WO2024128017A1 - スルホニウム塩、酸発生剤、及びフォトレジスト - Google Patents

スルホニウム塩、酸発生剤、及びフォトレジスト Download PDF

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WO2024128017A1
WO2024128017A1 PCT/JP2023/042981 JP2023042981W WO2024128017A1 WO 2024128017 A1 WO2024128017 A1 WO 2024128017A1 JP 2023042981 W JP2023042981 W JP 2023042981W WO 2024128017 A1 WO2024128017 A1 WO 2024128017A1
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sulfonium salt
acid
photoresist
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智仁 木津
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San Apro KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • the present invention relates to a novel sulfonium salt, an acid generator containing the sulfonium salt, and a photoresist containing the sulfonium salt.
  • Patent Document 1 discloses a positive resist containing triphenylsulfonium trifluoromethanesulfonate and a photosensitive resin. It also describes that the resist can be used to form fine patterns with high precision when irradiated with KrF excimer laser light.
  • An object of the present invention is to provide a novel sulfonium salt which rapidly decomposes to generate an acid when irradiated with light of an ultrashort wavelength. Another object of the present invention is to provide an acid generator having good sensitivity to light with an ultrashort wavelength. Another object of the present invention is to provide a photoresist capable of transferring fine patterns with high accuracy using light having an ultrashort wavelength.
  • the sulfonium salt represented by the following formula (1) has a structure in which an SF5 group (pentafluorosulfanyl group) is bonded to an arylsulfonium skeleton, and therefore has extremely high sensitivity to ultrashort wavelength light, and when irradiated with ultrashort wavelength light, it quickly decomposes to generate acid, and the sulfonium salt has excellent solubility in solvents.
  • the present invention was completed based on this finding.
  • the present invention provides a sulfonium salt represented by the following formula (1):
  • R 1 represents an organic group
  • m represents an integer of 1 to 3
  • n represents an integer of 1 to 5.
  • X - represents a monovalent counter anion.
  • the benzene ring shown in the formula may have a substituent other than the SF 5 group bonded thereto.
  • the two R 1s may be bonded to each other to form a ring together with the adjacent S + .
  • the present invention also provides the sulfonium salt, in which the monovalent counter anion is a sulfonate anion, a sulfonylimide anion, or a halogen ion.
  • the present invention also provides an acid generator containing the sulfonium salt.
  • the present invention also provides the acid generator, which is an acid generator for extreme ultraviolet rays or an acid generator for electron beams.
  • the present invention also provides a photoresist containing the sulfonium salt and an acid-reactive compound.
  • the sulfonium salt represented by the above formula (1) (hereinafter, sometimes referred to as "sulfonium salt (1)”) has excellent sensitivity to light having a wavelength of 20 nm or less, and can be easily decomposed to generate an acid (H + X - : X - is derived from X - in formula (1)) when irradiated with light having the above wavelength. Therefore, by performing photolithography using a photoresist containing the sulfonium salt (1) and light having a wavelength of 20 nm or less, fine patterns can be formed with high precision, making it possible to realize even larger capacities and even smaller sizes of electronic devices.
  • FIG. 1 shows the results of 1 H-NMR measurement of the sulfonium salt obtained in Example 4.
  • FIG. 19 shows the results of 19 F-NMR measurement of the sulfonium salt obtained in Example 4.
  • the sulfonium salt (1) of the present invention is a compound represented by the following formula (1).
  • R 1 represents an organic group
  • m represents an integer of 1 to 3
  • n represents an integer of 1 to 5.
  • X ⁇ represents a monovalent counter anion.
  • the benzene ring shown in formula (1) may have a substituent other than the SF5 group bonded thereto.
  • the compound represented by the above formula (1) has two R 1s .
  • the two R 1s may be the same or different.
  • the two R 1s may be linked to each other to form a ring together with the adjacent S + .
  • the compound represented by the above formula (1) has two groups shown in square brackets.
  • the two groups shown in square brackets may be the same or different.
  • the m represents an integer of 1 to 3, with 1 or 2 being preferred, and 1 being particularly preferred, in that it provides the effect of improving sensitivity to ultrashort wavelength light.
  • n an integer from 1 to 5, with 1 or 2 being preferred since it has the effect of improving sensitivity to ultrashort wavelength light.
  • Examples of the organic group for R 1 include a monovalent hydrocarbon group, a monovalent heterocyclic group, and a monovalent group in which two or more of the above groups are bonded via a single bond or a linking group.
  • the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded via a single bond.
  • Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 6), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl; alkenyl groups having 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as vinyl, allyl, and 1-butenyl; and alkynyl groups having 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as ethynyl and propynyl.
  • alkyl groups having 1 to 20 carbon atoms preferably 1 to 10, particularly preferably 1 to 6
  • alkenyl groups having 2 to 20 carbon atoms preferably 2 to 10, particularly preferably 2 to 3
  • alkynyl groups having 2 to 20 carbon atoms
  • Examples of the alicyclic hydrocarbon group include 3- to 20-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; 3- to 20-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group; and bridged cyclic hydrocarbon groups such as a perhydronaphthalene-1-yl group, a norbornyl group, an adamantyl group, a tricyclo[5.2.1.0 2,6 ]decan-8-yl group, and a tetracyclo[4.4.0.1 2,5 .
  • the aromatic hydrocarbon group may be, for example, an aryl group having 6 to 20 carbon atoms (preferably having 6 to 14 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), such as a phenyl group or a naphthyl group.
  • the monovalent heterocyclic group is a group obtained by removing one hydrogen atom from the structural formula of a heterocycle.
