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R10 represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Each v″ independently represents an integer of 0 to 3, each q″ independently represents an integer of 0 to 20, and n″ represents 0 or 1.]
As the aliphatic cyclic group as R″101, R″102, and R″103 which may have a substituent, the same groups as those for the cyclic aliphatic hydrocarbon group as R101 in Formula (b-1) are preferable. Examples of the substituent include the same groups as those for the substituent which may substitute the cyclic aliphatic hydrocarbon group as R101 in Formula (b-1).
As the aromatic cyclic group as R″103 which may have a substituent, the same groups as those for the aromatic hydrocarbon group in the cyclic hydrocarbon group as R101 in Formula (b-1) are preferable. Examples of the substituent include the same groups as those for the substituent which may substitute the aromatic hydrocarbon group as R101 in Formula (b-1).
As the chain-like alkyl group as R″101 which may have a substituent, the same groups as those for the chain-like alkyl group as R101 in Formula (b-1) are preferable.
As the chain-like alkenyl group as R″103 which may have a substituent, the same groups as those for the chain-like alkenyl group as R101 in Formula (b-1) are preferable.
Anions in Component (b-2)
In 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 groups as those for R101 in Formula (b-1). Here, R104 and R105 may be bonded to each other to form a ring.
R104 and R105 represent 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 has preferably 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 3 carbon atoms. It is preferable that the number of carbon atoms in the chain-like alkyl group as R104 and R105, decreases within the range of the number of carbon atoms from the viewpoint that the solubility in a solvent for a resist is also satisfactory. Further, in the chain-like alkyl group as Rr; and R105, it is preferable that the number of hydrogen atoms substituted with fluorine atoms is 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 ratio 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 is a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
In 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 groups as those for V101 in Formula (b-1).
In Formula (b-2), L101 and L102 each independently represent a single bond or an oxygen atom.
Anions in Component (b-3)
In 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 groups as those for R101 in Formula (b-1)
In Formula (b-3), L103 to L105 each independently represent a single bond, —CO—, or —SO2—.
Among the examples, as the anion moiety of the component (B), an anion in the component (b-1) is preferable.
In Formulae (b-1), (b-2), and (b-3), M′m+ represents an m-valent onium cation. Among these, a sulfonium cation and an iodonium cation are preferable.
in represents an integer of 1 or greater.
Preferred examples of the cation moiety ((M′m+)t/m) include organic cations each represented by General Formulae (ca-1) to (ca-3).
[In the formulae, R201 to R207 each independently represent an aryl group, an alkyl group, or an alkenyl group, which may have a substituent. R201 to R203, and R206 and R207 may be bonded to each other to form a ring with the sulfur atoms 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 a —SO2—containing cyclic group which may have a substituent. L201 represents —C(═O)— or —C(═O)—O—.]
In General Formulae (ca-1) to (ca-3), examples of the aryl group as R201 to R207 include an unsubstituted aryl group having 6 to 20 carbon atoms. Among these, a phenyl group or a naphthyl group is preferable.
As the alkyl group as R0″ to R207, a chain-like or cyclic alkyl group having 1 to 30 carbon atoms is preferable.
It is preferable that the alkenyl group as R201 to R207 has 2 to 10 carbon atoms.
Examples of the substituent that R201 to R207 and R210 may have 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 each 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. Further, the aliphatic hydrocarbon group may be saturated or unsaturated. In general, it is preferable that the aliphatic hydrocarbon group is saturated.
The aromatic hydrocarbon group as R′201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group has preferably 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms. particularly preferably 6 to 15 carbon atoms, and most preferably 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′102 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some carbon atoms constituting any of these aromatic rings have been substituted with heteroatoms. Examples of the heteroatom 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, 1-naphthylethyl group, or a 2-naphthylethyl group), The alkylene group (alkyl chain in the arylalkyl group) has preferably 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 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 having a ring in the structure thereof include an alicyclic hydrocarbon group (a group in which one hydrogen atom has been removed 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 the middle of a linear or branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group has preferably 3 to 20 carbon atoms and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane has preferably 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane is preferable, and the number of carbon atoms of the polycycloalkane is preferably in a range of 7 to 30. Among these, a polycycloalkane having a crosslinked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; and a polycycloalkane having a condensed ring polycyclic skeleton such as a cyclic group having a steroid skeleton are preferable as the polycycloalkane.
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 has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly 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—].
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(CH2(CH3)—, —C(CH3)2—, —C(CH3)(CH2CH3)—, —C(CH3)CH2CH2CH3)—, and —C(CH2CH3)2—; alkylethylene groups such as —CH(CH3)CH2—, —CH(CH3)CH(CH2, —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(CH)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.
Further, the cyclic hydrocarbon group as R′201 may have a heteroatom such as a heterocyclic ring. Specific examples thereof include lactone-containing cyclic groups each represented by General Formulae (a2-r-1) to (a2-r-7), —SO2—containing cyclic group each represented by General Formulae (b5-r-1) to (b5-r-4), and other heterocyclic groups each represented by 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.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, art ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group is more preferable, and a methoxy group or an ethoxy group is most preferable.
As the halogen atom as a substituent, a fluorine atom is preferable.
Example of the above-described halogenated alkyl group as the substituent include a group in which some or all 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 atoms. 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 has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
The branched alkyl group has preferably 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 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 examples, as the chain-like alkenyl group, a linear alkenyl group is preferable, a vinyl group or a propenyl group is more preferable, and a vinyl group is particularly preferable.
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 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 represents 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 in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group represented by any of General Formulae (a2-r-1) to (a2-r-7), and a —SO2—containing cyclic group represented by any of General Formulae (b5-r-1) to (b5-r-4).
In General Formulae (ca-1) to (ca-3), in a case where R201 to R203 and R206 and R207 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 heteroatom 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)— (RN represents an alkyl group having 1 to 5 carbon atoms). As a ring to be formed, a ring containing the sulfur atom in the formula in the ring skeleton thereof is preferably a 3- to 10-membered ring and particularly preferably a 5- to 7-membered ring containing the sulfur atom. Specific examples of the ring to be formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9-H-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 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 W210 include an unsubstituted aryl group having 6 to 20 carbon atoms. Among these., a phenyl group or a naphthyl group is preferable. As the alkyl group as R210, a chain-like or cyclic alkyl group having 1 to 30 carbon atoms is preferable.
It is preferable that the alkenyl group as R210 has 2 to 10 carbon atoms.
As the —SO2—containing cyclic group which may have a substituent as R210, “SO2—containing polycyclic group” is preferable, and a group represented by General Formula (b5-r-1) is more preferable.
Specific examples of suitable cations represented by Formula (ca-1) include cations each represented by Chemical Formulae (ca-1-1) to (ca-1-70).
[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 that R201 to R207 and R210 to R212 may have.]
