Dibenzothiophenium salt compound, method for producing same, and application of compound
Dibenzothiophenium salt compounds with electron-withdrawing groups address the need for high photodecomposition efficiency in EUV resists, enhancing photolithography by improving sensitivity and acid diffusion control in semiconductor manufacturing.
Patent Information
- Application Number
- PCT/JP2025/020143
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-02-28
- Filing Date
- 2025-06-04
- Publication Date
- 2025-12-26
AI Technical Summary
There is a demand for ionic photoacid generators with high photodecomposition efficiency, particularly for EUV resists, to meet the requirements of finer photolithography in semiconductor manufacturing.
Development of dibenzothiophenium salt compounds with electron-withdrawing groups, such as —SO2CF3, that enhance photosensitivity to active energy rays like EUV, EB, and X-rays, serving as photoacid generators and acid diffusion controllers for chemically amplified resists.
The dibenzothiophenium salt compounds exhibit high photodecomposition efficiency, enabling effective resist pattern formation with improved sensitivity and control over acid diffusion.
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Figure JP2025020143_26122025_PF_FP_ABST
Abstract
Description
Dibenzothiophenium salt compounds, their production methods, and uses of the compounds
[0001] The present invention relates to a dibenzothiophenium salt compound, a method for producing the same, and uses of the compound (photoacid generator, resist composition, resist pattern formation, etc.).
[0002] Dibenzothiophenium salt compounds are widely known as photoacid generators capable of generating acid upon irradiation with light, and are used, for example, as cationic photopolymerization initiators for initiating cationic polymerization of photocurable resins and as photoacid generators for chemically amplified resists used in semiconductor photolithography (see, for example, Patent Document 1).
[0003] When a dibenzothiophenium salt compound is used as a photoacid generator in a chemically amplified resist, the acid generated by irradiating the dibenzothiophenium salt compound with light acts as a catalyst to remove the protecting group in the resist resin component, converting the resin component into a component soluble in an alkaline developer. By this mechanism, in the semiconductor photolithography process, by exposing the resist through a photomask, the resin component in the exposed area is dissolved in the developer, leaving the resin component in the unexposed area covered by the photomask, allowing the formation of a fine pattern.
[0004] With the recent trend toward finer photolithography, there has been a demand for ionic photoacid generators with high photodecomposition efficiency, particularly for EUV resists, and there is room for further improvement.
[0005] Japanese Patent Application Laid-Open No. 2021-151989
[0006] An object of the present invention is to provide a novel dibenzothiophenium salt compound and a method for producing the same. Another object of the present invention is to provide a photoacid generator containing the dibenzothiophenium salt compound, a resist composition containing the photoacid generator, and a method for forming a resist pattern using the resist composition.
[0007] As a result of extensive research, the present inventors have found that the compound represented by chemical formula (I) can solve the above-mentioned problems. Based on this finding, the present inventors have conducted further research and have completed the present invention.
[0008] That is, the present invention includes the following aspects: [1] A compound represented by chemical formula (I): (In the formula, R １ and R ２ are the same or different and represent a hydrogen atom; a halogen atom; or —CF ３ ;-SO ２ R ３ an alkyl group having 1 to 10 prime numbers; —OH; a polymerizable group selected from formulas (S-1) to (S-4); or an acid-reactive group selected from formulas (R-1) to (R-7). ３ is -CF ３ , -CF ２ CF ３ , an alkyl group having 1 to 10 carbon atoms, or a phenyl group. [A] － is the trifluoromethanesulfonate anion (triflate anion: TfO － ) or a halide ion. (In the formula, R １ａ represents a hydrogen atom or a methyl group, and Y represents a single bond or an alkylene group having 1 to 3 carbon atoms. (wherein Y is the same as above. R ５１ ~R ５３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, or R ５１ and R ５２ may be linked to each other to form an aliphatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are attached. ５４ and R ５５ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ５６ represents an alkyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ２ - may be replaced by -O- or -S-. d represents an integer of 0 to 4. However, in formula (R-1), formula (R-3), and formulas (R-5) to (R-7), R ５１ ~R ５３are all hydrogen atoms.) [2] The compound according to [1], which is a compound represented by chemical formula (I-1). (In the formula, R １ , R ２ and [A] － is the same as above.) [3] R １ is a hydrogen atom; a halogen atom; a polymerizable group represented by formula (S-1); or —OH. [4] The compound according to [1] or [2], ２ is a hydrogen atom or a halogen atom. [5] A photoacid generator containing the compound according to any one of [1] to [4]. [6] A resist composition containing a polymer having a structural unit containing an acid-reactive group and the photoacid generator according to [5]. [7] A method for forming a resist pattern, comprising the steps of: applying the resist composition according to [6] to a substrate to form a resist film; exposing the resist film; and developing the exposed resist film to form a resist pattern. [8] A sulfoxide compound represented by chemical formula (II): (In the formula, R ２ are the same as above.) [9] A method for producing the compound represented by chemical formula (I) according to [1], comprising a step of reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (III) in the presence of an acid or an acid anhydride. (In the formula, R １ , R ２ and [A] － is the same as above.)
[0009] The compound of the present invention represented by the chemical formula (I) has an electron-withdrawing group (—SO ２ CF ３) can lower the intramolecular LUMO, resulting in high photosensitivity to active energy rays such as EUV (extreme ultraviolet light), EB (electron beam), and X-rays. Therefore, the compound of the present invention is useful as a photoacid generator or acid diffusion controller with high photodecomposition efficiency. The photoacid generator of the present invention is useful, for example, as a photoacid generator for resists (particularly chemically amplified resists) and as a photocationic polymerization initiator. A resist composition containing the photoacid generator of the present invention is suitable for use in forming a resist pattern.
[0010] The present invention is described in detail below. 1. Compounds of the Present Invention The present invention relates to compounds represented by the aforementioned chemical formula (I) (hereinafter, sometimes referred to as "compounds of the present invention"). The compounds of the present invention include compounds obtained by the reaction schemes (A) to (F) described below (e.g., compounds represented by chemical formulas (I-2) to (I-5)) and compounds represented by chemical formula (I-1).
[0011] R １ and R ２ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[0012] R １ ~R ３ Examples of the alkyl group having 1 to 10 carbon atoms, represented by the formula (I), include linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, a 1-adamantyl group, and a 2-adamantyl group, of which a methyl group, a t-butyl group, a cyclohexyl group, a 1-adamantyl group, and the like are preferred. By having such an alkyl group, the compound of the present invention is expected to have improved compatibility with a polymer having a structural unit containing an acid-reactive group.
[0013] R １ and R ２ is a group having a polymerizable functional group (for example, a carbon-carbon double bond), and examples thereof include groups represented by formulae (S-1) to (S-4).
[0014] (In the formula, R １ａ represents a hydrogen atom or a methyl group, and Y represents a single bond or an alkylene group having 1 to 3 carbon atoms.
[0015] Examples of the alkylene group having 1 to 3 carbon atoms represented by Y include a methylene group, an ethylene group (-CH2CH2- and -CH(CH3)-), and a propylene group (-CH2CH2CH2-, -CH2CH(CH3)-, and -CH(CH3)CH2-).
[0016] R １ and R ２ is a group having a structure in which a polar group such as a carboxyl group or a hydroxyl group is protected with a group that reacts by the action of an acid (for example, a group that decomposes and leaves (leaving group)), and examples thereof include groups represented by formulae (R-1) to (R-7).
[0017] (wherein Y is the same as above. R ５１ ~R ５３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aromatic group having 4 to 18 carbon atoms; R ５１ and R ５２ may be linked to each other to form an aliphatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are attached. ５４ and R ５５ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ５６ represents an alkyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ２ - may be replaced by -O- or -S-. d represents an integer of 0 to 4. However, in formula (R-1), formula (R-3), and formulas (R-5) to (R-7), R ５１ ~R ５３ Except when all are hydrogen atoms.)
[0018] R ５１ ~R ５３ , R ５６Examples of the alkyl group having 1 to 20 carbon atoms, represented by the formula (I), include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-adamantyl group, a 2-adamantyl group, a decahydronaphthyl group, a decahydrodimethanonaphthyl group, and a norbornyl group.
[0019] R ５４ and R ５５ Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.
[0020] R ５１ ~R ５３ Examples of the alkenyl group having 2 to 8 carbon atoms represented by the formula (I) include linear, branched, or cyclic alkenyl groups having 2 to 8 carbon atoms, and specific examples thereof include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, t-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, nonenyl, and norbornenyl groups.
[0021] R ５１ ~R ５３ Examples of the aromatic group having 4 to 18 carbon atoms and represented by the formula (I) include aromatic groups having a single ring or two or more rings (aryl groups, heteroaryl groups, etc.), such as aryl groups such as phenyl group, naphthyl group, anthryl group, biphenylyl group, and phenanthryl group, and heteroaryl groups such as furyl group.
[0022] R ５１ and R ５２Examples of the aliphatic hydrocarbon ring having 3 to 20 carbon atoms that is formed by linking these rings together with the carbon atoms to which they are bonded include a monocyclic or bicyclic or more saturated or unsaturated aliphatic hydrocarbon ring. Examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, an adamantane ring, a decahydronaphthalene ring, a decahydrodimethanonaphthalene ring, a norbornane ring, and a norbornene ring. In addition, the —CH ２ Examples of the ring in which - is replaced by -O- and / or -S- include a tetrahydrofuran ring, a (methoxymethyl)tetrahydrofuran ring, a tetrahydropyran ring, an oxathiane ring, and an oxabicyclohethane ring.