  • the heterocycle includes aromatic heterocycles and non-aromatic heterocycles. Examples of such heterocycles include 3- to 20-membered rings (preferably 3- to 10-membered rings, particularly preferably 4- to 6-membered rings) having carbon atoms and at least one heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.) as atoms constituting the ring, and condensed rings thereof.
  • heterocycles containing an oxygen atom as a heteroatom for example, three-membered rings such as an oxirane ring; four-membered rings such as an oxetane ring; five-membered rings such as a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, and a ⁇ -butyrolactone ring; six-membered rings such as a 4-oxo-4H-pyran ring, a tetrahydropyran ring, and a morpholine ring; condensed rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-chromene ring, a chroman ring, and an isochroman ring; 3-oxatricyclo[4.3.1.1 4,8 ]undecane-2-one ring, 3-oxatricyclo[4.2.1.0 4,
  • linking group examples include a C 1-5 alkylene group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond (—OCOO—).
  • the monovalent hydrocarbon group, the monovalent heterocyclic group, and the monovalent group formed by bonding two or more of the above groups via a single bond or a linking group may have a substituent.
  • substituents include a halogen atom, a haloalkyl group (e.g., a haloC 1-5 alkyl group such as a trifluoromethyl group), an oxo group, a hydroxyl group, a thiol group, a carboxyl group, a silyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group (e.g., a mono- or di-C 1-4 alkylamino group such as a methylamino, dimethylamino, ethylamino, or diethylamino group; a C 1-10 acylamino group such as an acetylamino, propionylamino, or benzoylamino group
  • the silyl group includes a tri(C 1-5 alkyl)silyl group such as a trimethylsilyl group.
  • the monovalent hydrocarbon group, the monovalent heterocyclic group, and the monovalent group formed by bonding two or more of the groups via a single bond or a linking group may be bonded to an acid-reactive compound (or a monomer constituting an acid-reactive compound) described below.
  • the cationic portion constituting the sulfonium salt (1) may contain an acid-reactive compound (or a monomer constituting an acid-reactive compound) described below in its structure.
  • At least one of the two R 1s is an aryl group, from the viewpoint of improving the sensitivity to light rays of ultrashort wavelengths, and a combination of an aryl group and an alkyl group, or a combination of an aryl group and an aryl group is preferable, and a combination of an aryl group and an aryl group is particularly preferable.
  • the heterocycle contains S + as described in formula (1) as a heteroatom, and may contain a heteroatom other than the S + (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.).
  • the heterocycle is, for example, a 5- to 6-membered heterocycle.
  • the heterocycle is preferably a condensed ring in which an aromatic hydrocarbon ring is condensed to a heterocycle, in that it improves sensitivity to ultrashort wavelength light, and is particularly preferably a condensed ring in which two or more aromatic hydrocarbon rings are condensed to a heterocycle.
  • one R 1 is preferably an alkyl group or an aryl group in that the sensitivity to ultrashort wavelength light is improved, and an aryl group is preferable in that the sensitivity to ultrashort wavelength light is improved and the solvent solubility is excellent.
  • the aryl group is preferably a phenyl group.
  • the aryl group may have a halogen atom, a haloalkyl group (e.g., a haloC 1-5 alkyl group), an alkyl group (e.g., a C 1-5 alkyl group), a silyl group, or the like as a substituent.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • the alkyl group may have a halogen atom or a silyl group as a substituent.
  • the sulfonium salt (1) is preferably a sulfonium salt represented by the following formula (1-1), a sulfonium salt represented by the following formula (1-2), a sulfonium salt represented by the following formula (1-3), or a sulfonium salt represented by the following formula (1-4).
  • n and X ⁇ are the same as defined above.
  • ring Z represents a heterocycle containing a sulfur atom (which is represented as S + in formula (1-4)).
  • the heterocycle may be condensed with one or more aromatic hydrocarbon rings.
  • the heterocycle is an aromatic heterocycle or a non-aromatic heterocycle, for example a 5- or 6-membered heterocycle.
  • the heterocycle may contain a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.) other than the sulfur atom shown in the formula.
  • the multiple n's in the formulas (1-2) and (1-3) may be the same or different.
  • the benzene ring shown in the above formula may have a substituent bonded thereto in addition to the SF5 group.
  • the substituent include a halogen atom, a haloalkyl group (e.g., a haloC1-5 alkyl group), an alkyl group (e.g., a C1-5 alkyl group), and a silyl group.
  • the position at which the SF5 group is bonded in the benzene ring in the above formula is not particularly limited, but in terms of improving the sensitivity to ultrashort wavelength light, the meta or para position relative to the position at which S + is bonded in the formula is preferred.
  • the position at which the substituent is bonded is not particularly limited, but in terms of improving the sensitivity to light rays of ultrashort wavelengths, the meta position or para position with respect to the position at which S + is bonded in the formula is preferable.
  • sulfonium salt (1) examples include compounds represented by the following formula.
  • X- in the following formula is the same as above.
  • the benzene ring shown in the following formula may have a substituent bonded thereto other than the SF5 group.
  • the substituent include a halogen atom, a haloalkyl group (e.g., a haloC1-5 alkyl group), an alkyl group (e.g., a C1-5 alkyl group), and a silyl group.
  • the sulfonium salts represented by the formulas (1-1) to (1-3) are preferred in terms of improving sensitivity to ultrashort wavelength light, and the sulfonium salts represented by the formulas (1-1-1) to (1-1-5) and (1-2-1) to (1-2-12) are particularly preferred.
  • the sulfonium salts represented by the formulas (1-1) to (1-3) are preferred, in terms of improving sensitivity to ultrashort wavelength light and excellent solvent solubility, and the sulfonium salts represented by the formulas (1-1-1) to (1-1-5) are particularly preferred, with the sulfonium salts represented by the formulas (1-1-1), (1-1-2), and (1-1-5) being the most preferred.
