Classifications

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  • 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
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
  • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
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  • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
  • C07C381/02—Thiosulfates
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  • 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
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/70—Sulfur atoms
  • C07D213/71—Sulfur atoms to which a second hetero atom is attached
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
  • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
  • C07D221/04—Ortho- or peri-condensed ring systems
  • C07D221/06—Ring systems of three rings
  • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/32—Oxygen atoms
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
  • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
  • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
  • C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
• • 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
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • 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
• • 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
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • 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
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • 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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

• the present invention relates to a novel sulfonate, a novel oxime sulfonate, a novel imide sulfonate, a novel amido sulfonate, an acid generator containing the novel compound, and a photoresist containing the acid generator.
• acid generators Compounds that decompose when exposed to light to generate acid (so-called acid generators) are used in a variety of fields. For example, in the field of semiconductor resists, they are used to change the solubility in the developer of chemically amplified resists used in photolithography. Also, in the fields of paints, adhesives, casting materials for various parts, sealing materials, etc., they are used to initiate cationic polymerization of cationic curable compounds and cause them to harden.
• Known examples of the acid generator include compounds represented by the following formulae (X-1) and (X-2) (see Patent Documents 1 and 2). These compounds have a perfluoromethyl group or a perfluoromethylene group at the ⁇ -position of the sulfonic acid group, and therefore can generate sulfonic acid with high acid strength.
• an object of the present invention is to provide a novel compound which does not contain a perfluoromethyl group or a perfluoromethylene group and which is easily decomposed by irradiation with light to generate a sulfonic acid having high acid strength.
• Another object of the present application is to provide an acid generator containing the novel compound.
• Another object of the present invention is to provide a photoresist containing the acid generator.
• Another object of the present invention is to provide a method for manufacturing an electronic device or an optical device using the photoresist.
• the present invention provides a compound which is a salt of an anion represented by the following formula (a-1) or (a-2) and a cation:
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L represents a single bond or a linking group
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the present invention also provides a compound represented by the following formula (b-1) or (b-2):
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L represents a single bond or a linking group
• R2 and R3 may be the same or different and each represents an organic group
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the present invention also provides a compound represented by the following formula (c-1) or (c-2):
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L and L' may be the same or different and represent a single bond or a linking group
• R4 and R5 may be the same or different and represent a hydrocarbon group which may have a substituent
• R4 and R5 may be linked to each other to form a ring together with the adjacent carbon atom
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the present invention also provides a compound represented by the following formula (d-1) or (d-2):
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent.
• L represents a single bond or a linking group.
• R6 and R7 may be the same or different and each represents a hydrocarbon group which may have a substituent.
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and n represents 0 or 1.
• the present invention provides an acid generator containing the above compound.
• the present invention also provides a photoresist containing the acid generator and an acid-reactive compound.
• the present invention also provides a method for manufacturing an electronic device or an optical device, which includes a step of forming a pattern by photolithography using the photoresist.
• the compounds of the present invention are compounds which are salts of anions represented by the above formula (a-1) or (a-2) and cations, compounds represented by the above formula (b-1) or (b-2), compounds represented by the above formula (c-1) or (c-2), and compounds represented by the above formula (d-1) or (d-2), which rapidly decompose when irradiated with light to generate sulfonic acids represented by the below-described formula (A-1) or (A-2).
• the compound of the present invention can generate a sulfonic acid having an acid strength equal to or greater than that of an acid generated by a conventional acid generator having a perfluoromethyl group or a perfluoromethylene group.
• a resist film having a high-resolution pattern with good accuracy can be manufactured.
• etching e.g., dry etching using reactive gas or plasma
• a semiconductor device having a high-resolution pattern e.g., a wiring pattern, a circuit pattern, etc.
• the sulfonate of the present invention is a compound which is a salt of an anion represented by the following formula (a-1) or (a-2) and a cation.
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L represents a single bond or a linking group
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the linking group in L is a divalent group having one or more atoms, and examples thereof include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), a sulfonyl group (-SO 2 -), an ester bond (-COO- or -OCO-), an amide bond (-CONH-), a carbonate bond (-OCOO-), and groups in which multiple of these are linked together.
• the divalent hydrocarbon group and the divalent heterocyclic group may have an electron-withdrawing group as a substituent (e.g., a carboxyl group, a C1-5 alkyl ester group, a nitro group, a halogen atom, a C1-14 acyl group, a cyano group, a tosyl group, a mesyl group, etc.)
• a substituent e.g., a carboxyl group, a C1-5 alkyl ester group, a nitro group, a halogen atom, a C1-14 acyl group, a cyano group, a tosyl group, a mesyl group, etc.
• L is preferably a group containing at least an ester bond (-COO- or -OCO-).
• the anion represented by the formula (a-1) is preferably an anion represented by the following formulas (a-1-1) and (a-1-2).