[0023] R ５６ Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms and represented by the formula (I) include saturated or unsaturated alicyclic hydrocarbon groups having a single ring or two or more rings. Examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-adamantyl group, a 2-adamantyl group, a decahydronaphthyl group, a decahydrodimethanonaphthyl group, a norbornyl group, and a norbornenyl ring. In addition, the —CH ２ Examples of the group in which - is replaced by -O- and / or -S- include a tetrahydrofuranyl group, a (methoxymethyl)tetrahydrofuranyl group, a tetrahydropyranyl group, an oxathianyl group, and an oxabicycloheptyl group.
[0024] Examples of the sulfonium cation that constitutes the compound of the present invention (compound represented by chemical formula (I)) include sulfonium cations represented by chemical formulas (C-1) to (C-137).
[0025]
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037] Of the compounds of the present invention (compounds represented by chemical formula (I)), compounds represented by chemical formula (I-1) are more preferred. (In the formula, R １ , R ２ and [A] － is the same as above.)
[0038] R １ is preferably a hydrogen atom; a halogen atom (preferably a fluorine atom or an iodine atom); ３ , -SO ２ R ３ a polymerizable group selected from formulas (S-1) to (S-4); or an acid-reactive group selected from formulas (R-1) to (R-7). ３ is preferably —CF ３ It is. １ More preferably, R is a hydrogen atom; a halogen atom (preferably a fluorine atom or an iodine atom); a polymerizable group represented by formula (S-1); or —OH. １ Particularly preferred is a hydrogen atom, a fluorine atom, an iodine atom, a vinyl group, or —OH.
[0039] R ２ is preferably a hydrogen atom; a halogen atom (preferably a fluorine atom or an iodine atom); ３ ;-SO ２ R ３a polymerizable group selected from formulas (S-1) to (S-4); or an acid-reactive group selected from formulas (R-1) to (R-7). ３ is preferably —CF ３ It is. ２ More preferably, R is a hydrogen atom; a halogen atom (preferably a fluorine atom or an iodine atom); or a polymerizable group represented by formula (S-1). ２ is particularly preferably a hydrogen atom or a halogen atom.
[0040] [A] － is a monovalent counter anion of the sulfonium cation, and is an anion corresponding to the acid generated by irradiating the compound of the present invention (the compound represented by chemical formula (I)) with light. － is the trifluoromethanesulfonate anion (triflate anion: TfO － ) or a halide ion. The halide ion is F － , Cl － ,Br － , I － [A] － Preferably, TfO － or Cl － is.
[0041] The compound of the present invention can be synthesized by, for example, synthesis methods (1) to (6).
[0042] <Synthesis Method (1)> The compound of the present invention (compound represented by chemical formula (I)) can be synthesized by reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (III) in the presence of an acid or acid anhydride (i) (see reaction scheme (A)). (In the formula, R １ , R ２ and [A] － is the same as above.)
[0043] Examples of the sulfoxide compound represented by the chemical formula (II) include sulfoxide compounds represented by the chemical formulas (II-1) to (II-17).
[0044]
[0045] These sulfoxide compounds can be synthesized in accordance with the methods described in, for example, JP-A-04-257558, J. Org. Chem., 2016, 81, 11360-11362, Angewandte Chemie, International Edition (2019), 58(14), 4552-4556, etc. Alternatively, they can also be synthesized according to the method described in the section <Synthesis of Compound Represented by Chemical Formula (II)> below.
[0046] Examples of the compound represented by chemical formula (III) include compounds represented by chemical formulas (III-1) to (III-34).
[0047] The compound represented by the chemical formula (III) can be purchased as a commercially available reagent or can be synthesized by a known method.
[0048] The amount of the compound represented by the chemical formula (III) used is preferably in the range of 1 to 10 times the molar amount of the sulfoxide compound represented by the chemical formula (II) used.
[0049] Examples of the acid or acid anhydride (i) include methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, propionic acid, benzoic acid, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, propionic anhydride, benzoic anhydride, dinitrogen pentoxide, diphosphorus pentoxide, diphosphorus trioxide, disulfuric acid, HF, HCl, HBr, and HI. These may be used alone or in combination of two or more. Trifluoromethanesulfonic anhydride is preferred.
[0050] The amount of the acid or acid anhydride (i) used is preferably in the range of 1 to 20 times by mole, more preferably in the range of 1 to 10 times by mole, relative to the amount of the sulfoxide compound represented by chemical formula (II) used.
[0051] In carrying out this reaction, a reaction solvent (ii) may be appropriately used, if necessary. The reaction solvent (ii) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane, methyltetrahydrofuran, methyltetrahydropyran, methyl-t-butyl ether, diisopropyl ether, diethyl ether, 1,4-dioxane, dimethoxyethane, and tetrahydropyran; hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and nitrobenzene; and halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, chloroform, and bromoform, and the like. These can be used in combination in appropriate amounts, if necessary.
[0052] In this reaction, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0053] After completion of the reaction, the target compound of the present invention (compound represented by chemical formula (I)) can be isolated from the resulting reaction mixture by, for example, concentrating the reaction mixture by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.
[0054] In this reaction, the compound represented by chemical formula (I) can be obtained by using, for example, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as the acid or acid anhydride (i). Alternatively, when a compound having a counter anion different from the compound represented by chemical formula (I) is obtained depending on the type of acid or acid anhydride (i) used, the compound can be reacted with an alkali metal cation (M ＋ ) and a monovalent counter anion ([A] － ) and salt (M ＋ [A] － ) (salt exchange reaction) to obtain the compound of formula (I).
[0055] <Synthesis Method (2)> The compound of the present invention (compound represented by chemical formula (I)) can be synthesized by reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (IV) in the presence of a reaction promoter (iii) (see reaction scheme (B)).
[0056] (In the formula, R １ , R ２ and [A] － is the same as above. １ represents a halogen atom.)
[0057] As the sulfoxide compound represented by the chemical formula (II), those exemplified in the synthesis method (1) can be used.
[0058] Examples of the compound represented by chemical formula (IV) include compounds represented by chemical formulas (IV-1) to (IV-19).
[0059]
[0060] The compound represented by the chemical formula (IV) can be obtained by purchasing a commercially available reagent or by using a known method (e.g., compound R １ -Ph-X １ It can be synthesized by the reaction of X with Mg. １ Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and an iodine atom.
[0061] The amount of the compound represented by the chemical formula (IV) used is preferably in the range of 1 to 10 times the molar amount of the sulfoxide compound represented by the chemical formula (II) used.
[0062] The reaction accelerator (iii) may be (CH ３ ) ３ SiCl or (CH ３ ) ３ SiCF ３ SO ３ These may be used alone or in combination of two or more.
[0063] The amount of the reaction accelerator (iii) used is preferably in the range of 1 to 20 times by mole, more preferably in the range of 1 to 10 times by mole, relative to the amount of the sulfoxide compound represented by chemical formula (II) used.
[0064] In carrying out this reaction, a reaction solvent (iv) may be used appropriately as necessary. The reaction solvent (iv) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include diethyl ether, tetrahydrofuran, dichloromethane, chlorobenzene, etc., and these can be used in combination in appropriate amounts as necessary.
[0065] In this reaction, the reaction temperature is preferably set in the range of −20 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0066] After completion of the reaction, the target compound of the present invention (compound represented by chemical formula (I)) can be isolated from the resulting reaction mixture by, for example, concentrating the reaction mixture by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.
[0067] In this reaction, the compound represented by formula (I) can be directly obtained. Alternatively, if necessary, the compound can be reacted with an alkali metal cation (M ＋ ) and a monovalent counter anion ([A] － ) and salt (M ＋ [A] － ) (salt exchange reaction) to obtain a different compound of formula (I).
[0068] <Synthesis Method (3)> The compound of the present invention (compound represented by chemical formula (I-2)) can be synthesized by reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (V) in the presence of an acid or acid anhydride (i) (Step 1), and then reacting the resulting compound represented by chemical formula (1) with a base (v) (Step 2) (see Reaction Scheme (C)).
[0069] (In the formula, R ２ , R １ａ and [A] － is the same as above. ２ represents a halogen atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). １ and R ２ At least one of the groups is -SO ２ CF ３ It is.) X ２ Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and an iodine atom.
[0070] As the sulfoxide compound represented by the chemical formula (II), those exemplified in the synthesis method (1) can be used.
[0071] Examples of the compound represented by chemical formula (V) include (2-chloroethyl)benzene, (2-chloro-1-methylethyl)benzene, (2-bromoethyl)benzene, (2-bromo-1-methylethyl)benzene, (2-iodoethyl)benzene, (2-iodo-1-methylethyl)benzene, phenethyl methanesulfonate, phenethyl tosylate, phenethyl triflate, etc. These compounds can be purchased as commercially available reagents.
[0072] In the reaction of the first step, the amount of the compound represented by the chemical formula (V) used is preferably in the range of 1 to 10 times the molar amount of the sulfoxide compound represented by the chemical formula (II) used.