  • a compound in which the ring Z is an aromatic heterocycle or a compound in which the ring Z is a condensed ring in which an aromatic hydrocarbon ring is condensed to a heterocycle is preferred in terms of improving sensitivity to ultrashort wavelength light
  • a compound in which the ring Z is a condensed ring in which two or more aromatic hydrocarbon rings are condensed to a heterocycle is particularly preferred in terms of improving sensitivity to ultrashort wavelength light and having excellent solvent solubility.
  • the sulfonium salt represented by the formula (1-4) are preferred in terms of improving sensitivity to ultrashort wavelength light, and the sulfonium salts represented by the formulas (1-4-9), (1-4-11) to (1-4-13) are particularly preferred in terms of improving sensitivity to ultrashort wavelength light and having excellent solvent solubility.
  • a sulfonium salt represented by the following general formula (1-4') is particularly preferred, in that it improves sensitivity to light of ultrashort wavelengths and has excellent solvent solubility.
  • X - and n are the same as defined above.
  • n is preferably 1 or 2 in terms of improving the sensitivity to ultrashort wavelength light.
  • L represents a single bond or a linking group, and examples thereof include a C 1-5 alkylene group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), and the like.
  • the benzene ring structure shown in the above formula may have a substituent bonded thereto, and examples of the substituent include a halogen atom, a haloalkyl group (for example, a haloC 1-5 alkyl group), an alkyl group (for example, a C 1-5 alkyl group), and a silyl group.
  • substituent include a halogen atom, a haloalkyl group (for example, a haloC 1-5 alkyl group), an alkyl group (for example, a C 1-5 alkyl group), and a silyl group.
  • X ⁇ represents a monovalent counter anion, and examples thereof include a halogen ion, a halogen oxo acid anion, a boron anion, a phosphate anion, a sulfate anion, a sulfonate anion, a sulfonylimide anion, a carboxylate anion, a methide anion, an antimony anion, OH ⁇ , SCN ⁇ , NO 2 ⁇ , NO 3 ⁇ , and the like.
  • halogen ion examples include Cl ⁇ , Br ⁇ , and I ⁇ .
  • halogen oxo acid anion examples include ClO 4 ⁇ , IO 3 ⁇ , and BrO 3 ⁇ .
  • boron anion examples include inorganic boron anions such as BF4- , and organic boron anions such as ( C6F5 ) 4B- , (( CF3 ) 2C6H3 ) 4B- , tetraphenylborate, tetrakis ( monofluorophenyl)borate, tetrakis( difluorophenyl )borate, and tetrakis(trifluorophenyl)borate.
  • inorganic boron anions such as BF4-
  • organic boron anions such as ( C6F5 ) 4B- , (( CF3 ) 2C6H3 ) 4B- , tetraphenylborate, tetrakis ( monofluorophenyl)borate, tetrakis( difluorophenyl )borate, and tetrakis(trifluorophenyl)borate.
  • phosphate anion examples include inorganic phosphate anions such as PF6- , PF( C2F5 ) 5- , PF2 ( C2F5 ) 4- , PF3 ( C2F5 ) 3- , PF4( C2F5 ) 2- , PF5 ( C2F5 ) - , and PO43- .
  • the sulfonate anion is represented, for example, by the following formula (s1).
  • R s1 -SO 3 - (s1) (In the formula, R represents an organic group.)
  • Examples of the organic group in R s1 include a C 1-30 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a group in which two or more of the above groups are linked by a single bond or a linking group selected from -O-, -CO 2 -, -S-, -SO 3 -, and -SO 2 N(R s2 )-.
  • the above group may be bonded to an acid-reactive compound described below (or a monomer constituting an acid-reactive compound described below).
  • the anion moiety constituting the sulfonium salt (1) may contain an acid-reactive compound described below (or a monomer constituting an acid-reactive compound) within its structure.
  • the R s2 represents a hydrogen atom or an alkyl group (for example, a C 1-30 alkyl group).
  • the substituents include, for example, halogen atoms such as fluorine atoms.
  • the C 1-30 hydrocarbon group includes a C 1-30 aliphatic hydrocarbon group, a C 3-30 alicyclic hydrocarbon group, a C 6-30 aromatic hydrocarbon group, and a group in which two of these are combined.
  • the C 1-30 hydrocarbon group is preferably a C 1-30 alkyl group, a C 6-15 aryl group, a C 6-15 cycloalkylene group, a C 6-15 bridged cyclic hydrocarbon group, or a group in which two of these are bonded together.
  • the heterocyclic group is a group in which one hydrogen atom has been removed from the structural formula of a heterocycle.
  • the heterocycle includes aromatic heterocycles and non-aromatic heterocycles. Examples of such heterocycles include 3- to 10-membered rings (preferably 4- to 6-membered rings) whose ring-constituting atoms include carbon atoms and at least one heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.), and condensed rings thereof.
  • sulfonate anion examples include CH3SO3- (sometimes referred to as “ MsO- " in this specification), C4H9SO3- , CF3SO3- ( sometimes referred to as “ TfO- " ), C2F5C4H4SO3-, C4F9SO3- , benzenesulfonate anion , p - toluenesulfonate anion , and camphorsulfonate anion .
  • the sulfonylimide anion is represented, for example, by the following formula (n1). (R n1 SO 2 ) 2 N - (n1) (In the formula, two R n1 are the same or different and each represents an organic group.)
  • Examples of the organic group in R n1 include the same organic groups as those in R s1 .