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L" represents a single bond or a linking group
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the linking group in L" may be any of the divalent groups listed as the linking group in L other than an ester bond (-COO- and -OCO-). Of these, L" is preferably a single bond, a divalent hydrocarbon group, or a divalent heterocyclic group.
• R 1 represents a (monovalent) hydrocarbon group or a (monovalent) heterocyclic group which may have a substituent.
• the monovalent hydrocarbon group includes a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and monovalent groups formed by combining these groups.
• the monovalent aliphatic hydrocarbon group includes a monovalent saturated aliphatic hydrocarbon group and a monovalent unsaturated aliphatic hydrocarbon group.
• the monovalent alicyclic hydrocarbon group is preferably a C 3-20 alicyclic hydrocarbon group, and examples thereof include cycloalkyl groups having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members), such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group; cycloalkenyl groups having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members), such as a cyclopentenyl group or 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, or a tetracyclo[4.4.0.1 2,5 .1 7,10 ]
• a C 6-14 (particularly a C 6-10 ) aromatic hydrocarbon group is preferred, and examples thereof include a phenyl group and a naphthyl group.
• Examples of the monovalent group in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are bonded include C 7-18 aralkyl groups such as benzyl group and phenylethyl group.
• ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group may be condensed with an aromatic or non-aromatic heterocycle.
• Examples of the substituent that the hydrocarbon group may have include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (for example, a C 1-4 alkoxy group, a C 6-10 aryloxy group, a C 7-16 aralkyloxy group, a C 1-4 acyloxy group, etc.), a thio group, a substituted thio group (for example, a C 1-6 alkylthio group or a C 6-10 arylthio group which may have a substituent, and examples of the substituent include a hydroxyl group, a cyano group, an alkoxy group, a hydroxyalkoxy group, a sulfo group, a carboxyl group, etc.), a carboxyl group, a substituted oxycarbonyl group (for example, a C 1-4 alkoxycarbonyl group, a C 6-10 aryloxycarbonyl group, a C 7-16 a
• hydrocarbon group examples include a C 7-14 aromatic acyl group), a substituted or unsubstituted carbamoyl group (for example, a C 1-4 alkyl-substituted carbamoyl group such as carbamoyl or methylcarbamoyl, and a C 6-10 aryl-substituted carbamoyl group such as a phenylcarbamoyl group), a cyano group, a nitro group, a sulfo group, a heterocyclic group, etc.
• the hydrocarbon group may have a group containing a perfluoromethyl group or a perfluoromethylene group (for example, a C 1-10 haloalkyl group, etc.).
• 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.
• the heterocycle constituting the heterocyclic group 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,
• Examples of the substituent that the heterocyclic group may have include, in addition to the substituents that the hydrocarbon group may have, alkyl groups (for example, C1-4 alkyl groups such as methyl group, ethyl group, etc.), alkenyl groups (for example, C2-4 alkenyl groups such as vinyl group, allyl group, 1-butenyl group, etc.), alkynyl groups (for example, C2-4 alkynyl groups such as ethynyl group, propynyl group, etc.), C3-8 cycloalkyl groups, and aryl groups (for example, C6-15 aryl groups such as phenyl group, naphthyl group, biphenyl group, etc.).
• alkyl groups for example, C1-4 alkyl groups such as methyl group, ethyl group, etc.
• alkenyl groups for example, C2-4 alkenyl groups such as vinyl group, allyl group, 1-butenyl group, etc.
• R 1 is preferably a group having a molecular weight of 100 or more (e.g., 100 to 200, preferably 100 to 150), since this has the effect of suppressing the diffusibility of the generated sulfonic acid and improving the pattern resolution when used in a photoresist.
• the divalent hydrocarbon group may be a group obtained by removing one hydrogen atom from the structural formula of the monovalent hydrocarbon group.
• preferred are, for example, C1-5 alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene; C3-6 cycloalkylene groups such as cyclopentylene and cyclohexylene; and C6-10 arylene groups such as phenylene, phenylenebis(methylene), biphenylene, and naphthylene.
• the divalent heterocyclic group may be a group in which two hydrogen atoms have been removed from the structural formula of the heterocycle.
• groups in which two hydrogen atoms have been removed from the structural formula of a heterocycle containing a nitrogen atom as a heteroatom such as a pyridylene group or a quinolylene group, are preferred.
• R 10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group.
• the aromatic hydrocarbon group in R10 is a monovalent aromatic hydrocarbon group, preferably a C6-14 (particularly, a C6-10 ) aromatic hydrocarbon group, such as a phenyl group or a naphthyl group.
• the aromatic hydrocarbon group may have a substituent. Examples of the substituent include the same examples as the substituents that the hydrocarbon group may have (e.g., a halogen atom, etc.).
• the aromatic heterocyclic group in R 10 is a monovalent aromatic heterocyclic group, which is a group obtained by removing one hydrogen atom from the structural formula of an aromatic heterocyclic ring.