[0073] The acid or acid anhydride (i) used in the reaction of the first step can be any of those exemplified in the synthesis method (1). The amount of the acid or acid anhydride (i) used is preferably in the range of 1 to 20 times, more preferably 1 to 10 times, the molar amount of the sulfoxide compound represented by chemical formula (II) used.
[0074] In the reaction of the first step, a reaction solvent (ii) may be used as needed. As the reaction solvent (ii), those exemplified in the synthesis method (1) can be used.
[0075] In this reaction, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0076] After completion of the reaction in the first step, the compound represented by chemical formula (1) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, or other methods. If necessary, the compound can be purified by washing with water or the like, or by treatment with activated carbon, silica gel chromatography, recrystallization, or other methods. The compound represented by chemical formula (1) may be subjected to the aforementioned concentration, extraction, purification, or the like before being submitted to the second step, or the reaction solution obtained after completion of the reaction in the first step may be submitted to the second step as is.
[0077] Examples of the base (v) used in the second step include trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), pyridine, 4-(N,N-dimethylamino)pyridine, picoline, N,N-dimethylaniline, N,N-diethylaniline, imidazole, lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, carbonate Examples of bases include sodium, potassium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium alkoxides (e.g., lithium methoxide), sodium alkoxides (e.g., sodium methoxide, sodium ethoxide), and potassium alkoxides (e.g., potassium t-butoxide). These may be used alone or in combination of two or more. The amount (charge amount) of the base (v) used is preferably 3 to 20 times the molar amount (charge amount) of the compound represented by chemical formula (1).
[0078] In carrying out Step 2, a reaction solvent (vi) may be used appropriately, if necessary. The reaction solvent (vi) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and water, and these can be used in combination in appropriate amounts, if necessary.
[0079] In the reaction of the second step, the reaction temperature is preferably set in the range of −10 to 100° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 80 hours.
[0080] After completion of the reaction in the second step, the target compound of the present invention (compound represented by chemical formula (I-2)) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.
[0081] In this reaction, the compounds represented by chemical formula (1) and chemical formula (I-2) can be obtained by using, for example, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as the acid or acid anhydride (i) in the first step. Alternatively, when a compound having a counter anion different from that of the compound represented by chemical formula (1) or chemical formula (I-2) is obtained depending on the type of acid or acid anhydride (i) used, the compound can be, for example, treated with an alkali metal cation (M ＋ ) and a monovalent counter anion ([A] － ) and salt (M ＋ [A] － ) (salt exchange reaction) to obtain the compound represented by chemical formula (1) or chemical formula (I-2).
[0082] <Synthesis Method (4)> The compound of the present invention (compound represented by chemical formula (I-3)) can be synthesized by reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (VI) in the presence of an acid or acid anhydride (i) (Step 1), and then reacting the resulting compound represented by chemical formula (2) with a compound represented by chemical formula (VII) in the presence of a base (v) (Step 2) (see Reaction Scheme (D)).
[0083] (In the formula, R ２ , Y and [A] － is the same as above. ２１represents a group selected from the following formulae (S-12) to (S-14), and X represents a halogen atom, —OH, or —OR ２１ where X is -OR. ２１ In the case of ２１ Except when it is also the formula (S-13).
[0084] (In the formula, R １ａ is the same as above.) Examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom.
[0085] As the sulfoxide compound represented by the chemical formula (II), those exemplified in the synthesis method (1) can be used.
[0086] Examples of the compound represented by chemical formula (VI) include phenol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc. These compounds can be purchased as commercially available reagents.
[0087] In the reaction of the first step, the amount of the compound represented by the chemical formula (VI) used is preferably in the range of 1 to 10 times the molar amount of the sulfoxide compound represented by the chemical formula (II) used.
[0088] The acid or acid anhydride (i) used in the reaction of the first step can be any of those exemplified in the synthesis method (1). The amount of the acid or acid anhydride (i) used is preferably in the range of 1 to 20 times, more preferably 1 to 10 times, the molar amount of the sulfoxide compound represented by chemical formula (II) used.
[0089] In the reaction of the first step, a reaction solvent (ii) may be used as needed. As the reaction solvent (ii), those exemplified in the synthesis method (1) can be used.
[0090] In this reaction, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0091] After completion of the reaction in the first step, the compound represented by chemical formula (2) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, or other methods. If necessary, the compound can be purified by washing with water or the like, or by treatment with activated carbon, silica gel chromatography, recrystallization, or other methods. The compound represented by chemical formula (2) may be subjected to the aforementioned concentration, extraction, purification, or the like before being submitted to the second step, or the reaction solution obtained after completion of the reaction in the first step may be submitted to the second step as is.
[0092] Examples of the compound represented by chemical formula (VII) include compounds represented by chemical formulas (VII-1) to (VII-36).
[0093]
[0094]
[0095] These compounds can be purchased as commercially available reagents or can be synthesized according to the method described in, for example, JP-A-2000-191590.
[0096] In the reaction of the second step, the amount of the compound represented by chemical formula (VII) used is preferably in the range of 1 to 10 times the amount of the compound represented by chemical formula (2) used (charge amount).
[0097] The base (v) used in the second step can be any of those exemplified in the synthesis method (3). The amount of base (v) used is preferably in the range of 1 to 20 times, more preferably 1 to 10 times, the molar amount used (charge amount) of the compound represented by chemical formula (2).
[0098] In carrying out the second step, it is preferable to use a polymerization inhibitor (vii) to suppress side reactions. If necessary, a reaction solvent (vi) may be used appropriately. The reaction solvent (vi) may be any of those exemplified in the synthesis method (3).
[0099] Examples of the polymerization inhibitor (vii) include hydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydroquinone, phenothiazine, copper chloride, copper sulfate, and copper dibutyldithiocarbamate. These may be used in combination as the polymerization inhibitor (vii). The amount (charge amount) of the polymerization inhibitor (vii) used is preferably in the range of 0.0001 to 1.0 times the molar amount (charge amount) of the compound represented by chemical formula (2).
[0100] In this reaction, the reaction temperature is preferably set in the range of −20 to 150° C., more preferably in the range of −10 to 100° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 48 hours.
[0101] After completion of the reaction in the second step, the target compound of the present invention (compound represented by chemical formula (I-3)) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.
[0102] In this reaction, the compounds represented by chemical formula (2) and chemical formula (I-3) can be obtained by using, for example, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as the acid or acid anhydride (i) in the first step. Alternatively, when a compound having a counter anion different from that of the compound represented by chemical formula (2) or chemical formula (I-3) is obtained depending on the type of acid or acid anhydride (i) used, the compound can be, for example, treated with an alkali metal cation (M ＋ ) and a monovalent counter anion ([A] － ) and salt (M ＋ [A] － ) (salt exchange reaction) to obtain the compound represented by chemical formula (2) or chemical formula (I-3).
[0103] <Synthesis Method (5)> The compound of the present invention (compound represented by chemical formula (I-4)) can be synthesized by reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (VI) in the presence of an acid or acid anhydride (i) (Step 1), and then reacting the resulting compound represented by chemical formula (2) with a compound represented by chemical formula (VIII) in the presence of a base (v) (Step 2) (see Reaction Scheme (E)).
[0104] (In the formula, R ２ , Y and [A] － is the same as above. ２２ represents a group represented by the following formula (R-11), formula (R-12), formula (R-16), or formula (R-17), and X ３ represents a halogen atom.)
[0105] (In the formula, R ５１ ~R ５６ and d are the same as above.
[0106] As the sulfoxide compound represented by the chemical formula (II), those exemplified in the synthesis method (1) can be used. ３ Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and an iodine atom.
[0107] Examples of the compound represented by chemical formula (VI) include phenol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc. These compounds can be purchased as commercially available reagents.
[0108] In the reaction of the first step, the amount of the compound represented by the chemical formula (VI) used is preferably in the range of 1 to 10 times the molar amount of the sulfoxide compound represented by the chemical formula (II) used.
[0109] The acid or acid anhydride (i) used in the reaction of the first step can be any of those exemplified in the synthesis method (1). The amount of the acid or acid anhydride (i) used is preferably in the range of 1 to 20 times, more preferably 1 to 10 times, the molar amount of the sulfoxide compound represented by chemical formula (II) used.
[0110] In the reaction of the first step, a reaction solvent (ii) may be used as needed. As the reaction solvent (ii), those exemplified in the synthesis method (1) can be used.
[0111] In this reaction, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0112] After completion of the reaction in the first step, the compound represented by chemical formula (2) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, or other methods. If necessary, the compound can be purified by washing with water or the like, or by treatment with activated carbon, silica gel chromatography, recrystallization, or other methods. The compound represented by chemical formula (2) may be subjected to the aforementioned concentration, extraction, purification, or the like before being submitted to the second step, or the reaction solution obtained after completion of the reaction in the first step may be submitted to the second step as is.
[0113] Examples of the compound represented by chemical formula (VIII) include compounds represented by chemical formulas (VIII-1) to (VIII-43).
[0114]
[0115] These compounds can be purchased and used as commercially available reagents, or, for example, JP 2001-089414 A, Reaction Chemistry & Engineering (2023), 8 (8), 1882-1887, Journal of Chemical Research, Synopses (1984), (4), 104-105, Angewandte Chemie (1980), 92 (11), 931-933, Organic Syntheses (1958), 38, 78-80, JP 2018-127408 A It can be synthesized in accordance with the method described in the publication.