  • sulfonylimide anion examples include (FSO 2 ) 2 N - , (CF 3 SO 2 ) 2 N - , (C 4 F 9 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , and the like.
  • the carboxylate anion is represented, for example, by the following formula (c1).
  • R c1 -COO - (c1) (In the formula, R represents an organic group.)
  • Examples of the organic group in R c1 include the same organic groups as those in R s1 .
  • carboxylate anion examples include CF 3 CO 2 ⁇ , CH 3 CO 2 ⁇ , C 2 H 5 CO 2 ⁇ , and PhCO 2 ⁇ .
  • Examples of the methide anion include a sulfonylmethide anion represented by the following formula (m1). ( Rm1SO2 ) 3C- ( m1 ) (In the formula, three R m1 are the same or different and each represents an organic group.)
  • Examples of the organic group in R m1 include the same organic groups as those in R s1 .
  • methide anion examples include (CF 3 SO 2 ) 3 C — .
  • the antimony anion may, for example, be SbF 6 ⁇ .
  • the monovalent counter anion includes, in addition to the above, the anions described in, for example, JP-A-2013-47211, JP-A-2021-81708, JP-A-2013-80245, JP-A-2013-80240, and JP-A-2013-33161.
  • the counter anion is preferably a sulfonate anion, a sulfonylimide anion, or a halogen ion, because they improve sensitivity to ultrashort wavelength light and have excellent solvent solubility.
  • the sulfonium salt (1) has high photosensitivity to light rays with wavelengths of 20 nm or less, such as EUV (extreme ultraviolet), EB (electron beam), X-rays, etc. Furthermore, even without using a photosensitizer, light energy is directly transmitted to the sulfonium salt (1) by simply irradiating it with light of the above wavelengths, and photodecomposition proceeds rapidly, generating an acid (H + X - ).
  • the sulfonium salt (1) has the above-mentioned properties, it can be suitably used as an acid generator (e.g., a photoacid generator).
  • an acid generator e.g., a photoacid generator
  • the sulfonium salt (1) has excellent solubility in organic solvents, and its solubility in an organic solvent (e.g., propylene glycol monomethyl ether acetate) at room temperature (e.g., 25° C.) and normal pressure is, for example, 2% by weight or more (e.g., 2 to 50% by weight), preferably 3% by weight or more, further preferably 4% by weight or more, particularly preferably 5% by weight or more, and most preferably 10% by weight or more.
  • organic solvent e.g., propylene glycol monomethyl ether acetate
  • the organic solvent may, for example, be aromatic hydrocarbons such as benzene, toluene, xylene, or ethylbenzene; carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, or diethyl carbonate; linear or cyclic esters such as ethyl acetate, butyl acetate, ethyl lactate, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, or ⁇ -caprolactone; ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, or dibutyl ether; Examples of such glycol diethers include propylene glycol dimethyl ether, triethylene glycol diethyl ether, and tripropylene glycol dibutyl ether; glycol monoether monoesters such as ethylene glycol monomethyl
  • the sulfonium salt (1) has excellent solvent solubility, so when added to a photoresist, it disperses uniformly and can impart good fine pattern forming properties to the photoresist.
  • the sulfonium salt represented by the formula (1-1) can be produced, for example, by the following reaction.
  • the sulfonium salt represented by the formula (1-2) can be produced, for example, by the following reaction.
  • the sulfonium salt represented by the formula (1-3) can be produced, for example, by the following reaction.
  • n is the same as above.
  • X- represents a monovalent counter anion as above, and M represents a protecting group for X- (counter anion) (e.g., a silyl group, etc.).
  • A represents a halogen atom, for example, bromine (Br).
  • the Grignard reaction can be carried out in the presence or absence of a solvent.
  • a typical solvent used in the Grignard reaction e.g., one or more solvents selected from diethyl ether, tetrahydrofuran, dichloromethane, etc.
  • the reaction temperature is about -20 to 150°C, depending on the boiling point of the solvent used.
  • the reaction time is about one to several tens of hours.
  • the atmosphere for the above reaction is not particularly limited as long as it does not inhibit the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, etc. Furthermore, the reaction may be carried out in any method, such as a batch method, a semi-batch method, or a continuous method.
  • reaction product obtained can be separated and purified by a separation method such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these.
  • the chemical structure of the sulfonium salt of the present invention can be identified, for example, by 1 H-, 11 B-, 13 C-, 19 F-, or 31 P-nuclear magnetic resonance spectroscopy, mass spectrometry, elemental analysis, or the like.
  • the acid generator of the present invention contains at least the sulfonium salt (1).
  • the acid generator may contain one type of the sulfonium salt (1) alone or in combination of two or more types.
  • the acid generator may contain components other than the sulfonium salt (1), but the proportion of the sulfonium salt (1) relative to all compounds (100% by weight) contained in the acid generator that decompose upon light irradiation to generate an acid is preferably, for example, 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • the acid generator may contain an acid generator other than the sulfonium salt (1), but the content of the other acid generator is preferably, for example, 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less, particularly preferably 20% by weight or less, most preferably 10% by weight or less, and particularly preferably 5% by weight or less, relative to all compounds (100% by weight) that decompose upon light irradiation to generate an acid.
  • the acid generator has excellent solubility in organic solvents, and the amount of the acid generator (or the sulfonium salt (1)) that dissolves in 100 parts by weight of organic solvent at 25°C is, for example, 5 parts by weight or more, preferably 10 parts by weight or more, particularly preferably 15 parts by weight or more, and most preferably 20 parts by weight or more.
  • the organic solvent include the same organic solvents in which the sulfonium salt (1) is soluble.