In the resist composition according to the present embodiment, the component (B) may be used alone or a combination of two or more kinds thereof may be used.
In a case where the resist composition contains the component (BI), the amount of the component (B) in the resist composition is preferably less than 50 parts by mass, more preferably in a range of 10 to 40 parts by mass, and still more preferably in a range of 20 to 40 parts by mass with respect to 100 parts by mass of the component (A).
In a case where the amount of the component (B) is set to be in the above-described preferable ranges, pattern formation can be sufficiently carried out. Further, it is preferable that each component of the resist composition is dissolved in an organic solvent from the viewpoint that a uniform solution is likely to be obtained and the storage stability of the resist composition is enhanced.
It is preferable that the resist composition according to the present embodiment further contains a base component (hereinafter, also referred to as “component (D)”) that traps (that is, controls the acid diffusion) an acid that is generated upon light exposure, in addition to the component (A). The component (D) acts as a quencher (an acid diffusion control agent) which traps the acid generated in the resist composition upon light exposure.
Examples of the component (D) include a photodecomposable base (D1) having acid diffusion controllability (hereinafter. referred to as “component (D1)”) which is lost by the decomposition upon light exposure and a nitrogen-containing organic compound (D2) (hereinafter, referred to as “component (D2)”) which does not correspond to the component (D1). Among these, the photodecomposable base (the component (D1)) is preferable from the viewpoint of easily enhancing the roughness reducing property. Further, in a case where the resist composition contains the component (D1), both the characteristics of increasing the sensitivity and suppressing occurrence of coating defects are likely to be enhanced.
In a case where a resist composition containing the component (D1) is obtained, the contrast between an exposed portion and an unexposed portion of the resist film can be further improved in a case of forming a resist pattern.
The component (D1) is not particularly limited as long as the component is decomposed upon light exposure and loses an acid diffusion controllability, and one or more compounds selected from the group consisting of a compound represented by General Formula (d1-1) (hereinafter, referred to as “component (d1-1)”), a compound represented by General Formula (d1-2) (hereinafter, referred to as “component (d1-2)”), and a compound represented by General Formula (d1-3) (hereinafter, referred to as “component (d1-3)”) are preferable.
Since the components (d1-1) to (d1-3) are decomposed and lose the acid diffusion controllability (basicity), the components (d1-1) to (d1-3) do not function as a quencher at the exposed portion of the resist film, but function as a quencher at the unexposed portion of the resist film.
[In the formulae, Rd1 to Rd4 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. Here, no fluorine atom is bonded to the carbon atom adjacent to the S atom in Rd2 of Formula (d1-2). Yd1 represents a single bond or a divalent linking group, m represents an integer of 1 or greater, and Mm+'s each independently represent an m-valent organic cation.]
[Component (d1-1)]
In Formula (d1-1), Rd1 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 groups as those for R′201.
Among these, it is preferable that Rd1 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, a lactone-containing cyclic group represented by any of General Formulae (a2-r-1) to (a2-r-7), an ether bond, an ester bond, and a combination thereof. In a case where an ether bond or an ester bond is included as the substituent, the substituent may be bonded through an alkylene group, and a linking group represented by any of Formulae (y-a1-1) to (y-a1-5) is preferable as the substituent. Further, in a case where the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain-like alkyl group as Rd1 contain a linking group represented by any of General Formulae (y-a1-1) to (y-a1-7) as a substituent, V′101 in General Formulae (y-a1-1) to (y-a1-7) is bonded to the carbon atom constituting the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain-like alkyl group as Rd1 in Formula (d3-1), in General Formulae (y-a1-1) to (y-a1-7).
Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure having a bicyclooctane skeleton (for example, a polycyclic structure formed of a bicyclooctane skeleton and a ring structure other than the bicyclooctane skeleton).
As the aliphatic cyclic group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane. tricyclodecane or tetracyclododecane is more preferable.
It is preferable that the chain-like alkyl group 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 decy 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 has preferably 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. The fluorinated alkyl group may have 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 preferred examples of the anion moiety in the component (d1-1) are described below.
In Formula (d1-1), Mm+ represents an in-valent organic cation.
Suitable examples of the organic cation as Mm+ include the same cations as those for the cations each represented by General Formulae (ca-1) to (ca-3). Among these, a cation represented by General Formula (ca-1) is more preferable, and a cation represented by any of Formulae (ca-1-1) to (ca-1-113) is still more preferable.
The component (d1-1) may be used alone or a combination of two or more kinds thereof may be used.
{Component (d1-2)}
In Formula (d1-2), Rd2 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 groups as those for R′201.
Here, no fluorine atom is bonded to the carbon atom adjacent to the S atom in Rd2 (the carbon atom is not substituted with fluorine). In this manner, the anion of the component (d1-2) is an appropriately weak acid anion, thereby improving the quenching ability of the component (D),
Rd2 represents preferably a chain-like alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent and more preferably 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,
The hydrocarbon group as Rd2 may have a substituent, and examples of the substituent include the same groups as those for the substituent that the hydrocarbon group (such as an aromatic hydrocarbon group, an aliphatic cyclic group, or a chain-like alkyl group) as Rd1 in Formula (d1-1) may have.
Specific preferred examples of the anion moiety in the component (d1-2) are described below.
In Formula (d1-2),Mm+ represents an m-valent organic cation and has the same definition as that for Mm+ in Formula (d1-1).
The component (d1-2) may, be used alone or a combination of two or more kinds thereof may be used.
[Component (d1-3)}
In Formula (d1-3), Rd3 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 groups as those for R′201. Among these, a cyclic group having a fluorine atom, a chain-like alkyl group, or a chain-like alkenyl group is preferable. Among these, a fluorinated alkyl group is preferable, and the same groups as those for the fluorinated alkyl group represented by Rd1 are more preferable.
In Formula (d1-3), Rd4 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 groups as those for R′201.
Among these, 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 is preferable.
It is preferable that the alkyl group as Rd4 is 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. Some hydrogen atoms in the alkyl group as Rd4 may be substituted with a hydroxyl group, a cyano group, or the like.
It is preferable that the alkoxy group as Rd4 is an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Among these, a methoxy group and an ethoxy group are preferable.
Examples of the alkenyl group as Rd4 include the same groups as those for the alkenyl group as R′201. Among these, a vinyl group, a propenyl group (an allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. These groups may have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.
Examples of the cyclic group as Rd4 include the same groups as those for the cyclic group as R′201. Among these, an alicyclic group in which one or more hydrogen atoms have been removed from a cycloalkane such as cyclopentane, cyclohexane., adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane or an aromatic group such as a phenyl group or a naphthyl group is preferable. In a case where Rd4 represents an alicyclic group, the resist composition is satisfactorily dissolved in an organic solvent so that the lithography characteristics are enhanced. Further, in a case where Rd4 represents an aromatic group, the resist composition has excellent light absorption efficiency in lithography using EUV or the like as an exposure light source, and thus the sensitivity and lithography characteristics are enhanced.