[0116] In the reaction of the second step, the amount of the compound represented by chemical formula (VIII) used is preferably an appropriate ratio in the range of 1 to 10 times the amount of the precursor compound 5 of the present invention used (charged amount).
[0117] As the base (v) used in the second step, those exemplified in the synthesis method (3) can be used. The amount of base (v) used is preferably in the range of 1 to 20 times, and more preferably in the range of 1 to 10 times, the amount used (charge amount) of the compound represented by chemical formula (2). In carrying out the second step, as necessary, those exemplified in the synthesis method (3) can be used as the reaction solvent (vi).
[0118] In this reaction, the reaction temperature is preferably set in the range of −20 to 150° C., more preferably in the range of −10 to 100° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 48 hours.
[0119] After completion of the reaction in the second step, the target compound of the present invention (compound represented by chemical formula (I-4)) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.
[0120] In this reaction, the compounds represented by chemical formula (2) and chemical formula (I-4) can be obtained by using, for example, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as the acid or acid anhydride (i) in the first step. Alternatively, when a compound having a counter anion different from that of the compound represented by chemical formula (2) or chemical formula (I-4) is obtained depending on the type of acid or acid anhydride (i) used, the compound can be, for example, treated with an alkali metal cation (M ＋ ) and a monovalent counter anion ([A] － ) and salt (M ＋ [A] － ) (salt exchange reaction) to obtain the compound represented by chemical formula (2) or chemical formula (I-4).
[0121] <Synthesis Method (6)> The compound of the present invention (compound represented by chemical formula (I-5)) can be synthesized by reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (IX) in the presence of a reaction promoter (iii) (Step 1), and then reacting the resulting compound represented by chemical formula (3) with a compound represented by chemical formula (X) in the presence of a base (v) (Step 2) (see Reaction Scheme (F)).
[0122] (In the formula, X １ and [A] － is the same as above. ２３ represents a group represented by the following formulas (R-13) to (R-15), and X ４ represents a halogen atom.)
[0123] (In the formula, R ５１ ~R ５６ and d are the same as above.) X ４ Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and an iodine atom.
[0124] As the sulfoxide compound represented by the chemical formula (II), those exemplified in the synthesis method (1) can be used.
[0125] The compound represented by the chemical formula (IX) can be obtained by purchasing a commercially available reagent or by using a known method (e.g., NaO ２ C-Ph-X １ and Mg).
[0126] Examples of the compound represented by chemical formula (IX) include compounds represented by chemical formulas (IX-1) to (IX-5).
[0127]
[0128] In the reaction of the first step, the amount of the compound represented by the chemical formula (IX) used is preferably in the range of 1 to 10 times the molar amount of the sulfoxide compound represented by the chemical formula (II) used.
[0129] As the reaction accelerator (iii) used in the reaction of step 1, those exemplified in synthesis method (2) can be used. The amount of reaction accelerator (iii) used is preferably in the range of 1 to 20 times, more preferably 1 to 10 times, the molar amount of the sulfoxide compound represented by chemical formula (II) used.
[0130] In the reaction of the first step, a reaction solvent (iv) may be used as needed. As the reaction solvent (iv), those exemplified in the synthesis method (2) can be used.
[0131] In this reaction, the reaction temperature is preferably set in the range of −20 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0132] After completion of the reaction in the first step, the compound represented by chemical formula (3) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. If necessary, the compound can be purified by washing with water or the like, or by activated carbon treatment, silica gel chromatography, recrystallization, or the like. The compound represented by chemical formula (3) may be subjected to the aforementioned concentration, extraction, purification, or the like before being submitted to the second step, or the reaction solution obtained after completion of the reaction in the first step may be submitted to the second step as is.
[0133] Examples of the compound represented by chemical formula (X) include compounds represented by chemical formulas (X-1) to (X-37).
[0134]
[0135] These compounds can be purchased as commercially available reagents and used, or can be synthesized in accordance with the methods described in, for example, Reaction Chemistry & Engineering (2023), 8 (8), 1882-1887, Journal of Chemical Research, Synopses (1984), (4), 104-105, Angewandte Chemie (1980), 92 (11), 931-933, Organic Syntheses (1958), 38, 78-80, JP-A-2018-127408, etc.
[0136] In the reaction of the second step, the amount of the compound represented by chemical formula (X) used is preferably in the range of 1 to 10 times the amount of the compound represented by chemical formula (3) used (charge amount).
[0137] As the base (v) used in the second step, those exemplified in the synthesis method (3) can be used. The amount of base (v) used is preferably in the range of 1 to 20 times, and more preferably in the range of 1 to 10 times, the amount used (charge amount) of the compound represented by chemical formula (3). In carrying out the second step, as necessary, those exemplified in the synthesis method (3) can be used as the reaction solvent (vi).
[0138] In this reaction, the reaction temperature is preferably set in the range of −20 to 150° C., more preferably in the range of −10 to 100° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 48 hours.
[0139] After completion of the reaction of the second step, the target compound of the present invention (compound represented by chemical formula (I-5)) can be isolated from the obtained reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction.
[0140] If necessary, the product can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, or the like.
[0141] In this reaction, a compound represented by the chemical formula (3) or (I-5) can be obtained. Alternatively, if necessary, the compound can be converted into a hydroxy group by, for example, reacting it with an alkali metal cation (M ＋ ) and a monovalent counter anion ([A] － ) and salt (M ＋ [A] － ) (salt exchange reaction) to obtain a compound represented by formula (3) or formula (I-5) having a different monovalent counter anion.
[0142] <Synthesis of Compound Represented by Chemical Formula (II)> The compound represented by chemical formula (II) (hereinafter, sometimes referred to as the "sulfoxide compound of the present invention") can be synthesized by reacting a chlorosulfonyl compound represented by chemical formula (XI) with a fluorinating agent (Step 1), then with a trifluoromethylating agent (Step 2), and subsequently with an oxidizing agent (Step 3) (see Reaction Scheme (X)).
[0143] (In the formula, R ２ is the same as above.)
[0144] Examples of the chlorosulfonyl compound represented by chemical formula (XI) include chlorosulfonyl compounds represented by chemical formulas (XI-1) to (XI-17).
[0145]
[0146] These chlorosulfonyl compounds can be purchased and used as commercially available reagents, or can be synthesized in accordance with the methods described in, for example, A European Journal, 2014, 20 (24), 7258-7261, ACS Catalysis, 2022, 12 (14), 8729-8739, U.S. Patent No. 3,705,909, J. Org. Chem. , 2016, 81, 11360-11362, Angew. Chem. Int. Ed. , 2009, 58, 4552-4556, etc.
[0147] Examples of the fluorinating agent used in the first step include potassium fluoride, potassium hydrogen fluoride, tetrabutylammonium fluoride, tetramethylammonium fluoride, and tetraethylammonium fluoride. These may be used alone or in combination of two or more. In the reaction of the first step, the amount of the fluorinating agent used is preferably in the range of 1 to 20 times, and more preferably in the range of 1 to 10 times, the amount of the chlorosulfonyl compound represented by chemical formula (XI) used.
[0148] In the reaction of the first step, a reaction promoter (x-1) and a reaction solvent (x-2) may be used as needed. Examples of the reaction promoter (x-1) include ammonium salt-type phase transfer catalysts such as tetramethylammonium chloride, benzyltrimethylammonium chloride, ethyltrimethylammonium bromide, ethyltrimethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrahexylammonium bromide, and tetrahexylammonium iodide; phosphonium salt-type phase transfer catalysts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide; and crown ethers such as 12-crown-4, 15-crown-5, 18-crown-6, benzo-18-crown-6, and dibenzo-18-crown-6. These may be used in combination as the reaction promoter (x-1). The amount (charge amount) of the reaction accelerator (x-1) used is preferably in the range of 0.001 to 2 times the molar amount of the chlorosulfonyl compound represented by the chemical formula (XI) used.
[0149] The reaction solvent (x-2) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane, methyltetrahydrofuran, methyltetrahydropyran, methyl-t-butyl ether, diisopropyl ether, diethyl ether, 1,4-dioxane, dimethoxyethane, and tetrahydropyran; halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, chloroform, and bromoform; and acetonitrile, and these can be used in combination in appropriate amounts, if necessary.
[0150] In the reaction of the first step, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0151] After completion of the reaction in the first step, the compound represented by chemical formula (4) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. If necessary, the compound can be purified by washing with water or the like, or by activated carbon treatment, silica gel chromatography, recrystallization, or the like. The compound represented by chemical formula (4) may be subjected to the aforementioned concentration, extraction, purification, or the like before being submitted to the second step, or the reaction solution obtained after completion of the reaction in the first step may be submitted to the second step as is.
[0152] Examples of the trifluoromethylating agent used in the second step include trimethyltrifluoromethylsilane, triethyltrifluoromethylsilane, etc. These may be used alone or in combination of two or more.
[0153] In the reaction of the second step, the amount of the trifluoromethylating agent used is preferably 1 to 20 times, more preferably 1 to 10 times, the molar amount of the compound represented by chemical formula (4).