  • the acid generator has excellent sensitivity not only to light rays on the longer wavelength side but also to light rays with ultrashort wavelengths (for example, wavelengths of 20 nm or less), and when irradiated with light rays, it easily decomposes to generate acid (H + X ⁇ ).
  • the acid generator has the above characteristics, it can be suitably used as a photoacid generator (particularly, an acid generator for extreme ultraviolet rays and an acid generator for electron beams). It can also be suitably used as an acid generator for photoresists [particularly, an acid generator for photoresists used in photolithography using light with an ultrashort wavelength (e.g., wavelength of 20 nm or less)].
  • the photoresist of the present invention contains the acid generator (or the sulfonium salt (1)) and an acid-reactive compound.
  • the sulfonium salt (1) and the acid-reactive compound may be contained in the photoresist as separate compounds, or the acid-reactive compound may be incorporated into the anion or cation portion of the sulfonium salt (1) and may be contained in the photoresist in an integrated state.
  • the content of the acid generator (or the sulfonium salt (1)) is, for example, 0.001 to 20% by weight, preferably 0.01 to 15% by weight, and particularly preferably 0.05 to 7% by weight, of the total amount of the acid-reactive compound.
  • the content of the acid generator (or the sulfonium salt (1)) is 0.001% by weight or more of the total amount of the acid-reactive compound, excellent sensitivity can be exhibited not only to light on the longer wavelength side, but also to light with a wavelength of 20 nm or less. Furthermore, if the content is 20% by weight or less of the total amount of the acid-reactive compound, the effect of improving the resolution of the photoresist can be obtained.
  • the content ratio of sulfonium salt (1) and acid-reactive compound in the photoresist is preferably in the same range as when the photoresist contains sulfonium salt (1) and acid-reactive compound as separate compounds.
  • the acid-reactive compound is a compound that has the property of changing its solubility in an alkaline developer by the action of an acid, and is a polymer.
  • the photoresist of the present invention may contain one type of the acid-reactive compound alone, or may contain two or more types in combination.
  • the acid-reactive compounds include those that are easily soluble in alkaline developers and react with a crosslinker in the presence of an acid to produce a compound that is poorly soluble or insoluble in alkaline developers, and those that are poorly soluble or insoluble in alkaline developers and whose solubility in alkaline developers increases due to the action of an acid.
  • the photoresist contains the following composition (1) and composition (2).
  • Composition (1) A composition comprising the acid generator and a negative-type photosensitive resin (QN) that is easily soluble in an alkaline developer and generates a compound that is poorly soluble or insoluble in the alkaline developer in the presence of an acid.
  • Composition (2) A composition comprising the acid generator and a positive-type photosensitive resin (QP) that is poorly soluble or insoluble in an alkaline developer and whose solubility in the alkaline developer increases under the action of an acid.
  • QN negative-type photosensitive resin
  • QP positive-type photosensitive resin
  • the negative photosensitive resin (or negative chemically amplified resin; QN) may be, for example, a composition containing a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).
  • Phenol-hydroxyl group-containing resin (QN1) is a resin containing phenolic hydroxyl groups that is easily soluble in alkaline developers and becomes poorly soluble or insoluble in alkaline developers upon reaction with a crosslinking agent.
  • examples include novolac resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic acid derivatives, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyimides containing phenolic hydroxyl groups, polyamic acids containing phenolic hydroxyl groups, phenol-dicyclopentadiene condensation resins, etc. These can be used alone or in combination of two or more.
  • the phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low molecular weight compound as part of its components.
  • the polystyrene equivalent weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin (QN1) measured by GPC is, for example, 2,000 to 20,000.
  • the crosslinking agent (QN2) is a compound that can crosslink the phenolic hydroxyl group-containing resin (QN1) by, for example, the acid generated from the acid generator.
  • the crosslinking agent include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, poly(hydroxystyrene)-based epoxy compounds, oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing phenol compounds, carboxymethyl group-containing melamine resins, carboxymethyl group-containing benzoguanamine resins, carboxymethyl group
  • the content of the crosslinking agent (QN2) is, for example, 10 to 40 mol % based on the total acidic functional groups in the phenolic hydroxyl group-containing resin (QN1), from the viewpoint of efficiently making the phenolic hydroxyl group-containing resin (QN1) less soluble or insoluble in an alkaline developer.
  • the positive-type photosensitive resin (or positive-type chemically amplified resin; QP) may be, for example, an alkali-soluble resin in which an acid-dissociable group has been introduced as a protecting group (protecting group-introduced resin; QP1).
  • Protective group-introduced resin is a resin in which some or all of the hydrogen atoms of acidic functional groups (e.g., phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, etc.) in an alkali-soluble resin have been substituted with acid-dissociable groups.
  • acidic functional groups e.g., phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, etc.
  • the protecting group-introduced resin (QP1) itself is a resin that is insoluble or poorly soluble in an alkaline developer, and when the acid-dissociable group is dissociated by the acid (H + X ⁇ ) generated from the acid generator, it changes into an alkali-soluble resin that is readily soluble in an alkaline developer.
  • the alkali-soluble resin is, for example, a resin with an HLB value of 4 to 19 (preferably 5 to 18, and particularly preferably 6 to 17).
  • Alkali-soluble resins include phenolic hydroxyl group-containing resins, carboxyl group-containing resins, and sulfonic acid group-containing resins.
  • phenolic hydroxyl group-containing resins examples include resins similar to the phenolic hydroxyl group-containing resin (QN1) described above.
  • carboxyl group-containing resin there are no particular limitations on the carboxyl group-containing resin as long as it is a polymer having a carboxyl group, and examples thereof include a homopolymer of a carboxyl group-containing vinyl monomer (Ba) and a homopolymer of a carboxyl group-containing vinyl monomer (Ba) and a hydrophobic group-containing vinyl monomer (Bb).