• the aromatic heterocyclic ring include 5-membered rings such as a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a furan ring, and a thiophene ring; 6-membered rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring; and condensed rings such as a quinoline ring and a benzofuran ring.
• a fluorine atom or an aromatic hydrocarbon group is preferable, and a fluorine atom is particularly preferable, because it has excellent photosensitivity and generates a sulfonic acid having high acid strength, thereby improving the resolution of the photoresist.
• n 0 or 1.
• anion represented by formula (a-1) an anion represented by the following formula (a-1') is preferred, and an anion represented by the following formula (a-1'-1) or (a-1'-2) is particularly preferred.
• R 1 , L and L" are the same as defined above.
• an anion represented by formula (a-1) is preferable, and an anion represented by the following formula (a-1"-1) or (a-1"-2) is particularly preferable.
• L and L" are the same as defined above.
• ring Z1 represents an alicyclic hydrocarbon, an aromatic hydrocarbon ring, or an aromatic heterocycle
• ring Z2 represents an aromatic hydrocarbon ring or an aromatic heterocycle
• ring Z1 is preferably an alicyclic hydrocarbon, and a C3-20 alicyclic hydrocarbon group is particularly preferred.
• ring Z2 is preferably an aromatic hydrocarbon ring, and particularly preferably a benzene ring.
• R 11 and R 12 are substituents bonded to rings Z 1 and Z 2.
• substituents include the same as those of the hydrocarbon group and heterocyclic group in R 1 and R 10 that may have. Of these, halogen atoms are preferred as the substituents.
• s and t may be the same or different and represent an integer of 0 to 5. Of these, s is preferably 0 or 1, and 1 is particularly preferred. Of these, t is preferably 0 or 1, and 0 is particularly preferred.
• an anion represented by the following formula (a-2) is preferable, and an anion represented by the following formula (a-2'-1) is particularly preferable.
• R 1 , L and L" are the same as defined above.
• an anion represented by the following formula (a-2) is preferable, and an anion represented by the following formula (a-2′′-1) is particularly preferable.
• L is the same as defined above.
• ring Z3 represents an alicyclic hydrocarbon, an aromatic hydrocarbon ring, or an aromatic heterocycle. Of these, ring Z3 is preferably an aromatic hydrocarbon ring or an aromatic heterocycle, and more preferably an aromatic hydrocarbon ring.
• R13 is a substituent bonded to ring Z3 .
• the substituent include the same as those of the hydrocarbon group or heterocyclic group in R1 or R10 that may have.
• the substituent is preferably a halogen atom, a nitro group, or a C1-4 acyloxy group.
• u represents an integer of 0 to 5. Among these, u is preferably 0 or 1, and 1 is particularly preferable.
• the cation constituting the sulfonate is not particularly limited, and may be a monovalent cation or a polyvalent cation having a valence of two or more. In the present invention, monovalent or divalent cations are preferred, and monovalent cations are particularly preferred.
• the cations include inorganic cations and organic cations.
• the sulfonate is a salt of an anion represented by the above formula (a-1) or (a-2) and an inorganic cation, it is called an inorganic sulfonate.
• the inorganic sulfonate can be suitably used, for example, as a raw material for organic sulfonate.
• the sulfonate is a salt of an anion represented by the above formula (a-1) or (a-2) and an organic cation, it is called an organic sulfonate.
• the above organic sulfonate can be suitably used as an acid generator.
• Examples of the inorganic cation include alkali metal ions such as sodium ions, potassium ions, and lithium ions; and alkaline earth metal ions such as calcium ions, magnesium ions, and barium ions.
• organic cation examples include onium cations such as sulfonium ions, iodonium ions, selenium ions, ammonium ions, and phosphonium ions.
• sulfonium ion examples include the sulfonium ion represented by the following formula (s).
• R11 and R12 are the same or different and represent a monovalent hydrocarbon group, a monovalent heterocyclic group, or a monovalent group formed by bonding two or more of the above groups via a single bond or a linking group. R11 and R12 may be bonded to each other to form a ring together with the adjacent S + .
• Examples of the monovalent hydrocarbon group and the monovalent heterocyclic group in R11 and R12 include the same examples as the hydrocarbon group and the heterocyclic group in R1 .
• the above groups may have a substituent, and examples of the above substituents include the same examples as the substituents that the hydrocarbon group and the heterocyclic group in R1 may have.
• the ring that may be formed by R 11 and R 12 bonding to each other and the adjacent S + is a heterocycle containing at least S + described in the formula.
• the heterocycle may contain a heteroatom (e.g., oxygen atom, nitrogen atom, sulfur atom, etc.) in addition to the S + .
• the heterocycle is, for example, a 5- to 6-membered heterocycle, and includes aromatic heterocycles and non-aromatic heterocycles.
• an aromatic hydrocarbon ring may be condensed to the heterocycle.