In Formula (d1-3), Yd1 represents a single bond or a divalent linking group. The divalent linking group as Yd1 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 heteroatom. Examples of the divalent linking groups are the same as those for the divalent hydrocarbon group which may have a substituent and the divalent linking group having a heteroatom described in the section of the divalent linking group as Ya21 in Formula (a2-1).
It is preferable that Yd1 represents a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. As the alkylene group, a linear or branched alkylene group is more preferable, and a methylene group or an ethylene group is still more preferable.
Specific preferred examples of the anion moiety in the component (d1-3) are described below.
In Formula (d1-3). Mm+ represents an m-valent organic cation and has the same definition as that for Mm+ in Formula (d1-1).
The component (d1-3) may be used alone or a combination of two or more kinds thereof may be used.
As the component (D1), only one of the above-described components (d1-1) to (d1-3) or a combination of two or more kinds thereof may be used.
In a case where the resist composition contains the component (D1), the amount of the component (D1) in the resist composition is preferably in a range of 0.5 to 25 parts by mass, more preferably in a range of 1 to 20 parts by mass, and still more preferably in a range of 3 to 15 parts by mass with respect to 100 parts by mass of the component (A1).
In a case where the amount of the component (D1) is greater than or equal to the lower limits of the above-described preferable ranges, satisfactory lithography characteristics and a satisfactory resist pattern shape are likely to be obtained. Meanwhile, in a case where the content is less than or equal to the upper limits of the above-described ranges, the sensitivity can be satisfactorily maintained and the throughput is also excellent.
In the resist composition according to the present embodiment, it is preferable that the component (D1) contains the component (d1-1).
The amount of the component (d1-1) in the total component (D) contained in the resist composition according to the present embodiment is preferably 50% by mass or greater, preferably 70% by mass or greater, and still more preferably 90% by mass or greater, and the component (D) may consist of only the component (d1-1).
The methods of producing the component (d1-1) and the component (d1-2) are not particularly limited, and these components can be produced by known methods.
Further, the method of producing the component (d1-3) is not particularly limited, and the component is produced by the same method as disclosed in United States Patent Application, Publication No. 2012-0149916.
The component (D) may contain a nitrogen-containing organic compound component (hereinafter, referred to as “component (D2)”) that does not correspond to the component (D1) described above.
The component (D21 is not particularly limited as long as the component functions as an acid diffusion control agent and does not correspond to the component (D1), and an optional component may be selected from known components and then used. Among the examples, an aliphatic amine is preferable., and particularly a secondary aliphatic amine and a tertiary aliphatic amine are more preferable.
The aliphatic amine is an amine containing one or more aliphatic groups, and the number of carbon atoms in the aliphatic group is preferably in a range of 1 to 12.
Examples of the aliphatic amine include amines in which at least one hydrogen atom of ammonia NIH; has been substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkylalcoholamines), and cyclic amines.
Specific examples of the alkylamines and the alkylalcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamrine, and n-decylamine; dialkylamines such as diethylarnine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylanine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylalcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, a trialkylamine having 6 to 30 carbon atoms is still more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.
Examples of the cyclic amine include a heterocyclic compound having a nitrogen atom as a heteroatom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specific examples thereof include 1, 5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.
Examples of other aliphatic amines include tri(2-methoxymethoxyethyl)amine, tris(2-(2-methoxyethoxy)ethyl )amine, tris[2 (2-2-methoxyethoxymethoxy)ethyl)amine, tris{2-(1-methoxyethoxy)ethyl}amine, this(2-(1-ethoxyethoxy)ethyl}amine, tris(2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, and triethanolamine triacetate. Among these, triethanolamine triacetate is preferable.
As the component (D2), an aromatic amine may be used.
Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole, and derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonyl pyrrolidine, and 2,6-di-tert-butylpyridine.
Among the examples, the component (D2) is preferably an alkylamine and more preferably a trialkylamine having 6 to 30 carbon atoms.
The component (D2) may be used alone or a combination of two or more kinds thereof may be used.
In a case where the resist composition contains the component (D2), the amount of the component (D2) in the resist composition is preferably in a range of 0.01 to 5 parts by mass, more preferably in a range of 0.1 to 5 parts by mass, and still more preferably in a range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A1).
In a case where the amount of the component (D2) is greater than or equal to the lower limits of the above-described preferable ranges, satisfactory lithography characteristics and a satisfactory resist pattern shape are likely to be obtained. Meanwhile, in a case where the content is less than or equal to the upper limits of the above-described ranges, the sensitivity can be satisfactorily maintained and the throughput is also excellent.
«At Least One Compound (E) Selected from Group Consisting of Organic Carboxylic Acids, Phosphorus Oxo Acids, 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 “component (E)”) selected from the group consisting of an organic carboxylic acid, and a phosphorus oxo acid and a derivative thereof.
Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Among these, 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.
In the resist composition of the present embodiment, the component (E) may be used alone or a combination of two or more kinds thereof may be used.
In a case where the resist composition contains the component (E), the amount 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). Within the above range, the lithography characteristics are further improved.
The resist composition according to the present embodiment may further contain a fluorine additive component (hereinafter, referred to as “component (F)”) as a hydrophobic resin. The component (F) is used to impart water repellency to the resist film and used as a resin different from the component (A), whereby the lithography characteristics can be improved. As the component (F), for example, the fluorine-containing polymer compounds described in Japanese Unexamined Patent Application, First Publication Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 can be used.
Specific examples of the component (F) include a polymer having a constitutional unit (f1) represented by General Formula (f1-1). As the polymer, a polymer (homopolymer) formed of only the constitutional unit (f1) represented by Formula (f1-1); a copolymer of the constitutional unit (f1) and the constitutional unit (a1); or a copolymer of the constitutional unit (f1), a constitutional unit derived from acrylic acid or methacrylic acid, and the constitutional unit (a1) is preferable, and a copolymer of the constitutional unit (f1) and the constitutional unit (a1) is more preferable. Here, as the constitutional unit (a1) copolymerized with the constitutional unit (f1), a constitutional unit derived from 1-ethyl-1-cyclooctyl(meth)acrylate or a constitutional unit derived from 1-methyl-1-adamantyl (meth)acrylate is preferable, and a constitutional unit derived from 1-ethyl-1-cyclooctyl(meth)acrylate is more preferable.
[In the formula, R has the same definition as described above, Rf102 and Rf103 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf102 and Rf103 may be the same as or different from each other, nf1 represents an integer of 0 to 5, and Rf101 represents an organic group having a fluorine atom.]
In Formula (f1-1), R bonded to the carbon atom at the α-position has the same definition as described above. It is preferable that R represents a hydrogen atom or a methyl group.