  • carboxyl group-containing vinyl monomer (Ba) is (meth)acrylic acid.
  • hydrophobic group-containing vinyl monomer (Bb) examples include (meth)acrylic acid esters (Bb1) such as C1-20 alkyl (meth)acrylates and alicyclic group-containing (meth)acrylates, and aromatic hydrocarbon monomers (Bb2) such as hydrocarbon monomers having a styrene skeleton and vinyl naphthalene.
  • the sulfonic acid group-containing resin is a polymer having a sulfonic acid group, and it can be obtained, for example, by vinyl polymerization of a sulfonic acid group-containing vinyl monomer (Bc) such as vinyl sulfonic acid or styrene sulfonic acid, and, if necessary, a hydrophobic group-containing vinyl monomer (Bb).
  • Bc sulfonic acid group-containing vinyl monomer
  • Bb hydrophobic group-containing vinyl monomer
  • Examples of the acid-dissociable groups possessed by the protecting group-introduced resin (QP1) include 1-substituted methyl groups such as methoxymethyl, benzyl, and tert-butoxycarbonylmethyl; 1-substituted ethyl groups such as 1-methoxyethyl and 1-ethoxyethyl; 1-branched alkyl groups such as tert-butyl; silyl groups such as trimethylsilyl; germyl groups such as trimethylgermyl; alkoxycarbonyl groups such as tert-butoxycarbonyl; acyl groups; and cyclic acid-dissociable groups such as tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, and tetrahydrothiofuranyl. These may be contained alone or in combination of two or more.
  • the introduction rate of the acid-dissociable group in the protecting group-introduced resin (QP1) (the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the protecting group-introduced resin (QP1)) cannot be generally determined depending on the type of acid-dissociable group and the alkali-soluble resin into which the group is introduced, but is preferably 10 to 100%, and more preferably 15 to 100%.
  • the weight average molecular weight (Mw) of the protecting group-introduced resin (QP1) measured by GPC in terms of polystyrene is, for example, 1,000 to 150,000, and preferably 3,000 to 100,000.
  • the photoresist of the present invention can be prepared, for example, by dissolving the acid generator (or the sulfonium salt (1)) in an organic solvent and mixing it with a photosensitive resin.
  • the photoresist of the present invention may contain one or more other components as necessary in addition to the acid generator (or the sulfonium salt (1)) and the photosensitive resin.
  • other components include organic solvents, pigments, dyes, photosensitizers, dispersants, surfactants, fillers, leveling agents, defoamers, antistatic agents, UV absorbers, pH adjusters, surface modifiers, plasticizers, drying accelerators, etc.
  • the ratio of the total content of the acid generator (or the sulfonium salt (1)) and the acid-reactive compound to the total amount of non-volatile matter contained in the photoresist is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.
  • the non-volatile matter means the residue excluding volatile components such as organic solvents, and is, for example, a component whose boiling point at atmospheric pressure exceeds 200°C.
  • the organic solvent may be any solvent capable of dissolving the photosensitive resin and imparting good coating properties to the photoresist, but it is preferable to use one having a boiling point of 200°C or less, since it allows the photoresist to be easily dried after coating.
  • Preferred organic solvents include aromatic hydrocarbons such as toluene; alcohols such as ethanol and methanol; ketones such as cyclohexanone, methyl ethyl ketone and acetone; esters such as ethyl acetate, butyl acetate and ethyl lactate; and glycol monoether monoesters such as propylene glycol monomethyl ether acetate (PGMEA). These can be used alone or in combination of two or more.
  • aromatic hydrocarbons such as toluene
  • alcohols such as ethanol and methanol
  • ketones such as cyclohexanone, methyl ethyl ketone and acetone
  • esters such as ethyl
  • the organic solvent preferably contains at least one selected from ketones, esters (particularly linear esters), and glycol monoether monoesters.
  • the photoresist of the present invention contains a sulfonium salt that has high photosensitivity to ultrashort wavelength light such as X-rays, electron beams, and EUV. Therefore, by using the photoresist of the present invention, it is possible to produce a resist film having a high-resolution fine pattern by photolithography using ultrashort wavelength light.
  • An example of a method for forming a pattern by photolithography using the photoresist includes the following steps 1 to 3.
  • Step 1 A step of forming a coating film of the photoresist on a substrate.
  • Step 2 A step of transferring a pattern by irradiating the coating film with light.
  • Step 3 A step of performing alkaline development.
  • Step 1 This step is a step of forming a coating film of the photoresist on a substrate to be etched.
  • the coating film of the photoresist can be formed by applying the photoresist to the substrate by a known method such as spin coating, curtain coating, roll coating, spray coating, screen printing, etc., and drying the applied photoresist.
  • the photoresist may be dried naturally, but since the sulfonium salt is thermally stable, it can also be dried by heating (for example, at a temperature of 50°C or higher and lower than 200°C (preferably 50°C or higher and 150°C or lower) for 1 to 5 minutes), which is easy to work with.
  • the thickness of the coating is, for example, 1 to 1000 nm.
  • Step 2 This step is a step of transferring a pattern to the coating film obtained through step 1 by irradiating the coating film with light through a photomask having a pattern, for example.
  • the light used for the light irradiation is not particularly limited as long as it can decompose the sulfonium salt contained in the coating film to generate an acid (H + X - ; X - represents a counter anion), but from the viewpoint of making the pattern finer, it is preferable to use light having an ultrashort wavelength, and the wavelength of the light is, for example, preferably 100 nm or less (e.g., 1 to 100 nm), more preferably 80 nm or less, particularly preferably 50 nm or less, most preferably 30 nm or less, and particularly preferably 20 nm or less.