• the benzene ring shown in the above formula may have an alkyl group (e.g., a C1-5 alkyl group) or an aryl group (e.g., a C6-15 aryl group) bonded thereto.
• An aromatic hydrocarbon ring may be condensed with the benzene ring.
• a substituent may be bonded to the benzene ring, the alkyl group or aryl group bonded to the benzene ring, or the condensed ring of the benzene ring and the aromatic hydrocarbon ring.
• substituents examples include a hydroxyl group, an SF5 group, a halogen atom, a silyl group, a substituted oxy group (e.g., a C1-4 alkoxy group, a C6-15 aryloxy group, a C7-16 aralkyloxy group, a C1-4 acyloxy group, etc.), a substituted thio group (e.g., a C1-6 alkylthio group, a C6-15 arylthio group), etc.
• a substituted oxy group e.g., a C1-4 alkoxy group, a C6-15 aryloxy group, a C7-16 aralkyloxy group, a C1-4 acyloxy group, etc.
• substituted thio group e.g., a C1-6 alkylthio group, a C6-15 arylthio group
• the sulfonium ion may also be bonded to an acid-reactive compound, which will be described later.
• the sulfonium ion may contain an acid-reactive compound, which will be described later, within its structure.
• sulfonium ion represented by the above formula (s) a triarylsulfonium ion represented by the following formula (s-1) or a sulfonium ion represented by the following formula (s-2) is preferable.
• the ring Z in the above formula (s-2) is a heterocycle containing at least a sulfur atom as a heteroatom.
• the heterocycle may contain other heteroatoms (e.g., oxygen atoms, nitrogen atoms, sulfur atoms, etc.) in addition to the sulfur atom.
• the heterocycle may be, for example, a 5- or 6-membered heterocycle, and includes aromatic heterocycles and non-aromatic heterocycles.
• an aromatic hydrocarbon ring may be condensed to the heterocycle.
• iodonium ion examples include an iodonium ion represented by the following formula (i).
• the benzene ring shown in the above formula may have an alkyl group (e.g., a C1-5 alkyl group) or an aryl group (e.g., a C6-15 aryl group) bonded thereto.
• An aromatic hydrocarbon ring may be condensed with the benzene ring.
• a substituent may be bonded to the benzene ring, the alkyl group or aryl group bonded to the benzene ring, or the condensed ring of the benzene ring and the aromatic hydrocarbon ring.
• substituents examples include a hydroxyl group, an SF5 group, a halogen atom, a silyl group, a substituted oxy group (e.g., a C1-4 alkoxy group, a C6-15 aryloxy group, a C7-16 aralkyloxy group, a C1-4 acyloxy group, etc.), a substituted thio group (e.g., a C1-6 alkylthio group, a C6-15 arylthio group), etc.
• a substituted oxy group e.g., a C1-4 alkoxy group, a C6-15 aryloxy group, a C7-16 aralkyloxy group, a C1-4 acyloxy group, etc.
• substituted thio group e.g., a C1-6 alkylthio group, a C6-15 arylthio group
• iodonium ion examples include aryl iodonium ions such as p-cumenyl (p-tolyl) iodonium ion, diphenyl iodonium ion, di-p-tolyliodonium ion, bis(4-tert-butylphenyl) iodonium ion, bis(4-dodecylphenyl) iodonium ion, bis(4-methoxyphenyl) iodonium ion, and (4-octyloxyphenyl) phenyl iodonium ion.
• aryl iodonium ions such as p-cumenyl (p-tolyl) iodonium ion, diphenyl iodonium ion, di-p-tolyliodonium ion, bis(4-tert-butylphenyl) iodonium ion, bis
• selenium ion examples include arylselenium ions such as triphenylselenium ion, tri-p-tolylselenium ion, tri-o-tolylselenium ion, tris(4-methoxyphenyl)selenium ion, 1-naphthyldiphenylselenium ion, tris(4-fluorophenyl)selenium ion, tri-1-naphthylselenium ion, and tri-2-naphthylselenium ion.
• arylselenium ions such as triphenylselenium ion, tri-p-tolylselenium ion, tri-o-tolylselenium ion, tris(4-methoxyphenyl)selenium ion, 1-naphthyldiphenylselenium ion, tri
• ammonium ion examples include quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tetraoctylammonium ion, trimethylhexylammonium ion, and trimethyloctylammonium ion.
• quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammoni
• the phosphonium ions include, for example, tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacy
• a sulfonium ion or an iodonium ion is preferable, and an arylsulfonium ion or an aryl iodonium ion is particularly preferable.
• the sulfonate quickly decomposes upon irradiation with light to generate sulfonic acid.
• the sulfonate contains the anion represented by formula (a-1), it generates a sulfonic acid represented by the following formula (A-1).
• the sulfonate contains the anion represented by the formula (a-2), it generates a sulfonic acid represented by the following formula (A-2).