In Formula (f1-1), a fluorine atom is preferable as the halogen atom as Rf102 and Rf103. Examples of the alkyl group having 1 to 5 carbon atoms as Rf102 and Rf103 include the same groups as, those for the Alky group having 1 to 5 carbon atoms as R, Among the examples, a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms as Rf102 and Rf103 include groups in which some or all hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Among these, a fluorine atom is preferable as the halogen atom. Among these, Rf102 and Rf103 represent preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom.
In Formula (f1-1), nf1 represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.
In Formula (f1-1), Rf101 represents an organic group having a fluorine atom and preferably a hydrocarbon group having a fluorine atom.
The hydrocarbon group having a fluorine atom may be linear, branched, or cyclic, and the number of carbon atoms thereof is preferably in a range of 1 to 20, more preferably in a range of 1 to 15, and particularly preferably in a range of 1 to 10.
In the hydrocarbon group having a fluorine atom, preferably 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more thereof are fluorinated, and particularly preferably 60% or more thereof are fluorinated from the viewpoint of increasing the hydrophobicity of the resist film during immersion exposure.
Among the examples, Rf101 represents more 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, or —CH2—CH2—CF2—CF2—CF2—CF3.
The weight-average molecular weight (Mw) (in terms of polystyrene according to gel permeation chromatography) of the component (F) is preferably in a range of 1000 to 50000, more preferably in a range of 5000 to 40000, and most preferably in a range of 10000 to 30000. In a case where the weight-average molecular weight thereof is less than or equal to the upper limits of the above-described ranges, the resist composition exhibits satisfactory solubility in a solvent for a resist enough to be used as a resist. Meanwhile, in a case where the weight-average molecular weight thereof is greater than or equal to the lower limits of the above-described ranges, water repellency of the resist film is enhanced.
Further, the dispersity (Mw/Mn) of the component (F) is preferably in a range of 1.0 to 5.0, more preferably in a range of 1.0 to 3.0, and most preferably in a range of 1.0 to 2.5.
In the resist composition according to the present embodiment, the component (F) may be used alone or a combination of two or more kinds thereof may be used.
In a case where the resist composition contains the component (F), the amount of the component (F) is preferably in a range of 0.5 to 10 parts by mass and more preferably in a range of 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).
The resist composition of the present embodiment can be produced by dissolving the resist materials in an organic solvent component (hereinafter, referred to as “component (S)”).
The component (S) may be any organic solvent which can dissolve each component to be used to obtain a uniform solution, and an optional organic solvent can be appropriately selected from those which have been known as solvents of a chemically amplified resist composition and then used.
Examples of the component (S) include lactones such as y-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 of compounds having an ether bond such as monoalkyl ether or monophenyl ether, such as monomethylether, monoethylether, monopropylether, or monobutylether of polyhydric alcohols or compounds having an ester bond [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol ronomethyl 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, ethylbenzylether, cresylnmethylether, diphenylether, dibenzylether, phenetole, butylphenylether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethylsulfoxide (DMSO). in the resist composition of the present embodiment, the component (S) may be used alone or in the forn of a mixed solvent of two or more kinds thereof. Amrt)ong these, PGME A, PGME, γ-butyrolactone, EL, or cyclohexanone is preferable.
Further, 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 in consideration of the compatibility between PGMEA and 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 mass ratio of PGNMEA to EL or cyclohexanone is preferably in a range of 1:9 to 9:1 and more preferably in a range of 2:8 to 8:2. Further, in a case where PGME is blended as the polar solvent, the mass ratio of PGMEA to PGME is preferably in a range of 1:9 to 9:1, more preferably in a range of 2:8 to 8:2, and still more preferably in a range of 3:7 to 7:3. Further., a mixed solvent of PGMEA, PGME, and cyclohexanone is also preferable.
Further, a mixed solvent of γ-butyrolactorne and at least one selected from PGMEA and EL is also preferable as the component (S). In this case, as the mixing ratio, the mass ratio between the former and 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 to have a concentration which enables coating a substrate or the like depending on the thickness of the coated film. The component (S) is typically used in an amount such that the solid content concentration of the resist composition is set to be in a range of 0.1% to 20% by mass and preferably in a range of 0.2% to 15% by mass.
After the resist material is dissolved in the component (S), impurities may be removed from the resist composition of the present embodiment using a porous polyimide film, a porous polyamideimide film, or the like. For example, the resist composition may be filtered using a filter formed of a porous polyimide film, a filter formed of a porous polyamideimide film, a filter formed of a porous polyimide film and a porous polyamideimide film, or the like. Examples of the porous polyimide film and the porous polyamideimide film include those described in Japanese Unexamined Patent Application, First Publication No. 2016-155121.
The resist composition according to the present embodiment described above contains a resin component (A1) having the above-described constitutional unit (a01). The constitutional unit (a01) contains an aryl group in which some or all hydrogen atoms have been substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms have been substituted with iodine atoms. Since the constitutional unit (a01) has iodine atoms, the constitutional unit (a01) has high absorption efficiency of extreme ultraviolet (EUV) and electron beams (EB).
Further, the constitutional unit (a01) contains a divalent linking group in a side chain. Therefore, in the resin component (A1) having the constitutional unit (a01), the three-dimensional structure of the resin component is different from the three-dimensional structure of a resin component having a constitutional unit that contains no divalent linking group in a side chain, and thus the solubility in a developing solution is enhanced.
Therefore, it is assumed that the resist composition containing the resin component (A1) according to the present embodiment is capable of forming a resist pattern with high sensitivity and a satisfactory roughness reducing property.
A method for forming a resist pattern according to the second aspect of 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 to light, and a step of developing the resist film exposed to light to form a resist pattern.
According to the embodiment of the method for forming a resist pattern, a method for forming a resist pattern, which is performed in the following manner is an exemplary example.
First, a support is coated with the resist composition of the present embodiment using a spinner or the like, and a bake (post applied bake (PAB)) treatment is performed under a temperature condition of 80° C. to 150° C. for 40 to 120 seconds and preferably 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, a bake treatment (post exposure bake (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 conducted using an alkali developing solution in a case of an alkali developing process and using a developing solution containing an organic solvent (organic developing solution) in a 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 a case of the alkali developing process, and water rinsing using a rinse solution containing an organic solvent is preferable in a case of the solvent developing process. in a case of the solvent developing process, after the developing treatment or the rinse treatment, the developing solution or the rinse solution attached onto the pattern may be removed by a treatment using a supercritical fluid.
After the developing treatment or the rinse treatment, drying is conducted. As desired, a bake treatment (post bake) may be conducted after the developing treatment.
In this manner, a resist pattern can be formed.