[0154] In the reaction of Step 2, a reaction solvent (x-3) may be used appropriately, if necessary. The reaction solvent (x-3) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane, methyltetrahydrofuran, methyltetrahydropyran, methyl-t-butyl ether, diisopropyl ether, diethyl ether, 1,4-dioxane, dimethoxyethane, and tetrahydropyran; and amides such as dimethylformamide and dimethylacetamide; and these can be used in combination in appropriate amounts, if necessary.
[0155] In the reaction of the second step, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0156] After completion of the reaction in the second step, the compound represented by chemical formula (5) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. If necessary, the compound can be purified by washing with water or the like, treating with activated carbon, silica gel chromatography, recrystallization, or the like. The compound represented by chemical formula (5) may be subjected to the aforementioned concentration, extraction, purification, or the like before being submitted to the third step, or the reaction solution obtained after completion of the reaction in the second step may be submitted to the third step as is.
[0157] Examples of the oxidizing agent used in the third step include hydrogen peroxide, metachloroperbenzoic acid, sodium periodate, etc. These may be used alone or in combination of two or more kinds.
[0158] In the reaction of the third step, the amount of the oxidizing agent used is preferably in the range of 1 to 20 times, more preferably 1 to 10 times, the amount of the compound represented by chemical formula (5) used.
[0159] In the reaction of Step 3, a reaction solvent (x-4) may be used appropriately as necessary. The reaction solvent (x-4) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include carboxylic acids such as formic acid, acetic acid, propionic acid, and trifluoroacetic acid; alcohols such as methanol, ethanol, 2-propanol, and butanol; and halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, chloroform, and bromoform, and these can be used in combination in appropriate amounts as necessary.
[0160] In the reaction of the third step, the reaction temperature is preferably set in the range of −80 to 60° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 30 minutes to 24 hours.
[0161] After completion of the reaction in the third step, the sulfoxide compound of the present invention (compound represented by chemical formula (II)) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, crystallization, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.
[0162] Examples of the compound represented by chemical formula (II) include the sulfoxide compounds represented by chemical formulas (II-1) to (II-17) exemplified in synthesis method (1).
[0163] In the compound represented by formula (II), R ２ is a hydrogen atom; a halogen atom (preferably a fluorine atom or an iodine atom); ３ ;-SO ２ R ３ -OH; a polymerizable group selected from formulas (S-1) to (S-4); or an acid-reactive group selected from formulas (R-1) to (R-7). ３ But, -CF ３ It is preferable that R ２ is more preferably a hydrogen atom or a halogen atom.
[0164] 2. Photoacid Generator and Resist Composition The photoacid generator and resist composition of the present invention contain the compound of the present invention. The compound of the present invention is expected to have high photosensitivity to actinic energy rays such as EUV (extreme ultraviolet light), EB (electron beam), and X-rays, and can therefore be suitably used as a photoacid generator, acid diffusion controller, or the like in a resist composition. Note that the resist composition of the present invention may contain, in addition to the compound of the present invention and a polymer having a structural unit containing an acid-reactive group, other photoacid generators, other acid diffusion controllers, other resins, solvents, additives, and the like as necessary. Furthermore, in the present invention, the resist composition refers to a mixture before curing.
[0165] [Polymer Having a Structural Unit Containing an Acid-Reactive Group] The polymer having a structural unit containing an acid-reactive group used in the resist composition of the present invention is not particularly limited as long as it is a material commonly used in resist compositions. The acid-reactive group preferably has a structure in which a polar group is protected by a group that reacts under the action of acid (e.g., a group that decomposes and leaves (leaving group)). Examples of the polar group include acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), such as a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.
[0166] Examples of the acid-reactive group include the aforementioned R １ and R ２ The acid reactive group can be selected from those exemplified as the acid reactive group represented by the formula (R-1) to the formula (R-7) above. Examples include the groups represented by the formulas (R-1) to (R-7) above. Examples of polymers having a structural unit containing an acid reactive group include those containing structural units (or monomers) shown in the following documents:・ WO 2023 / 162907 ([Chemical formula 2] to [Chemical formula 36]) ・ JP 2023-016886 A ([Chemical formula 28], [Chemical formula 29], [Chemical formula 49] to [Chemical formula 53]) ・ JP 2023-116251 A ([Chemical formula 8] to [Chemical formula 16]) ・ JP 2023-116474 A ([Chemical formula 13] to [Chemical formula 20]) ・ JP 2023-117394 A (
[0091] to
[0188] ) ・ JP 2023-118096 A (
[0021] to
[0120] ) ・ JP 2023-131576 A (
[0101] to
[0216] ) JP 2023-132684 A ([Chemical Formula 51] to [Chemical Formula 63]) JP 2023-133148 A ([Chemical Formula 114] to [Chemical Formula 123])
[0167] The polymer having a structural unit containing an acid-reactive group can be obtained by heating a monomer having the structural unit described above together with a radical polymerization initiator in an organic solvent to polymerize it. In this polymerization, the compound of the present invention, a photoacid generator described below, an acid diffusion controller, etc. can be used.
[0168] Examples of organic solvents include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Examples of radical polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The polymerization temperature is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, and more preferably 5 to 20 hours.
[0169] The polymer having a structural unit containing an acid-reactive group preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent of 1,000 to 500,000, more preferably 2,000 to 30,000. If the Mw is within this range, the resist film will have good heat resistance and solubility in an alkaline developer.
[0170] To obtain a resist composition that is suitable for use in fine pattern dimensions, the polymer having a structural unit containing an acid reactive group preferably has a narrow dispersity of Mw / Mn of 1.0 to 2.0, and particularly 1.0 to 1.5. Furthermore, the polymer having a structural unit containing an acid reactive group may contain two or more polymers with different composition ratios, Mw, and Mw / Mn.
[0171] [Compound of the Present Invention] Depending on the type of counter anion, the compound of the present invention has (A) the effect of generating an acid upon irradiation with light, and (B) the effect of controlling the diffusion phenomenon in the resist film of an acid generated from an acid generator or the like upon exposure, thereby suppressing undesirable chemical reactions (e.g., dissociation reaction of an acid-dissociable group) in unexposed areas. Therefore, the compound of the present invention functions as a photoacid generator or an acid diffusion controller (quencher) depending on the type of counter anion.
[0172] When the compound of the present invention functions as a photoacid generator, the amount of the compound of the present invention in the resist composition is not particularly limited and is, for example, 1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid reactive group. When the compound of the present invention functions as an acid diffusion controller, the amount of the compound of the present invention in the resist composition is not particularly limited and is, for example, 1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid reactive group.
[0173] [Other Photoacid Generators] The resist composition of the present invention may contain a photoacid generator other than the compound of the present invention (other photoacid generators). As the other photoacid generator, widely known ones can be used, and examples thereof include salts in which a cation and anion are paired, as shown in the following documents: <Cations> International Publication No. 2023 / 162907 ([Chemical Formula 49] to [Chemical Formula 55]) JP 2023-090803 A ([Chemical Formula 20]) JP 2023-116251 A ([Chemical Formula 25], [Chemical Formula 26]) JP 2023-116474 A ([Chemical Formula 5], [Chemical Formula 7], [Chemical Formula 8], [Chemical Formula 25]) JP 2023-117394 A (
[0040] ,
[0045] ) JP 2023-118096 A (
[0132] ,
[0180] ) JP 2023-131576 A ([Chemical Formula 11] to [Chemical Formula 17]) JP 2023-131926 A ([Chemical Formula 58] to [Chemical Formula 64]) JP 2023-132684 A ([Chemical Formula 23] to [Chemical Formula 46]) JP 2023-133148 A ([Chemical Formula 40] to [Chemical Formula 63]) JP 2023-145385 A ([Chemical Formula 19] to [Chemical Formula 21]) JP 2023-145543 A ([Chemical Formula 21] to [Chemical Formula 23]) JP 2023-152629 A ([Chemical Formula 66] to [Chemical Formula 91]) <Anion> WO 2023 / 162907 A ([Chemical Formula 38] to [Chemical Formula 46]) JP 2023-116251 A ([Chemical Formula 27]) JP 2023-116474 A ([Chemical Formula 29]) JP 2023-118096 A (
[0175] to
[0176] ) JP 2023-132684 A ([Chemical Formula 67] to [Chemical Formula 78]) JP 2023-133148 A ([Chemical Formula 77] to [Chemical Formula 80]) JP 2023-135555 A (counter anion of [Chemical Formula 102] to [Chemical Formula 105]) JP 2023-145543 A ([Chemical Formula 24] to [Chemical Formula 25])
[0174] The amount of the other photoacid generator blended in the resist composition of the present invention is not particularly limited as long as the effects of the present invention can be exhibited, and is, for example, 0 to 10 parts by weight, and preferably 0 to 5 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid reactive group.