  • the light include X-rays, electron beams, EUV, etc.
  • the film After light irradiation, it is preferable to heat the film at a temperature of 60 to 200°C for about 0.1 to 120 minutes, as this increases the difference in solubility in an alkaline developer between the exposed and unexposed areas.
  • Step 3 the photoresist coating film that has been subjected to step 2 is subjected to an alkali development treatment.
  • alkaline developers used in alkaline development include aqueous sodium hydroxide solutions, aqueous potassium hydroxide solutions, sodium bicarbonate solutions, and aqueous tetramethylammonium salt solutions.
  • the alkaline developer may contain methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N-methylpyrrolidone, etc.
  • the alkaline developing process is carried out by applying the alkaline developer to the coating film by a method such as dipping, showering, or spraying.
  • the temperature of the alkaline developer is, for example, 25 to 40°C.
  • the alkaline development time is determined appropriately depending on the thickness of the resist, but is, for example, about 1 to 5 minutes.
  • the photoresist of the present invention contains a sulfonium salt with a carboxyl group, and therefore the developability of the resist is improved during alkaline development, making it possible to reduce development residues. As a result, defect-free products can be manufactured with a high yield.
  • step 3 a resist film having a highly accurate fine pattern can be formed on the substrate. By etching the substrate using the resist film thus obtained, highly accurate electronic devices can be manufactured.
  • the electronic devices include, for example, display devices such as organic electroluminescence displays and liquid crystal displays; input devices such as touch panels; light-emitting devices; sensor devices; and MEMS (Micro Electro Mechanical Systems) devices such as optical scanners, optical switches, acceleration sensors, pressure sensors, gyroscopes, microchannels, and inkjet heads.
  • display devices such as organic electroluminescence displays and liquid crystal displays
  • input devices such as touch panels
  • light-emitting devices such as light-emitting devices
  • sensor devices such as MEMS (Micro Electro Mechanical Systems) devices
  • MEMS Micro Electro Mechanical Systems
  • Preparation Example 1 (Preparation of 4-pentafluorosulfanylphenylmagnesium bromide) Into a reaction vessel equipped with a reflux condenser and a dropping funnel that had been dried in a dryer and substituted with nitrogen, 0.13 g of magnesium (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 4 g of diethyl ether (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added, and 0.071 g of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise with stirring.
  • magnesium manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • diethyl ether manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • Preparation Example 2 (Preparation of 3-pentafluorosulfanylphenylmagnesium bromide) A diethyl ether solution of 3-pentafluorosulfanylphenylmagnesium bromide was obtained in the same manner as in Preparation Example 1, except that 4-bromophenylsulfur pentafluoride was changed to 3-bromophenylsulfur pentafluoride (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • Preparation Example 4 (Preparation of bis(3-pentafluorosulfanylphenyl)sulfoxide) To the diethyl ether solution of 3-pentafluorosulfanylphenylmagnesium bromide obtained in Preparation Example 2, a solution prepared by diluting 0.29 g of thionyl chloride in 0.50 g of diethyl ether was added dropwise within a range in which the temperature in the system did not exceed ⁇ 5° C. After completion of the dropwise addition, the reaction was continued at room temperature for 1 hour to complete the reaction. The obtained reaction liquid was added to 5 g of ion-exchanged water so that the temperature did not exceed 15°C, and the mixture was stirred for 1 hour.
  • Preparation Example 5 (Preparation of bis ⁇ 3,5-bis(pentafluorosulfanyl)phenyl ⁇ sulfoxide) Bis ⁇ 3,5-bis(pentafluorosulfanyl)phenyl ⁇ sulfoxide was obtained in the same manner as in Preparation Example 4, except that the diethyl ether solution of 3,5-bis(pentafluorosulfanyl)phenylmagnesium bromide obtained in Preparation Example 3 was used instead of the diethyl ether solution of 4-pentafluorosulfanylphenylmagnesium bromide obtained in Preparation Example 1.
  • Example 1 Preparation of 4-pentafluorosulfanylphenyl diphenylsulfonium trifluoromethanesulfonate
  • Example 2 (Preparation of 3-pentafluorosulfanylphenyl diphenylsulfonium trifluoromethanesulfonate)
  • Into a reaction vessel that had been dried in a dryer and substituted with nitrogen 0.20 g of diphenyl sulfoxide and 2.9 g of tetrahydrofuran were placed, and the contents were stirred and placed in an ice bath.
  • 1.6 g of trimethylsilyl trifluoromethanesulfonate was slowly added dropwise to the mixture, followed by the slowly added dropwise of the diethyl ether solution of 3-pentafluorosulfanylphenylmagnesium bromide obtained in Preparation Example 2.
  • Example 13 (Preparation of bis(3-pentafluorosulfanylphenyl)trimethylsilylmethylsulfonium bromide)
  • the same procedure as in Example 2 was repeated except that bis(3-pentafluorosulfanylphenyl)sulfoxide obtained in Preparation Example 4 was used instead of diphenyl sulfoxide, and a trimethylsilylmethylmagnesium chloride tetrahydrofuran solution was used instead of the diethyl ether solution of 3-pentafluorosulfanylphenylmagnesium bromide, to obtain 0.2 g of bis(3-pentafluorosulfanylphenyl)trimethylsilylmethylsulfonium triflate.