The support is not particularly limited and a known support of the related art can be used, and examples thereof include a substrate for an electronic component and a substrate on which a predetermined wiring pattern has been formed. Specific examples thereof include a metal substrate such as a silicon wafer, copper, chromium, iron, or aluminum; and a glass substrate. As the materials of the wiring pattern, copper, aluminum, nickel, or gold can be used.
The wavelength used for light exposure is not particularly limited and the exposure can be conducted using radiation such as an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, extreme ultraviolet (ELUV), vacuum ultraviolet rays (VUV), electron beams (EB), X-rays, and soft X-rays. The resist composition is useful for a KrF excimer laser, an Ark excimer laser, EB, and EUV, more useful for an ArF excimer laser, EB, and 1EUV, and particularly useful for EB and EUV. That is, the resist pattern formation method according to the present embodiment is a method particularly useful in a case where the step of exposing the resist film to light includes a process of exposing the resist film to extreme ultraviolet (EUV) or electron beams (EB).
The method of exposing the resist film to light can be general exposure (dry exposure) conducted in air or an inert gas such as nitrogen, or liquid immersion exposure (liquid immersion lithography).
The liquid immersion exposure is an exposure method in which the region between the resist film and the lens at the lowermost position of the exposure apparatus is filled with a solvent (liquid immersion medium) in advance that has a greater refractive index than the refractive index of air, and the exposure (immersion exposure) is conducted in this state.
As the liquid immersion medium, a solvent having a refractive index greater than the refractive index of air but smaller than the refractive index of the resist film to be exposed is preferable, 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.
As the alkali developing solution used for the developing treatment in the alkali developing process, a 0.1 to 10 mass % tetramethylanunonium hydroxide (TMAH) aqueous solution is an exemplary example.
The organic solvent contained in the organic developing solution used for the developing treatment in the solvent developing process may be any solvent that is capable of dissolving the component (A) (the component (A) before light exposure) and can be appropriately selected from known organic solvents. Specific examples thereof include a polar solvent such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, a nitrile-based solvent, an amide-based solvent, and an ether-based solvent, and a hydrocarbon-based solvent.
Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol nonamethyl ether acetate, ethylene glycol monoethyl ether acetate., diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate., ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
Examples of the nitrile-based solvent include acetonitrile, propionitrile, valeronitrile, and butyronitrile.
Known additives can be blended into the organic developing solution as necessary. Examples of the additive include a surfactant. 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 into the solution, the amount of the surfactant to be blended 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 performed according to a known developing method, and examples thereof include a method of immersing a support in a developing solution for a certain time (a dip method), a method of raising a developing solution on the surface of a support using the surface tension and maintaining the state for a certain time (a puddle method), a method of spraying a developing solution to the surface of a support (spray method), and a method of continuously ejecting a developing solution onto a support rotating at a certain rate while scanning a developing solution ejection nozzle at a certain rate (dynamic dispense method).
As the organic solvent contained in the rinse solution used for the rinse treatment after the developing treatment in the solvent developing process., a solvent that is unlikely to dissolve a resist pattern can be appropriately selected from the organic solvents described as the organic solvent used in the organic developing solution and then used. Typically, at least one solvent selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, and an ether-based solvent is used. Among these, at least one 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 solvent selected from an alcohol-based solvent and an ester-based solvent is more preferable, and an alcohol-based solvent is particularly preferable.
As the alcohol-based solvent used in the rinse solution, a monohydric alcohol having 6 to 8 carbon atoms is preferable, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples thereof include 1-hexanol, 1-heptanol, I-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 a combination of two or more kinds thereof may be used. Further, an organic solvent other than the above-described solvents and water may be mixed and used. However, in consideration of the development characteristics, the amount of water to be blended into the rinse solution 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 solution.
A known additive can be blended into the rinse solution as necessary. Examples of the additive include a surfactant. As the surfactant, the same surfactants as those described above are exemplary examples. Among these, 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 into the solution, the amount of the surfactant to be blended 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 solution.
The rinse treatment carried out using a rinse solution (washing treatment) can be performed according to a known rinse method. Examples of the method of performing the rinse treatment include a method of continuously ejecting a rinse solution onto a support rotating at a certain rate (rotary coating method), a method of immersing a support in a rinse solution for a certain time (dip method), and a method of spraying a rinse solution to the surface of a support (spray method).
According to the method for forming a resist pattern according to the present embodiment described above, since the resist composition described above is used, a resist pattern in which high sensitivity is achieved and the roughness reducing property is satisfactory can be formed.
It is preferable that various materials that are used in the resist composition according to the above-described embodiment and the pattern forming method according to the above-described embodiment (for example, a resist solvent, a developing solution, a rinse solution, a composition for forming an antireflection film, and a composition for forming a top coat) do not contain impurities such as a metal, a metal salt containing halogen, an acid, an alkali, and a component having 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 amount 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, particularly preferably 10 ppt or less, and most preferably substantially zero (less than or equal to the detection limit of the measuring device).
A compound according to a third aspect of the present invention is a compound represented by General Formula (a0-1).
[In the formula, R01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. L 1 represents a divalent linking group. Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
The compound represented by General Formula (a0-1) according to the present embodiment is the same as the compound represented by General Formula (a0-1) in the resist composition according to the first aspect of the present invention.
It is preferable that the compound according to the present embodiment is a compound represented by General Formula (a0-1-1).
[In the formula, R01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. L001 represents an ester bond, an aromatic hydrocarbon group, a lactone-containing cyclic group, or a divalent linking group having a group consisting of a combination of these groups, Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
The compound represented by General Formula (a0-1-1) according to the present embodiment is the same as the compound represented by General Formula (a0-1-1) in the resist composition according to the first aspect of the present invention.
The compound according to the present embodiment can be produced, for example, by an esterification reaction of a compound represented by General Formula (C0-1) and a compound represented by General Formula (AL0-1).
[in the formula, R01 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. L01 represents a divalent linking group. Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
The temperature condition of the esterification reaction is not particularly limited, and is, for example, about −10° C. to 120′C.
The reaction time of the esterification reaction is not particularly limited, and is, for example, about 1 to 72 hours.
Examples of the reaction solvent that is used in the esterification reaction include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N′-dimethylacetamide, and dimethylsulfoxide.
In addition, in the above esterification reaction, a condensing agent and a basic catalyst may be used.
Specific examples of the condensing agent include N,N′-dicyclohexylcarbodiimide. N,N′-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and carbonyldiim-idazole (CDI).
Specific examples of the basic catalyst include tertiary amines such as trimethylamine, triethylanine, and tributylamine, aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolidinopyridine, diazabicyclononene (DBN), and diazabicycloundecene (DBU).
The compound represented by General Formula (C0-1) may be a carboxylic acid chloride in order to improve electrophilicity and increase reactivity. That is, the hydroxyl group in the compound represented by General Formula (C0-1) may be substituted with a chlorine atom.