• the sulfonic acid has a SF 4 R 10 group or a SF 4 group and therefore exhibits high acid strength. (wherein R 1 , L, R 10 and n are the same as defined above).
• the gas-phase acidity ⁇ G (Kcal/mol) of the sulfonic acid is, for example, 300 or less, preferably 290 or less, particularly preferably 285 or less, particularly preferably 280 or less, and most preferably 275 or less.
• the lower limit of the gas-phase acidity ⁇ G (Kcal/mol) is, for example, 250, particularly 255, and particularly 260.
• gas-phase acidity refers to the acidity in the gas phase, and is defined by IUPAC (International Union of Pure and Applied Chemistry) as the Gibbs energy change associated with acid dissociation.
• the gas-phase acidity can be calculated using known calculation software. The smaller the gas-phase acidity value, the greater the acid strength.
• the oxime sulfonate of the present invention is a compound represented by the following formula (b-1) or (b-2).
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L represents a single bond or a linking group
• R2 and R3 may be the same or different and each represents an organic group
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the oxime sulfonate is rapidly decomposed by irradiation with light to generate sulfonic acid.
• the oxime sulfonate is a compound represented by the formula (b-1)
• it generates a sulfonic acid represented by the formula (A-1).
• the oxime sulfonate is a compound represented by the formula (b-2)
• it generates a sulfonic acid represented by the formula (A-2).
• the sulfonic acid has a SF 4 R 10 group or a SF 4 group and therefore exhibits high acid strength.
• R 1 and L in the above formulae (b-1) and (b-2) are the same as R 1 and L in the above formulae (a-1) and (a-2).
• Examples of the organic group in R2 and R3 include a hydrocarbon group (R), an RO group, an RCO group, a ROCO group, an RS group (wherein each of the R groups represents a hydrocarbon group), a carboxyl group, a cyano group, an isocyanate group, a carbamoyl group, an isothiocyanate group, a substituted amino group, a heterocyclic group, and groups in which two or more of these are bonded via a single bond.
• the organic group in R 2 and R 3 may also be a group in which two or more hydrocarbon groups (R) are bonded via a divalent group represented by the following formula (L-1). (wherein R 1 and L are the same as defined above. The bond marked with a wavy line in the formula bonds to the hydrocarbon group in R 2 or R 3 .
• R 10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and n represents 0 or 1.
• Examples of the hydrocarbon group (R) and heterocyclic group include the same as the hydrocarbon group and heterocyclic group in R 1.
• the hydrocarbon groups in R 2 and R 3 may have a substituent, and examples of the substituent include the same as the substituents that the hydrocarbon group in R 1 may have.
• R2 and R3 is preferably a hydrocarbon group which may have a substituent.
• the other of R2 and R3 is preferably an electron-withdrawing group, particularly preferably a group selected from a cyano group, an RCO group (R represents a hydrocarbon group), an isocyanate group, a carbamoyl group, and an isothiocyanate group, and is particularly preferably a cyano group.
• the imidosulfonate of the present invention is a compound represented by the following formula (c-1) or (c-2).
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent
• L and L' may be the same or different and represent a single bond or a linking group
• R4 and R5 may be the same or different and represent a hydrocarbon group which may have a substituent
• R4 and R5 may be linked to each other to form a ring together with the adjacent carbon atom
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• n represents 0 or 1.
• the imide sulfonate is rapidly decomposed by irradiation with light to generate sulfonic acid.
• the imidosulfonate is a compound represented by the formula (c-1)
• it generates a sulfonic acid represented by the formula (A-1).
• the imide sulfonate is a compound represented by the formula (c-2)
• it generates a sulfonic acid represented by the formula (A-2).
• the sulfonic acid has a SF 4 R 10 group or a SF 4 group and therefore exhibits high acid strength.
• R 1 , L, R 10 and n in the above formulae (c-1) and (c-2) are the same as R 1 , L, R 10 and n in the above formulae (a-1) and (a-2).
• R1 is preferably a monovalent alicyclic hydrocarbon group or a monovalent aromatic heterocyclic group, since it has excellent photosensitivity and generates a sulfonic acid having high acid strength, thereby obtaining the effect of improving the resolution of the photoresist.
• a fluorine atom or an aromatic heterocyclic group is preferable, and a fluorine atom is particularly preferable, because it has excellent photosensitivity and generates a sulfonic acid having high acid strength, thereby improving the resolution of the photoresist.
• the linking group in L' can be the same as the linking group in L.
• the L' a single bond is preferred, since it has excellent photosensitivity, generates a sulfonic acid with high acid strength, and has the effect of improving the resolution of the photoresist.
• Examples of the hydrocarbon group in R4 and R5 include the same as the monovalent hydrocarbon group in R1 .
• Examples of the substituent that the hydrocarbon group in R4 and R5 may have include the same as the substituent that the monovalent hydrocarbon group in R1 may have.