[0175] [Other Acid Diffusion Controllers] The resist composition of the present invention may contain an acid diffusion controller other than the compound of the present invention (other acid diffusion controllers). Examples of other acid diffusion controllers include salts in which a cation and an anion are paired, as described in the following documents: <Cations> International Publication No. 2023 / 162907 ([Chemical Formula 49] to [Chemical Formula 55]) JP 2023-090803 A ([Chemical Formula 20]) JP 2023-116251 A ([Chemical Formula 25], [Chemical Formula 26]) JP 2023-116474 A ([Chemical Formula 5], [Chemical Formula 7], [Chemical Formula 8], [Chemical Formula 25]) JP 2023-117394 A (
[0040] ,
[0045] ) JP 2023-118096 A (
[0132] ,
[0180] ) JP 2023-131576 A ([Chemical Formula 11] to [Chemical Formula 17]) JP 2023-131926 A ([Chemical Formula 58] to [Chemical Formula 64]) JP 2023-132684 A ([Chemical Formula 23] to [Chemical Formula 46]) JP 2023-133148 A ([Chemical Formula 40] to [Chemical Formula 63]) JP 2023-145385 A ([Chemical Formula 19] to [Chemical Formula 21]) JP 2023-145543 A ([Chemical Formula 21] to [Chemical Formula 23]) JP 2023-152629 A ([Chemical Formula 66] to [Chemical Formula 91]) <Anions> WO 2023 / 157455 A ([Chemical Formula 25], [Chemical Formula 31], [Chemical Formula 32]) WO 2023 / 157456 ([Chemical Formula 29]) WO 2023 / 171527 (
[0355] to
[0358] , [Chemical Formula 76] to [Chemical Formula 78]) JP 2023-116474 A ([Chemical Formula 38] to [Chemical Formula 39]) JP 2023-136980 A ([Chemical Formula 31] to [Chemical Formula 34]) JP 2023-145543 A (counter anion of [Chemical Formula 69])
[0176] The amount of the other acid diffusion controller blended in the resist composition of the present invention is not particularly limited as long as the effects of the present invention can be exhibited, and is, for example, 0 to 10 parts by weight, and preferably 0 to 5 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid reactive group.
[0177] [Other Resins] The resist composition of the present invention may contain other resins as needed. Examples of other resins include resins containing fluorine atoms (hereinafter, may be referred to as "fluorine-containing resins"). When the other resin is a fluorine-containing resin, it is preferably a resin having, as a partial structure, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. Examples of other resins include those containing structural units (or monomers) shown in the following documents: JP 2023-133148 A ([Chemical Formula 118] to [Chemical Formula 120]) JP 2023-132684 A ([Chemical Formula 57] to [Chemical Formula 60]) JP 2023-117394 A (
[0142] to
[0171] ) JP 2023-016886 A ([Chemical Formula 28], [Chemical Formula 52], [Chemical Formula 53])
[0178] [Solvent] The resist composition of the present invention may contain a solvent as needed. Any solvent can be appropriately selected from those known as solvents for conventional chemically amplified resist compositions, as long as it can dissolve the various components used to form a homogeneous solution. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; monohydric alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; polyhydric alcohols (glycols) such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), and dipropylene glycol monomethyl ether; glycol diethers such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and cyclic ethers such as dioxane. Monocarboxylic acid alkyl esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, tert-butyl acetate, methyl pyruvate, ethyl pyruvate, tert-butyl propionate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; glycol monoesters such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol mono-tert-butyl ether acetate; lactones such as γ-butyrolactone;Examples of suitable organic solvents include aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO). These may be used alone or in combination of two or more. Among these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.
[0179] [Additives] The resist composition of the present invention may contain additives as needed. Examples of additives include surfactants, dissolution inhibitors (dissolution suppressors), crosslinking agents, water repellency improvers, acetylene alcohols, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc.
[0180] Examples of surfactants include those described in JP 2008-111103 A (paragraphs
[0165] to
[0166] ). Addition of these surfactants can further improve or control the coatability of the resist composition. There are no particular restrictions on the amount of surfactant added to the resist composition of the present invention, and it is usually 0 to 10 parts by weight per 100 parts by weight of the polymer having a structural unit containing an acid reactive group.
[0181] Examples of dissolution inhibitors (dissolution suppressors) include compounds having a molecular weight of 100 to 1,000, preferably 150 to 800, and containing two or more phenolic hydroxy groups in the molecule, in which the hydrogen atoms of the phenolic hydroxy groups have been substituted with acid labile groups at a rate of 0 to 100 mol % overall, or compounds containing carboxy groups in the molecule, in which the hydrogen atoms of the carboxy groups have been substituted with acid labile groups at an average rate of 50 to 100 mol % overall. Specific examples include compounds in which the hydrogen atoms of the hydroxy groups and carboxy groups of bisphenol A, trisphenol, phenolphthalein, cresol novolak, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid have been substituted with acid labile groups, as well as those described in JP 2008-122932 A (
[0155] to
[0178] ). When the resist composition of the present invention is a positive resist composition, the incorporation of these dissolution inhibitors (dissolution suppressors) can further increase the difference in dissolution rate between exposed and unexposed areas, thereby further improving resolution. The amount of the dissolution inhibitor (dissolution suppressor) blended in the resist composition of the present invention is not particularly limited, and is typically 0 to 50 parts by weight, and preferably 0 to 40 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid reactive group.
[0182] Examples of crosslinking agents include epoxy compounds, melamine compounds, guanamine compounds, glycoluril compounds or urea compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, isocyanate compounds, azide compounds, and compounds containing double bonds such as alkenyloxy groups. These may be added and used, or may be introduced as pendant groups into polymer side chains. Compounds containing hydroxy groups may also be used as crosslinking agents. When the resist composition of the present invention is a positive resist composition, the addition of a crosslinking agent can reduce the dissolution rate of the exposed area, thereby enabling a negative resist pattern to be obtained.
[0183] Examples of epoxy compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether.
[0184] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.
[0185] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.
[0186] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 methylol groups of tetramethylol glycoluril have been methoxymethylated or mixtures thereof, compounds in which 1 to 4 methylol groups of tetramethylol glycoluril have been acyloxymethylated or mixtures thereof, etc. Examples of urea compounds include tetramethylol urea, tetramethoxymethyl urea, compounds in which 1 to 4 methylol groups of tetramethylol urea have been methoxymethylated or mixtures thereof, tetramethoxyethyl urea, etc.
[0187] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.
[0188] Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.
[0189] Examples of compounds containing an alkenyloxy group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.
[0190] There are no particular restrictions on the amount of crosslinking agent added to the resist composition of the present invention, and it is usually 0 to 50 parts by weight, and preferably 0 to 40 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid-reactive group.
[0191] The water repellency improver is not particularly limited as long as it is soluble in an alkaline developer or an organic solvent developer. Examples include polymers containing a fluorinated alkyl group, polymers containing a 1,1,1,3,3,3-hexafluoro-2-propanol residue of a specific structure, and those described in JP-A Nos. 2007-297590 and 2008-111103. By incorporating these water repellency improvers, the resist film surface can be improved in water repellency, allowing the resist film to be used in immersion lithography without a topcoat. The amount of water repellency improver in the resist composition of the present invention is not particularly limited, and is 0 to 20 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the polymer having a structural unit containing an acid-reactive group.
[0192] Examples of acetylene alcohols include those described in JP 2008-122932 A (paragraphs
[0179] to
[0182] ). There are no particular restrictions on the amount of acetylene alcohols added in the resist composition of the present invention, and it is usually 0 to 5 parts by weight per 100 parts by weight of the polymer having a structural unit containing an acid reactive group.
[0193] [Method for Preparing Resist Composition] The resist composition of the present invention can be prepared, for example, by mixing the compound of the present invention, the polymer having a structural unit containing an acid-reactive group, and, if necessary, other photoacid generators, other acid diffusion controllers, other resins, solvents, and additives in predetermined ratios. Furthermore, after mixing, the resist composition of the present invention is preferably filtered, for example, through a filter having a pore size of approximately 0.05 μm to 0.2 μm. The solids concentration of the resist composition of the present invention is typically 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferably 1% to 20% by mass.
[0194] 3. Method for Forming Resist Patterns When the resist composition of the present invention is used in the manufacture of various integrated circuits, known lithography techniques can be applied. For example, a pattern formation method using the resist composition of the present invention can include a method comprising the steps of: applying the resist composition of the present invention directly or indirectly onto a substrate to form a resist film (coating step); exposing the resist film formed in the coating step to active energy rays (exposure step); and developing the exposed resist film using a developer to form a resist pattern (developing step).
[0195] [Coating Step] The resist composition of the present invention is applied to a substrate (Si, SiO ２ , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection coating, etc.) or substrates for mask circuit manufacturing (Cr, CrO, CrON, MoSi ２ , SiO ２The resist is applied onto the substrate (or substrates) by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., to a coating thickness of 0.01 to 2 μm, and then prebaked on a hot plate preferably at 60 to 150° C. for 10 seconds to 30 minutes, more preferably at 80 to 120° C. for 30 seconds to 20 minutes, to form a resist film.
[0196] [Exposure Step] The resist film formed in the coating step is exposed to active energy rays. Examples of active energy rays include ultraviolet rays, far ultraviolet rays, EB, EUV rays with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation are used as active energy rays, the exposure dose is preferably 1 to 200 mJ / cm, either directly or using a mask for forming a desired pattern. ２ approximately, more preferably 10 to 100 mJ / cm ２ When EB is used as the active energy ray, the exposure dose is preferably 0.1 to 1000 μC / cm ２ approximately, more preferably 0.5 to 200 μC / cm ２ As the active energy ray, i-rays with a wavelength of 365 nm, KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, γ-rays, and synchrotron radiation are suitable for fine patterning, with EB and EUV being more suitable for fine patterning.