After completion of the reaction, the compound represented by General Formula (a0-1) in the reaction solution may be isolated and purified.
Known methods of the related art can be used for the isolation and the purification, and for example, any one or a combination of two or more of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, and the like can be used.
The structure of the compound obtained as described above can be identified by typical organic analysis methods such as 1H-nuclear magnetic resonance (NMR) spectroscopy, 13C-NMR spectroscopy, 19F-NMR spectroscopy, infrared (IR) absorption spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction.
As a compound represented by Formula (AL0-1), a commercially available product may be used or the compound may be synthesized.
For example, as shown below, the compound represented by Formula (AL0-1) may be synthesized by the Grignard reaction of reacting a ketone represented by General Formula (AL0-1 pre) with an organic magnesium halide as represented by Ra02 MgBr.
[In the formulae, Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
Examples of the reaction solvent used in the Grignard reaction include the same reaction solvents as those used in the esterification reaction.
The temperature condition of the Grignard reaction is not particularly limited, and is, for example, about −10° C. to 120° C.
The reaction time of the Grignard reaction is not particularly limited, and is, for example, about 1 to 72 hours.
Further, the compound represented by Formula (AL0-1) may be synthesized by a nucleophilic addition reaction of an aromatic compound having an iodine atom and a ketone in the presence of a strong base (potassium hexamethyldisilazide (KHMDS) or the like).
Further, a compound represented by Formula (AL0-1), which is different from the compound described above, may be synthesized by reacting the compound represented by Formula (AL0-1) with other compounds.
For example, a compound represented by General Formula (AL0-1′) may be synthesized by reacting the compound represented by Formula (AL0-1) with a 5-norbornene-2,3-dicarboxylic anhydride.
[In the formulae, Ra01 and Ra02 each independently represent a hydrocarbon group which may have a substituent. Ar01 represents an aryl group in which some or all hydrogen atoms are substituted with iodine atoms or a heteroaryl group in which some or all hydrogen atoms are substituted with iodine atoms. The aryl group and the heteroaryl group may have a substituent other than the iodine atoms.]
The compound according to the present embodiment described above is useful for producing a resin according to a fourth aspect described below.
The fourth aspect of the present invention relates to a resin having a constitutional unit derived from a compound represented by General Formula (a0-1).
The resin according to the fourth aspect of the present invention is the same as the above-described component (A1).
The resin according to the fourth aspect of the present invention is a resin useful for a resist composition.
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples,
20 g of 4-Iodoacetophenone (AC-1) was Dissolved in 80 g of THF, the Solution was added dropwise to 200 mL of methylmagnesium bromide (THF solution, 1.0 mol/L) at a temperature of 0° C. or lower, and the solution was stirred for 2 hours. Thereafter, the reaction was stopped by adding 100 g of saturated ammonium chloride to perform extraction with 200 g of ethyl acetate. The solvent of the obtained organic layer was distilled off, and the resultant was purified by silica gel chromatography, thereby obtaining an intermediate AL-1.
An intermediate AL-2 was obtained by the same production method as that for the intermediate AL-1 except that the methyhnagnesium bromide solution was changed to art equimolar ethynylmagnesium bromide solution.
25 g of 2-iodothiophene (AC-2) was added to a flask and dissolved in 150 g of T-IF, a 0.6 M KHMDS toluene solution (240.7 g) was added dropwise to the solution at −30° C. or lower, and the resultant was stirred at 0° C. or lower for 30 minutes. Thereafter, acetone (10.0 g) was added dropwise thereto at 0° C. or lower, and the resultant was stirred for 3 hours. Thereafter, 100 g of a saturated ammonium chloride aqueous solution was added dropwise thereto to stop the reaction, and extraction was performed with ethyl acetate (200 g). Next, the solvent was distilled off, and the resultant was purified by silica gel chromatography, thereby obtaining an intermediate AL-3.
20 g of 2,4,6-triiodoacetophenone (AC-3) was dissolved in 120 g of THE, and the solution was added dropwise to 80 mL of methylmagnesium bromide (THF solution, 1.0 mol/L) at 0° C. or lower, and the resultant was stirred for 2 hours. Thereafter, the reaction was stopped by adding 100 g of saturated ammonium chloride to perform extraction with 200 g of ethyl acetate. The solvent of the obtained organic layer was distilled off, and the resultant was purified by silica gel chromatography, thereby obtaining an intermediate AL-4.
An intermediate AL-5 was obtained by the same production method as that for the intermediate AL-4 except that the methylmagnesium bromide solution was changed to an equimolar vinylmagnesium bromide solution.
A 5-norbornene-2,3-dicarboxylic anhydride (20 g) was placed in a three-necked flask, and THF (200 g) was added thereto and dissolved. Next, AL-1 (35 g) and NaH (3.5 g) were added thereto, and the resultant was stirred at room temperature for 4 hours. Next, a saturated ammonium chloride aqueous solution (200 g) was added thereto to terminate the reaction. Next, extraction was performed with 400 g of ethyl acetate, and the organic solvent was distilled off. The obtained concentrate was dissolved in 300 g of ethyl acetate, acetone (35 g), sodium hydrogen carbonate (19 g), and oxone (90 g) were added thereto, and the resultant was stirred for 8 hours. The reaction was stopped by adding 300 g of pure water to the reaction solution, 120 g of ethyl acetate was added thereto for extraction, and the solvent was distilled off. The obtained concentrate was purified by silica gel chromatography, thereby obtaining an intermediate AL-6.
An intermediate AL-7 was obtained by the same production method as that for the intermediate AL-6 except that the 5-norbornene-2,3-dicarboxylic anhydride was changed to an equimolar exo-3.6-epoxy-1 ,2.3,6-tetrahydrophthalic anhydride.
The intermediate AL-](25 g) was added to a flask and dissolved in dichlorourethane (250 g). Next, glycolic acid methacrylate (19 g), triethylamine (18 g), and DMAP (650 ng) were added thereto, diisopropylcarbodiimide (21 g) was added dropwise thereto, and the resultant was stirred for 4 hours. The reaction solution was filtered, the filtrate was washed with 1% hydrochloric acid and pure water, the organic solvent was distilled off, and the resultant was purified by silica gel chromatography, thereby obtaining a compound (a0-01-4).
The obtained compound (a0-01-1) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results,
δ (ppm)=7.66 (m, C═CH, C═CH, 2H), 7.11 (m, C═CH, C═CH, l2H), 6.40-6.50 (in. C═CH2, 2H), 5.09 (s, CH2, 2H), 2.01 (s, CH, 3H), 1.58 (s, CH3, CH3, 6H)
A compound (a0-01-2) was obtained by the same production method as that for the compound (a0-01-1) except that glycolic acid methacrylate was changed to equimolar 4-vinylbenzoic acid.
The obtained compound (a0-01-2) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results.