• Examples of the ring that R 4 and R 5 may combine with each other to form together with the adjacent carbon atom include an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocycle.
• the alicyclic hydrocarbon is preferably a C3-20 alicyclic hydrocarbon group, and examples thereof include a C3-12 cycloalkane ring such as cyclohexane, bicyclohexane, etc.; a C3-12 cycloalkene ring such as cyclohexene, etc.; and a bridged ring such as norbornane, norbornene, adamantane, tricyclo[ 5.2.1.02,6 ]decane, tricyclo[ 4.3.1.12,5 ]undecane, tetracyclo [ 4.4.0.12,5.17,10 ]dodecane, perhydro-1,4-methano-5,8-methanonaphthalene, etc.
• a C3-12 cycloalkane ring such as cyclohexane, bicyclohexane, etc.
• a C3-12 cycloalkene ring such as cyclohexene,
• aromatic hydrocarbon ring examples include benzene, naphthalene, and anthracene.
• the heterocycle may be the same as the heterocycle forming the heterocyclic group.
• amidosulfonate The amidosulfonate of the present invention is a compound represented by the following formula (d-1) or (d-2).
• R1 represents a hydrocarbon group or a heterocyclic group which may have a substituent.
• L represents a single bond or a linking group.
• R6 and R7 may be the same or different and each represents a hydrocarbon group which may have a substituent.
• R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and n represents 0 or 1.
• the amidosulfonate is rapidly decomposed by irradiation with light to generate sulfonic acid.
• the amidosulfonate is a compound represented by the formula (d-1)
• it generates a sulfonic acid represented by the formula (A-1).
• the imide sulfonate is a compound represented by the formula (d-2)
• it generates a sulfonic acid represented by the formula (A-2).
• the sulfonic acid has a SF 4 R 10 group or a SF 4 group and therefore exhibits high acid strength.
• R 1 , L, R 10 and n in the above formulae (d-1) and (d-2) are the same as R 1 , L, R 10 and n in the above formulae (a-1) and (a-2).
• R1 is preferably a monovalent alicyclic hydrocarbon group or a monovalent aromatic heterocyclic group, since it has excellent photosensitivity and generates a sulfonic acid having high acid strength, thereby obtaining the effect of improving the resolution of the photoresist.
• R 10 is preferably a fluorine atom, since it has excellent photosensitivity and generates a sulfonic acid having high acid strength, thereby obtaining the effect of improving the resolution of the photoresist.
• Examples of the hydrocarbon group in R6 and R7 include the same as the monovalent hydrocarbon group in R1 .
• Examples of the substituent that the hydrocarbon group in R6 and R7 may have include the same as the substituent that the monovalent hydrocarbon group in R1 may have.
• the acid generator of the present invention contains the above-mentioned sulfonate, oxime sulfonate, imide sulfonate, or amide sulfonate, which is rapidly decomposed by irradiation with light to generate a sulfonic acid.
• the acid generator has excellent solubility in a solvent (e.g., PGMEA), and the amount of the acid generator (or the sulfonate, or the oxime sulfonate, or the imide sulfonate, or the amide sulfonate) that dissolves in 100 parts by weight of PGMEA at room temperature and normal pressure is, for example, 1 part by weight or more, preferably 5 parts by weight or more, and particularly preferably 10 parts by weight or more.
• the upper limit is, for example, 30 parts by weight.
• the acid generator has excellent sensitivity to light, and when irradiated with light, it rapidly generates sulfonic acid.
• the wavelength of the light is, for example, 1 to 1000 nm. Examples of the light include infrared light, visible light, ultraviolet light, X-rays, electron beams, and EUV (Extreme Ultraviolet).
• the acid generator has the above-mentioned properties, it can be suitably used as an acid generator for photoresists (e.g., chemically amplified resists) and as a cationic polymerization initiator for cationic polymerizable compounds.
• photoresists e.g., chemically amplified resists
• cationic polymerization initiator for cationic polymerizable compounds.
• the photoresist of the present invention comprises the acid generator and an acid-reactive compound.
• the acid generator and the acid-reactive compound may be contained in the photoresist as separate compounds, or the acid-reactive compound may be incorporated into the acid generator and contained in the photoresist in an integrated state.
• the content of the acid generator 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 content of the acid-reactive compound (the total amount when two or more types are contained).
• the content of the acid generator is 0.001% by weight or more of the content 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 content of the acid-reactive compound, the effect of improving the resolution of the photoresist can be obtained.
• the content ratio of the acid generator and the acid-reactive compound in the photoresist is preferably in the same range as when the acid generator and the acid-reactive compound are each contained 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 the following 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 in an organic solvent and mixing this 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 and 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 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 light rays with wavelengths such as g-line (436 nm), h-line (405 nm), i-line (365 nm), excimer lasers such as KrF, ArF, and F2 , ultraviolet rays, X-rays, electron beams, and EUV. Therefore, by using the photoresist of the present invention, a resist film having a high-resolution fine pattern can be produced by photolithography using light rays with the above wavelengths.