[0197] After exposure to actinic rays, post-exposure baking (PEB) may be performed on a hot plate or in an oven, preferably at 50 to 150° C. for 10 seconds to 30 minutes, more preferably at 60 to 120° C. for 30 seconds to 20 minutes.
[0198] [Development Step] After exposure or PEB, the exposed resist film is developed using an alkaline aqueous solution or an organic solvent developer for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, by a conventional method such as immersion, puddle, or spray, to form the desired pattern. In the case of a positive resist composition, the irradiated portion dissolves in the developer, while the unexposed portion does not, forming the desired positive pattern on the substrate. In the case of a negative resist composition, the opposite is true of the positive resist material; the irradiated portion becomes insoluble in the developer, while the unexposed portion dissolves.
[0199] Examples of aqueous alkaline developer solutions include 0.1 to 10% by mass, preferably 2 to 5% by mass, of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), etc. Examples of organic solvent developers include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, Examples of the developer include methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. These developers may be used alone or in combination of two or more.
[0200] At the end of development, rinsing is performed. Examples of solvents used for rinsing include water, alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents having 6 to 12 carbon atoms. Rinsing can reduce the occurrence of collapse and defects in the resist pattern. Furthermore, rinsing is not necessarily required, and the amount of solvent used can be reduced by not performing rinsing.
[0201] The developed hole or trench pattern can also be shrunk using thermal flow, RELACS, or DSA techniques. A shrink agent is applied to the hole pattern, and the diffusion of an acid catalyst from the resist film during baking causes crosslinking of the shrink agent on the surface of the resist film, resulting in adhesion of the shrink agent to the sidewalls of the hole pattern. The baking temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and the baking time is preferably 10 to 300 seconds. Excess shrink agent is removed, and the hole pattern is shrunk.
[0202] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The main raw materials used in the examples are as follows.
[0203] [Main raw materials and reagents] 2-Trifluoromethyldibenzothiophene: synthesized in accordance with the methods described in U.S. Pat. No. 3,705,909, J. Org. Chem., 2016, 81, 11360-11362, and Angew. Chem. Int. Ed., 2009, 58, 4552-4556. 2-Methanesulfonyldibenzothiophene: synthesized in accordance with the methods described in Chinese Patent Application Publication No. 106631937 and Organic Syntheses (1958), 38, 62-65.・Formic acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・35% hydrogen peroxide: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Benzene: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Fluorobenzene: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Iodobenzene: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・2-Bromoethylbenzene: Manufactured by Tokyo Chemical Industry Co., Ltd. ・Trifluoromethanesulfonic anhydride: Manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. ・Chloroform: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Triethylamine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・t-Butyl methyl ether: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (hereinafter sometimes referred to as "MTBE")
[0204] Example 1 (1) Synthesis of 2-trifluoromethanesulfonyldibenzothiophene oxide 31.63 g (100.0 mmol) of 2-trifluoromethyldibenzothiophene, 50.00 g of formic acid, and 9.72 g (100.0 mmol) of 35% aqueous hydrogen peroxide were placed in a 500 mL four-necked recovery flask and stirred for 24 hours at 30° C. Next, 100.00 g of water was added to the reaction solution, and the precipitated crystals were filtered to obtain 20.93 g of white crystals (yield: 63%).
[0205] This white crystal １ H-NMR spectral data, １９ The F-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 8.95 (d, 1H), 8.57 (d, 1H), 8.53 (d, 1H), 8.31 (dd, 1H), 8.20 (d, 1H), 7.80 (dt, 1H), 7.71 (dt, 1H). ・ 19F-NMR (d6-DMSO) δ: 82.4 (s, 3F). From these spectral data, the obtained white crystals were identified as the compound represented by the title chemical formula (II-1).
[0206] (2) <Synthesis of 2-trifluoromethanesulfonyl-5-phenyldibenzothiophenium triflate> A 500 mL four-necked recovery flask was charged with 33.23 g (100.0 mmol) of 2-trifluoromethanesulfonyldibenzothiophene oxide obtained in (1) above and 100.00 g of benzene, and then 56.43 g (200.0 mmol) of trifluoromethanesulfonic anhydride was added dropwise and stirred for 24 hours at 30° C. Next, 200.00 g of water and 50.00 g of MTBE were added to the reaction solution, and the precipitated crystals were filtered to obtain 36.35 g of white crystals (yield: 67%).
[0207] This white crystal １ H-NMR spectral data, １９ The F-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 9.35 (s, 1H), 8.93 (d, 1H), 8.82 (d, 1H), 8.50 (d, 1H), 8.44 (d, 1H), 8.03 (t, 1H), 7.86 (t, 1H), 7.71 (q, 3H), 7.59 (t, 2H). ・ 19 F-NMR (d6-DMSO) δ: 82.1 (s, 3F), 82.3 (s, 3F). From these spectral data, the obtained white crystals were identified as the title compound. This compound is designated as "PAG1."
[0208] Example 2 Synthesis of 2-trifluoromethanesulfonyl-5-(4-fluorophenyl)-dibenzothiophenium triflate Salt A 500 mL four-necked recovery flask was charged with 33.23 g (100.0 mmol) of 2-trifluoromethanesulfonyldibenzothiophene oxide obtained in Example 1(1), 9.61 g (100.0 mmol) of fluorobenzene, and 200.00 g of chloroform, followed by dropwise addition of 56.43 g (200.0 mmol) of trifluoromethanesulfonic anhydride and stirring for 24 hours at 30° C. Next, 200.00 g of water and 100.00 g of MTBE were added to the reaction solution, and the precipitated crystals were filtered to obtain 33.07 g of white crystals (yield: 59%).
[0209] This white crystal １ H-NMR spectral data, １９ The F-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 9.33 (s, 1H), 8.91 (d, 1H), 8.79 (d, 1H), 8.49 (d, 1H), 8.41 (d, 1H), 8.02 (t, 1H), 7.86 (t, 1H), 7.78 (dd, 2H), 7.46 (d, 2H). ・ 19 F-NMR (d6-DMSO) δ: 82.1 (s, 3F), 82.3 (s, 3F), 107.7 (sep, 1F). From these spectral data, the obtained white crystals were identified as the title compound.
[0210] Example 3 Synthesis of 2-trifluoromethanesulfonyl-5-(4-iodophenyl)-dibenzothiophenium triflate Salt A 500 mL four-necked recovery flask was charged with 33.23 g (100.0 mmol) of 2-trifluoromethanesulfonyldibenzothiophene oxide obtained in Example 1(1), 20.40 g (100.0 mmol) of iodobenzene, and 200.00 g of chloroform, followed by dropwise addition of 56.43 g (200.0 mmol) of trifluoromethanesulfonic anhydride and stirring for 24 hours at 30° C. Next, 200.00 g of water and 100.00 g of MTBE were added to the reaction solution, and the precipitated crystals were filtered to obtain 27.40 g of white crystals (yield: 41%).
[0211] This white crystal １ H-NMR spectral data, １９ The F-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 9.34 (s, 1H), 8.92 (d, 1H), 8.80 (d, 1H), 8.49 (d, 1H), 8.43 (d, 1H), 8.03 (t, 1H), 7.96 (d, 2H), 7.86 (t, 1H), 7.43 (d, 2H). ・ 19 F-NMR (d6-DMSO) δ: 82.1 (s, 3F), 82.3 (s, 3F). From these spectral data, the obtained white crystals were identified as the title compound.
[0212] Example 4 Synthesis of 2-trifluoromethanesulfonyl-5-(4-ethenylphenyl)-dibenzothiophenium triflate Salt A 500 mL four-necked recovery flask was charged with 13.29 g (40.0 mmol) of 2-trifluoromethanesulfonyldibenzothiophene oxide obtained in Example 1(1) above and 14.80 g (80 mmol) of 2-bromoethylbenzene, and then 22.57 g (80 mmol) of trifluoromethanesulfonic anhydride was added dropwise and the mixture was stirred at 30°C for 24 hours. Next, 80.00 g of water was added to the reaction mixture, and the mixture was separated. The organic layer was concentrated at 40°C, and then 100.0 g of THF was added. The mixture was cooled to 10°C, and 8.10 g (80 mmol) of triethylamine was added dropwise and the mixture was stirred at 30°C for 24 hours. Next, 200.00 g of water was added to the reaction mixture, and the precipitated crystals were filtered to obtain 13.2 g of white crystals (yield: 58%).
[0213] This white crystal １ H-NMR spectral data, １９ The F-NMR spectrum data was as follows: 1 H-NMR(d6-DMSO)δ: 9.30 (s, 1H), 8.91 (d, 1H), 8.85 (d, 1H), 8.51 (d, 1H), 8.40 (d, 1H), 8.0 3 (t, 1H), 7.94 (d, 2H), 7.88 (t, 1H), 7.40 (d, 2H), 6.92 (q, 1H), 6.20 (d, 1H), 5.66 (d, 1H). ・ 19 F-NMR (d6-DMSO) δ: -81.8 (s, 3F), -82.6 (s, 3F). From these spectral data, the obtained white crystals were identified as the title compound.