δ (ppm)=7.70 (m, C═CH, C=C1H, 2H), 7.59 (m, C═CH, C═CH, 2H), 7.45 (mu, C═CH, C═CH, 211), 7.08 (m, C=—CH, C═CH, 21H), 6.72 (dd, C═CH, 11H), 5.50-5.75 (n, C═CH2, 2H), 1.58 (s, CH3, CH3, 6H)
The intermediate AL-6 (25 g) was dissolved in 250 g of THF, the solution was cooled to 0° C., and triethylamine (9 g) and methacrylic acid chloride (8 g) were added dropwise thereto. The temperature was returned to room temperature, the resultant was stirred for 5 hours, a 5% sodium hydrogen carbonate aqueous solution (50 g) was added thereto to stop the reaction, and extraction was performed with t-butyl methyl ether (150 g). The solvent of the obtained organic layer was distilled off, and the resultant was purified by silica gel chromatography, thereby obtaining a compound (a0-01-3).
The obtained compound (a0-01-3) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results.
δ (ppm)=7.70 (i, C═CH—, C=CH, 2H), 7.10 (m, C═CH, C═CH, 211), 6.20-6.40 (m, C═CH2, 2H), 5.05-5.10 (m, C—CH, C—CH, 2H), 2.70-3.00 (m, C—CH, C—CH, 21H) 2.50-2.70 (m, C—H, C—H, 2H), 2.00-2.30 (m, CH2, 2H), 1.95 (s, CR3, 3H), 1.58 (s, CH3, CH3, 6H)
A compound (a0-01-4) was obtained by the same production method as that for the compound (a0-01-2) except that the intermediate AL−1 was changed to the equimolar intermediate AL-2.
The obtained compound (a0-01-4) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results.
δ (ppm)=7.70 (m, C═CH, C═CH, 2H), 7.59 (m, C═CH, C═CH, 2H), 7.45 (i, C═CH. C=CH, 2H), 7,08 (m, C═CH, C=—CH, 2H), 6.72 (dd, C=CH, 1H), 5,50-5.75 (m, C=CH2, 2H), 3.65 (s, C≡CH, 1H), 1.60 (s, CH3, 3H)
A compound (a0-01-5) was obtained by the same production method as that for the compound (a0-01-2) except that the intermediate AL−1 was changed to the equimolar intermediate AL-3.
The obtained compound (a0-01-5) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results.
δ (ppm)=7.70 (m, C═CH, C═C—H, 2H), 7.47 (m, C═CH, C═CH, 2H), 7.45 (m, C═CH, C═CH, 2H), 7.08 (d, C═CH, 1H), 6.60-6.75 (m, C═CH, C═CH, 2H), 5.75 (dd, C═CH, 1H), 5.23 (dd, C═CH, 1H), 1.60 (s, CH3, CH3, 6H)
The intermediate AL−1 (25 g) was added to a flask and dissolved in dichloromethane (250 g), 5-vinylsalicylic acid (15 g, CD (17 g), and DBU (13 g) were added thereto, and the solution was stirred for 6 hours. Subsequently, 1% citric acid (200 g) was added to the reaction solution to stop the reaction, and the organic layer was extracted and washed with pure water. The organic solvent was distilled off, and the resultant was purified by silica gel column chromatography, thereby obtaining a compound (a0-01-6).
The obtained compound (a0-01-6) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results,
δ (ppm)=8.80 (s, —OH, 1H, 7.65-7.55 (a, C═CH, C═CH, C═CH, 3H), 7.20-6.60 (m, C═CH, C═CH, C═C—H, C═CH, C═CH, 51), 5.30-5,85 (m, C═CH2, 2H), 1.61 (s, CH—, CH—, 6H)
A compound (a0-01-7) was obtained by the same production method as that for the compound (a0-01-3) except that the intermediate AL-6 was changed to the equimolar intermediate AL-7.
The obtained compound (a0-01-7) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results.
δ (ppm)=7,70 (m, C═CH, C═CH, 2H), 7.10 (m, C═CH, C═CH, 2H), 6.20-6.50 (m, C═CH2, 2H), 5.15-5.40 (m, C—CH, C—CH, 2H), 4.40-4.70 (In, C—CH, C—CH, 2H), 3.00-3.20 (m, C—H, C—H, 2R), 2.05 (s, CH3, 3H), 1.66 (s, CH3, CH3, 6H)
A compound (a0-01-8) was obtained by the same production method as that for the compound (a0-01-6) except that the intermediate AL-1 was changed to the equimolar intermediate AL-4.
The obtained compound (a0-01-8) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results,
δ (ppm)=8.20 (s, —OH, 1H), 7.75-7.50 (m, C═CH, C═CH, C═CH, 3H), 7.20 (s, C═CH, 1H), 6.60-6.90 (m, C═CH, C═CH, 2H ), 5.30-5.85 (m, C═CH2, 2H), 1.68 (s, CH3, CH3, 6H)
A compound (a0-01-9) was obtained by the same production method as that for the compound (a0-01-6) except that the intermediate AL-1 was changed to the equimolar intermediate AL-5,
The obtained compound (a0-01-9) was subjected to NMR measurement (CDCl3), and the structure thereof was identified from the following results.
δ (ppm)=8.20 (s. —OH, 1H), 7.75-7.50 (m, C═CH, C═CH, C═CH, 3H), 7.20 (s, C═CH, 1H), 6.60-6.90 (m, C═CH, C═CH, 2H), 5.30-5.85 (m, C═CH2, 2H), 5.10-5.30 (m, C═CH2, 21H), 4.80-4.95 (m, C═CH, 1H), 1.68 (s, CH3, 3H)
A dropping solution obtained by dissolving 32.4 g of the compound (a0−1-1), 10.0 g of the compound (m-a10-1 pre), and 2.38 g of dimethyl azobis(isobutyrate) (V-601) as a polymerization initiator in 20.3 g of methyl ethyl ketone (MEK) was prepared. 33.7 g of MEK was added to a three-necked flask connected with a thermometer, a reflux pipe, and a nitrogen introduction pipe, the solution was heated to 85° C. in a nitrogen atmosphere, and the above-described dropping solution was added dropwise thereto over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 85° C. for 1 hour. Then, the reaction solution was cooled to room temperature. After completion of the reaction, the obtained reaction solution was precipitated in 2,600 g of heptane, followed by washing. The obtained white solid substance was filtered and dried under reduced pressure overnight to obtain the target polymer compound (A1-1).
Polymer compounds (A1-2) to (A1-15) were synthesized by the same method as in Synthesis Example 1 of the polymer compound by using the compounds (a0-01-1) to (a0-01-9) described above and compounds (m-a1-1 pre) to (n-a10-3 pre) and (m-a2-1) to (m-a2-3) described below.