• 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 130°C 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 a light beam with a short wavelength, and the wavelength of the light beam is, for example, preferably 450 nm or less (e.g., 1 to 450 nm), more preferably 400 nm or less, even more preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 30 nm or less.
• the wavelength of the light beam is, for example, preferably 450 nm or less (e.g., 1 to 450 nm), more preferably 400 nm or less, even more preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 30 nm or less.
• Examples of the light beam include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), excimer lasers such as KrF, ArF, and F2 , ultraviolet rays, X-rays, electron beams, EUV, and the like.
• the film After 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 alkaline 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 photoresist coating, but is, for example, about 1 to 5 minutes.
• the photoresist of the present invention contains a sulfonium salt with a carboxyl group as described above, the developability of the resist is improved during alkaline development, and development residues can be reduced. 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 or optical 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
• the optical devices include, for example, optical waveguides, metalenses, semiconductor lasers, etc.
• the cationic polymerization initiator of the present invention contains the above-mentioned sulfonate, the above-mentioned oxime sulfonate, the above-mentioned imide sulfonate, or the above-mentioned amide sulfonate, which is rapidly decomposed by irradiation with light to generate sulfonic acid.
• the cationic polymerization initiator has excellent solubility in a solvent (e.g., PGMEA), and the amount of the cationic polymerization initiator (or the sulfonate, or the oxime sulfonate, or the imide sulfonate, or the amide sulfonate) that dissolves in 100 parts by weight of PGMEA at room temperature and normal pressure is, for example, 1 part by weight or more, preferably 5 parts by weight or more, and particularly preferably 10 parts by weight or more. The upper limit is, for example, 30 parts by weight.
• a solvent e.g., PGMEA
• the amount of the cationic polymerization initiator (or the sulfonate, or the oxime sulfonate, or the imide sulfonate, or the amide sulfonate) that dissolves in 100 parts by weight of PGMEA at room temperature and normal pressure is, for example, 1 part by weight or more,
• the cationic polymerization initiator has excellent sensitivity to light rays, and when irradiated with the light rays, it rapidly generates sulfonic acid.
• the wavelength of the light rays is, for example, 1 to 1000 nm.
• the light rays include, for example, g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), excimer lasers such as KrF, ArF, and F2 , ultraviolet rays, infrared rays, visible light, ultraviolet rays, X-rays, electron beams, EUV, and the like.
• the curable composition of the present invention contains the cationic polymerization initiator and a cationic polymerizable compound as a resin component.
• the cationic polymerization initiator and the cationic polymerizable compound may each be contained alone or in combination of two or more kinds.
• the content of the cationic polymerization initiator is, for example, 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the cationic polymerizable compound.
• the cationic polymerizable compound is a compound having one or more cationic polymerizable groups selected from an epoxy group, an oxetanyl group, a vinyl ether group, etc.
• the epoxy group is a group containing a three-membered cyclic ether skeleton
• the oxetanyl group is a group containing a four-membered cyclic ether skeleton.
• epoxy compounds include epoxy-modified siloxane compounds, alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like.
• Epoxy-modified siloxane compound examples include epoxy-modified silicone and epoxy-modified polyorganosilsesquioxane.
• the alicyclic epoxy compound may be a known or commonly used compound having one or more alicyclic rings and one or more epoxy groups in the molecule, and is not particularly limited.
• Examples of the compound (1) having an alicyclic epoxy group include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy Examples include bis(3,4-epoxycyclohexylmethyl)-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane metadioxane, bis(3,4-epoxycyclohexy
• Examples of the compound (2) having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, compounds obtained by hydrogenating bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl] Examples of such compounds include hydrogenated bisphenol F type epoxy compounds such as bis[3,5-dimethyl-4-(2,3-epoxypropoxy
• aromatic epoxy compounds examples include epi-bis-type glycidyl ether type epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high molecular weight epi-bis-type glycidyl ether type epoxy resins obtained by further addition reaction of these epi-bis-type glycidyl ether type epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol, etc.]; novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols (e.g., phenol F, bisphenol S, etc.) with aldehydes (e.g., formaldehyde,
• aliphatic epoxy compound examples include glycidyl ethers of alcohols not having a q-valent cyclic structure (q is a natural number); glycidyl esters of monovalent or polyvalent carboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized products of oils and fats having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxidized products of polyolefins (including polyalkadienes), such as epoxidized polybutadiene.
• glycidyl esters of monovalent or polyvalent carboxylic acids e.g., acetic
• Examples of the q-valent alcohol not having a cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.
• the q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate poly
• oxetane compounds examples include 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and biphenyl.