  • the obtained compound was dissolved in 2.5 mL of dichloromethane, and 0.13 g of benzyldimethyldodecylammonium bromide and 7.5 mL of deionized water were added thereto, followed by stirring at room temperature for 30 minutes. After removing the organic layer, the aqueous layer was washed twice with dichloromethane. After washing, the remaining aqueous layer was concentrated with an evaporator and dried in a vacuum dryer at 40° C. This gave 0.14 g of bis(3-pentafluorosulfanylphenyl)trimethylsilylmethylsulfonium bromide.
  • Example 14 (Synthesis of S-3,5-bis(pentafluorosulfanyl)phenylbenzothiophenium trifluoromethanesulfonate) To a solution of benzothiophene in chloroform, 3,5-bis(pentafluorosulfanyl)phenylmesityliodonium trifluoromethanesulfonate and copper(II) acetate were added. The mixture was refluxed for 8 hours, then filtered and washed with 1% dilute hydrochloric acid and deionized water three times each. After washing, the organic layer was concentrated and the resulting solid was dried in a vacuum dryer to obtain S-3,5-bis(pentafluorosulfanyl)phenylbenzothiophenium trifluoromethanesulfonate.
  • Evaluation criteria Excellent ( ⁇ ): Sulfonium salt concentration is 10% by weight or more; Good ( ⁇ ): Sulfonium salt concentration is 5% by weight or more but less than 10% by weight; Acceptable ( ⁇ ): Sulfonium salt concentration is 3% by weight or more but less than 5% by weight; Unacceptable ( ⁇ ): Sulfonium salt concentration is less than 3% by weight.
  • the sulfonium salts of the Examples and Comparative Examples were mixed with a positive photosensitive resin (copolymer of polyhydroxystyrene and t-butoxyacrylate) in an amount of 20 times by weight, and dissolved in PGMEA so that the molar concentration of the sulfonium salt was 2.0 mM to prepare photoresists.
  • a positive photosensitive resin copolymer of polyhydroxystyrene and t-butoxyacrylate
  • PGMEA hexamethyldisilazane
  • the resulting coating film was placed in BL-3 at the NewSUBARU Synchrotron Radiation Facility of the University of Hyogo, and irradiated with 13.5 nm synchrotron radiation.
  • the sample after the light irradiation was heated at 110° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and rinsed with running water for 30 seconds. After development and rinsing, the sample was observed under a microscope to determine the minimum exposure dose (Eth) at which the resist film was completely removed.
  • l, m, n, and o each represent the number of repeating units shown in parentheses and are numbers of 1 or more.
  • the sulfonium salt of the present invention has a higher sensitivity to 13.5 nm radiation than a sulfonium salt not containing a SF5 group. It can also be seen that the solubility in a solvent is good. Since the sulfonium salt of the present invention has both of the above properties, it is suitable for photoresist applications (especially photoresist applications using ultrashort wavelength light).
  • X - represents a monovalent counter anion.
  • At least one sulfonium salt selected from the group consisting of compounds represented by the following formulas (1-1) to (1-4): (In the formula, n represents an integer of 1 to 5.
  • X- represents a monovalent counter anion.
  • Ring Z represents a heterocycle containing a sulfur atom. One or more aromatic hydrocarbon rings may be condensed to the heterocycle.
  • a substituent other than the SF5 group may be bonded to the benzene ring shown in the formula.
  • the benzene ring shown in the formula may have a substituent other than the SF5 group bonded thereto.
  • the sulfonium salt according to any one of [1] to [4] which has a solubility in propylene glycol monomethyl ether acetate at 25° C. of 2% by weight or more.
  • An acid generator comprising the sulfonium salt according to any one of [1] to [5].
  • the acid generator according to [6] which is an acid generator for use with extreme ultraviolet rays or an acid generator for use with electron beams.
  • a photoresist comprising the sulfonium salt according to any one of [1] to [5] and an acid-reactive compound.
  • a photoresist comprising the sulfonium salt according to any one of [1] to [5] and an acid-reactive compound, wherein the content of the sulfonium salt is 0.05 to 7 wt % of the content of the acid-reactive compound.
  • a photoresist comprising the acid generator according to [6] or [7] and an acid-reactive compound.
  • a photoresist comprising the acid generator according to [6] or [7] and an acid-reactive compound, wherein the content of the acid generator is 0.05 to 7 wt % of the content of the acid-reactive compound.
  • [14] Use of a photoresist containing the sulfonium salt according to any one of [1] to [5] and an acid-reactive compound as a photoresist for use in photolithography using light having a wavelength of 20 nm or less.
  • a method for producing a photoresist comprising mixing the sulfonium salt according to any one of [1] to [5] with an acid-reactive compound.
  • a method for producing a photoresist for use in photolithography using extreme ultraviolet rays or electron beams comprising mixing the sulfonium salt according to any one of [1] to [5] with an acid-reactive compound.
  • a method for producing a photoresist for use in photolithography using a light beam having a wavelength of 20 nm or less comprising mixing the sulfonium salt according to any one of [1] to [5] with an acid-reactive compound.
  • the sulfonium salt represented by formula (1) of the present application has excellent sensitivity to light having a wavelength of 20 nm or less, and can easily decompose to generate acid when irradiated with light having said wavelength. Therefore, by performing photolithography using light having a wavelength of 20 nm or less with a photoresist containing the sulfonium salt, fine patterns can be formed with high precision, and it is possible to realize large-capacity, miniaturized electronic devices.

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JP7805544B1 (ja) * 2025-07-31 2026-01-23 信越化学工業株式会社 オニウム塩、光酸発生剤、化学増幅レジスト組成物及びパターン形成方法
JP7813423B1 (ja) * 2025-07-31 2026-02-12 信越化学工業株式会社 オニウム塩、光酸発生剤、化学増幅レジスト組成物及びパターン形成方法

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