The weight-average molecular weight (Mw) and the polydispersity (Mw/Mn) of each of the obtained polymer compounds were determined by GPC measurement (in terms of the standard polystyrene).
In addition, the copolymerization composition ratio (the proportion (molar ratio) of each constitutional unit in the structural formula) of each of the obtained polymer compounds was determined from the carbon 1.3 nuclear magnetic resonance spectrum (600 MHz 13C-NMR).
Polymer compound (A1-1): weight-average molecular weight (Mw) of 7500, polydispersity (Mw/Mn) of 1.65, l/m=50/50
Polymer compound (A 1-2): weight-average molecular weight (Mw) of 7400, polydispersity (Mw/Mn) of 1.67,H/m=50/50
Polymer compound (A1-31): weight-average molecular weight (Mw) of 7500, polydispersity (Mw/Min) of 1.64, 1/m=50/50
Polymer compound (A1-4): weight-;average molecular weight (Mw) of 7600, polydisperisty (Mw/Mn) of 1,65,1/m=50/50
Polymer compound (A1-5): weight-average molecular weight (Mw) of 7400, polydispersity (Mw/Mn) of 1.6:3, 1/m=50/50
Polymer compound (A1-1): weight-average molecular weight (Mw) of 7500, polydispersity (Mw/Mn) of 1,65, /n=50/50
Polymer compound (A 1-7): weight-average molecular weight (Mw) of 7500, polydispersity (Mw/Mn) of 1.64, l/m=50/50
Polymer compound (A]-8): weight-average molecular weight (Mw) of 7600, polydispersity (Mw/Mn) of 1.67, l/m=50/50
Polymer compound (A]-9): weight-average molecular weight (Mw) of 7400, polydispersity (Mw/Mn) of 1.66, h/m=50/50
Polymer compound (A]-10): weight-average molecular weight (Mw) of 7400, polydispersity (Mw/Mn) of 1.67, l/m=50/50
Polymer compound (A1-11): weight-average molecular weight (Mw) of 7600, polydispersity (Mw/Mn) of 1.63, l/m/n=50/40/10
Polymer compound (A1-12): weight-average molecular weight (Mw) of 7,500, polydispersity (Mw/Mn) of 166, l/m/n=50/40/10
Polymer compound (A1-13): weight-average molecular weight (Mw) 1 of 7,500, polydispersity (Mw/Mn) of 1.66, l/m/n=50/40/10
Polymer compound (A]1-14): weight-average molecular weight (Mw) 1 of 7,500, polydispersity (Mw/Mn) of 167, 1/m/n=50/40/10
Polymer compound (A]1-15): weight-average molecular weight (Mw) 1 of 7,400, polydispersity (Mw/Mn) of 1.66, 1/lm/n=50/40/101
Each of the components listed 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 the brackets are blending amounts (parts by mass).
(A1)-1 to (A1)-15: polymer compounds (A 1-1) to (A1-15) described above
(A2)-1: polymer compound represented by Chemical Formula (A2-1) The weight-average molecular weight (Mw) of the polymer compound (A2)-2 in terms of standard polystyrene determined by GPC measurenment was 7500, and the polydispersity (Mw/Mn) thereof was 1.64. The copolymerization composition ratio (the ratio (molar ratio) of each constitutional unit in the structural formula) determined by 13C-NMR was 1m=50150.
(A2)-2: polymer compound represented by Chemical Formula (A2-2) The weight-average molecular weight (Mw) of the polymer compound (A2)-2 in terms of standard polystyrene determined by GPC measurement was 7400, and the polydispersity (Mw/Mn) thereof was 1.65. The copolymerization composition ratio (the ratio (molar ratio) of each constitutional unit in the structural formula) determined by 13C-NMR was l/m=50/50.
(A2)-3: polymer compound represented by Chemical Formula (A2-3) The weight-average molecular weight (Mw) of the polymer compound (A2)-3 in terms of standard polystyrene determined by GPC measurement was 7600, and the polydispersity (Mw/Mn) thereof was 1.68. The copolymerization composition ratio (ratio (molar ratio) between the constitutional units in the structural formula) determined by 13C-NMR was l/m/n/o=38/46/11/5.
(A2)-4: polymer compound represented by Chemical Formula (A2-4) The weight-average molecular weight (Mw) of the polymer compound (A2)-4 in terms of standard polystyrene determined by GPC measurement was 7400, and the polydispersity (Mw/Mn) thereof was 1.67. The copolymerization composition ratio (the ratio (molar ratio) of each constitutional unit in the structural formula) determined by 13C-NMR was l/m=50/50.
An 8-inch silicon substrate which had been subjected to a hexamethyldisilazane (HMDS) treatment was coated with the resist composition of each example using a spinner, and subjected to a pre-bake (PAB) treatment on a hot plate at a temperature of 110° C. for 60 seconds so that the substrate was dried, thereby forming a resist film having a film thickness of 70 nm.
Next, drawing (exposure) was performed on the resist film by using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.), with the target size being set to a line width of 50 nm of a 1:1 line-and-space pattern (hereinafter, referred to as “LS pattern”), at an acceleration voltage of 100 kV, and the post exposure bake (PEB) treatment was performed at 100° C. for 60 seconds.
Subsequently, alkali development was performed at 23° C. for 60 seconds using a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” (trade name, manufactured by TOKYO OHKA KOGYO CO., LTD).
Thereafter, water rinsing was carried out with pure water for 15 seconds.
As a result, a 1:1 LS pattern having a line width of 50 nm was formed.
According to <resist pattern formation>described above, an optimum exposure amount Eop (μC/cm2) in which a pattern having the target size was formed was determined. The results are listed in Tables 4 and 5 in the columns of “Eop (μC/1 m2)”.
Using the LS pattern formed in the section of “formation of resist pattern”, the 3G which is the scale that indicates the LWR was acquired. The results are listed in the columns of “LWR (nm)” in Tables 4 and 5.
In regard to “3σ”, the triple value (3σ) of the standard deviation (σ) determined from measurement results, obtained by measuring 400 line positions in the longitudinal direction of the line with a scanning electron microscope (trade name: S-9380, manufactured by Hitachi High-Tech Corporation, acceleration voltage: 800 V), denotes “LWR” (unit: nm). In a case where the value of the 3G is small, this indicates that the roughness of a line side wall is small and an LS pattern with a uniform width is obtained.
As listed in Tables 4 and 5, it was confirmed that the resist compositions of the examples had higher sensitivity and more satisfactory LWR in the resist pattern formation as compared with the resist compositions of the comparative examples.
While preferred embodiments of the present invention have been described and illustrated above, it should be understood that these are exemplary of the present invention and are not to be considered as limiting. Additions, omissions, substitutions, and other modifications can be made without departing from the scope 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 |
|---|---|---|---|
| 2022-007875 | Jan 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/001104 | 1/17/2023 | WO |