[0214] Comparative Example 1 (1) Synthesis of 2-methanesulfonyldibenzothiophene oxide 10.49 g (40 mmol) of 2-methanesulfonyldibenzothiophene, 80.00 g of formic acid, and 3.89 g (40.0 mmol) of 35% aqueous hydrogen peroxide were placed in a 500 ml four-necked recovery flask and stirred for 24 hours at 30° C. Next, 160.00 g of water was added to the reaction solution, and the precipitated crystals were filtered to obtain 8.80 g of white crystals (yield: 79%).
[0215] This white crystal １ The H-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 8.94 (d, 1H), 8.55-8.60 (m, 1H), 8.34 (d, 1H), 8.12-8.16 (m, 1H), 8.01-8.05 (m, 1H), 7.58-7.65 (m, 2H), 3.35 (s, 3H). From this spectral data, the obtained white crystals were identified as the title compound.
[0216] (2) <Synthesis of 2-methanesulfonyl-5-phenyldibenzothiophenium triflate> A 500 mL four-necked recovery flask was charged with 11.13 g (40 mmol) of 2-methanesulfonyldibenzothiophene oxide obtained in (1) above and 100.00 g of benzene, and then 22.57 g (80 mmol) of trifluoromethanesulfonic anhydride was added dropwise and stirred for 24 hours at 30° C. Next, 80.00 g of water was added to the reaction solution, and the precipitated crystals were filtered to obtain 15.05 g of white crystals (yield: 77%).
[0217] This white crystal １ H-NMR spectral data, １９ The F-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 9.08 (d, 1H), 8.72 (d, 1H), 8.64 (d, 1H), 8.43 (d, 1H), 8.26 (d, 1H), 8.03 (t, 1H), 7.84 (t, 1H), 7.73-7.58 (m, 5H), 3.35 (s, 3H). ・ 19 F-NMR (d6-DMSO) δ: -78.11 (s, 3F). From these spectral data, the obtained white crystals were identified as the title compound. This compound is designated as "PAG6".
[0218] Examples 5 to 8 and Comparative Examples 2 and 3: Preparation of Resist Compositions The main raw materials listed below were mixed in the proportions shown in Table 1 to prepare a homogeneous solution, which was then filtered through a membrane filter with a pore size of 0.2 μm to prepare resist compositions (Examples 5 to 8 and Comparative Examples 2 and 3).
[0219] [Main raw materials and reagents] (A) Polymer having a structural unit containing an acid-reactive group - Copolymer of 4-hydroxystyrene and 1-ethylcyclopentyl methacrylate: synthesized in accordance with the method described in JP 2021-196578 A. (Hereinafter, this may be referred to as "Polymer 1.") (B) Photoacid Generator 2-Trifluoromethanesulfonyl-5-phenyldibenzothiophenium triflate salt: Compound of Example 1 (PAG1) 2-Trifluoromethanesulfonyl-5-(4-fluorophenyl)-dibenzothiophenium triflate salt: Compound of Example 2 (PAG2) 2-Trifluoromethanesulfonyl-5-(4-iodophenyl)-dibenzothiophenium triflate salt: Compound of Example 3 (PAG3) 2-Trifluoromethanesulfonyl-5-(4-ethenylphenyl)-dibenzothiophenium triflate salt: Compound of Example 4 (PAG4) Phenyldibenzothiophenium triflate salt: Synthesized in accordance with the method described in Nature Catalysis (2020), 3(2), 163-169. (Hereinafter, this may be referred to as "PAG5") 2-Methanesulfonyl-5-phenyldibenzothiophenium triflate salt: the compound of Comparative Example 1 (PAG6) (C) Acid diffusion controller Salicylic acid triphenylsulfonium salt: synthesized in accordance with the method described in WO 2015 / 019983 (Hereinafter, this may be referred to as "PDB1") (D) Solvent Propylene glycol monomethyl ether acetate: manufactured by Kanto Chemical Co., Ltd. (Hereinafter, this may be referred to as "PGMEA") γ-Butyrolactone: manufactured by Kanto Chemical Co., Ltd. (Hereinafter, this may be referred to as "GBL")
[0220] Test Example 1: Evaluation of Sensitivity The sensitivity of the resist compositions (Examples 5 to 8 and Comparative Examples 2 and 3) was evaluated as follows. (1) The resist composition was applied to a 2 cm square silicon substrate using a spin coater, and then prebaked (PAB) on a hot plate at 110°C for 90 seconds to form a 50 nm thick resist film. (2) The formed resist film was exposed to light using an electron beam lithography system (Elionix Corporation's "ELS-7500EX"), with the exposure dose gradually changed so that a line-and-space pattern (half pitch 100 nm) would result after development. (3) The exposed substrate was subjected to a post-exposure bake (PEB) treatment at 110°C for 90 seconds. (4) The PEB-treated substrate was subjected to alkaline development for 60 seconds at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (Tokyo Ohka Kogyo Co., Ltd.'s "NMD-3"). (5) After the alkali development, the substrate was washed with pure water for 15 seconds to obtain a substrate (test piece) on which a resist pattern was formed. (6) The resist pattern of the obtained test piece was observed with a scanning electron microscope ("S-4800" manufactured by Hitachi High-Technologies Corporation) to confirm the exposure dose required to obtain a line and space pattern with a half pitch of 100 nm. The lower this exposure dose, the higher the sensitivity is considered to be.
[0221] The evaluation results of the sensitivity are shown in Table 1.
[0222] The resist compositions (Examples 5 to 8) containing the compounds of the present invention (PAG1 to 4) formed resist patterns with a lower exposure dose than the resist compositions (Comparative Examples 2 and 3) containing the conventional compounds (PAG5 and 6). This demonstrates that the compounds of the present invention (PAG1 to 4) exhibit higher sensitivity to actinic rays than the conventional compounds (PAG5 and 6).
[0223] The compound of the present invention represented by the chemical formula (I) has an electron-withdrawing group (—SO ２ CF ３By providing a sulfonium cation having the above structure, the LUMO in the molecule can be lowered, and the compound has high photosensitivity to actinic energy rays such as EUV (extreme ultraviolet light), EB (electron beam), and X-rays. Therefore, the compound of the present invention is useful as a photoacid generator or an acid diffusion controller having high photodecomposition efficiency.
Claims
1. A compound represented by chemical formula (I). (In the formula, R １ and R ２ are the same or different and represent a hydrogen atom; a halogen atom; or —CF ３ ;-SO ２ R ３ an alkyl group having 1 to 10 carbon atoms; —OH; a polymerizable group selected from formulas (S-1) to (S-4); or an acid-reactive group selected from formulas (R-1) to (R-7). ３ is -CF ３ , -CF ２ CF ３ , an alkyl group having 1 to 10 carbon atoms, or a phenyl group. [A] － is the trifluoromethanesulfonate anion (TfO － ) or a halide ion. (In the formula, R １ａ represents a hydrogen atom or a methyl group, and Y represents a single bond or an alkylene group having 1 to 3 carbon atoms. (wherein Y is the same as above. R ５１ ~R ５３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, or R ５１ and R ５２ may be linked to each other to form an aliphatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are attached. ５４ and R ５５ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ５６ represents an alkyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ２ - may be replaced by -O- or -S-. d represents an integer of 0 to 4. However, in formula (R-1), formula (R-3), and formulas (R-5) to (R-7), R ５１ ~R ５３ Except when all are hydrogen atoms.) 2. The compound according to claim 1, which is a compound represented by chemical formula (I-1). (In the formula, R １ , R ２ and [A] － is the same as above.) 3. A photoacid generator containing the compound according to claim 1 or 2.
4. A resist composition comprising a polymer having a structural unit containing an acid-reactive group and the photoacid generator according to claim 3.
5. A method for forming a resist pattern, comprising the steps of: applying the resist composition according to claim 4 to a substrate to form a resist film; exposing the resist film to light; and developing the exposed resist film to form a resist pattern.
6. A sulfoxide compound represented by the chemical formula (II). (In the formula, R ２ represents a hydrogen atom; a halogen atom; ３ ;-SO ２ R ３ an alkyl group having 1 to 10 carbon atoms; —OH; a polymerizable group selected from formulas (S-1) to (S-4); or an acid-reactive group selected from formulas (R-1) to (R-7). ３ is -CF ３ , -CF ２ CF ３ , an alkyl group having 1 to 10 carbon atoms, or a phenyl group. (In the formula, R １ａ represents a hydrogen atom or a methyl group, and Y represents a single bond or an alkylene group having 1 to 3 carbon atoms. (wherein Y is the same as above. R ５１ ~R ５３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, or R ５１ and R ５２ may be linked to each other to form an aliphatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are attached. ５４ and R ５５ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ５６ represents an alkyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ２ - may be replaced by -O- or -S-. d represents an integer of 0 to 4. However, in formula (R-1), formula (R-3), and formulas (R-5) to (R-7), R ５１ ~R ５３ Except when all are hydrogen atoms.) 7. A method for producing a compound represented by chemical formula (I) according to claim 1, comprising the step of reacting a sulfoxide compound represented by chemical formula (II) with a compound represented by chemical formula (III) in the presence of an acid or an acid anhydride. (In the formula, R １ , R ２ and [A] － is the same as above.)
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