• vinyl ether compounds examples include aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 2-hydroxybutyl vinyl ether; and polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether and triethylene glycol divinyl ether.
• aryl vinyl ethers such as phenyl vinyl ether
• alkyl vinyl ethers such as n-butyl vinyl ether and n
• the curable composition may contain one or more other components in addition to the above components, as necessary.
• other components include sensitizers, sensitization assistants, antioxidants, stabilizers, surfactants, solvents, rheology control agents, leveling agents, silane coupling agents, fillers, conductive particles, polymerization inhibitors, light stabilizers, plasticizers, defoamers, foaming agents, UV absorbers, tackifiers, curing retarders, ion adsorbents, pigments, dyes, fluorescent materials, release agents, antistatic agents, flame retardants, radical polymerizable compounds, polyimide resins, polyamide resins, phenoxy resins, poly(meth)acrylate resins, polyurethane resins, polyurea resins, polyester resins, polyvinyl butyral resins, SBS, and SEBS.
• the content of these components is, for example, about 0.05 to 50% by weight, preferably 0.05 to 10% by weight, and particularly preferably 0.1 to 5% by weight, of the total amount of the curable composition (100% by weight).
• the curable composition can be produced by uniformly mixing the cationic polymerization initiator, the cationic polymerizable compound, and other components added as necessary using commonly known mixing equipment such as a self-rotating stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, or a bead mill.
• mixing equipment such as a self-rotating stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, or a bead mill.
• the components may be mixed simultaneously or sequentially.
• the uses of the curable composition are not particularly limited, and examples include paints, coating agents, inks, positive resists, resist films, liquid resists, photosensitive materials, adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, sealing materials, sealing materials, encapsulants, and materials for photopolymerization.
• the curable composition contains a cationic polymerization initiator that generates sulfonic acid with excellent acid strength, so that a cured product can be formed quickly by irradiation with light.
• the curable composition contains a cationic polymerization initiator with excellent solvent solubility, precipitation of the cationic polymerization initiator can be suppressed even if the composition is kept in a low temperature environment after preparation (for example, a temperature environment of 0°C or less, preferably a temperature environment of -25°C or less). Therefore, there is a sufficient time before use after preparation, and the composition is easy to handle.
• the cured product of the present invention is a cured product of the above-mentioned curable composition.
• the cured product is obtained by curing the curable composition.
• the curable composition can be cured by irradiating it with light.
• Any light can be used as long as it has enough energy to induce decomposition of the salt contained in the acid generator.
• light having a wavelength in the ultraviolet to visible light range obtained from low, medium, high or ultra-high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, fluorescent lamps, semiconductor solid state lasers, argon lasers, He-Cd lasers, KrF excimer lasers, ArF excimer lasers, F2 lasers, etc. is used.
• High energy radiation such as electron beams and X-rays can also be used.
• the irradiation time of the light depends on the intensity of the energy beam and the transmittance of the light to the curable composition, but is usually about 0.1 to 10 seconds at room temperature. If necessary, the composition may be heated at room temperature to 150°C for several seconds to several hours after the light irradiation.
• Example 1 (Preparation of Sulfonic Acid Salt) 2.9 g of 3,3,4-trifluoro-4-(pentafluorosulfanyl)-1,2-oxathietane-2,2-dioxide and 20 mL of hexane were added to a reaction vessel and stirred. 1.7 g of 1-adamantanemethanol was gradually added thereto. Then, the mixture was reacted at room temperature for 5 hours, and 10 mL of water was added. The organic layer and the aqueous layer were separated by a separation operation. The obtained aqueous layer was extracted twice with 10 mL of diisopropyl ether, and the obtained organic layer was combined and washed three times with 10 mL of water.
• Example 2 The same procedure as in Example 1 was carried out except that 6.0 g of triphenylsulfonium chloride was changed to 8.6 g of bis(4-tert-butylphenyl)iodonium chloride, and 14.2 g of a white solid was obtained (yield 86%). From 1 H-NMR and 19 F-NMR, the obtained white solid was confirmed to be bis(4-tert-butylphenyl)iodonium 1-adamantanemethyloxycarbonyl-1-fluoro-1-(pentafluorosulfanyl)-methanesulfonate.
• Example 3 2.9 g of 3,3,4-trifluoro-4-(pentafluorosulfanyl)-1,2-oxathietane-2,2-dioxide and 20 mL of hexane were added to a reaction vessel and stirred. 0.5 g of ethanol was gradually added thereto. Then, the mixture was reacted at room temperature for 5 hours, and 10 mL of water was added. The organic layer and the aqueous layer were separated by a separation operation. The obtained aqueous layer was extracted twice with 10 mL of diisopropyl ether, and the obtained organic layer was combined and washed three times with 10 mL of water.
• Example 4 2.9 g of 3,3,4-trifluoro-4-(pentafluorosulfanyl)-1,2-oxathietane-2,2-dioxide and 20 mL of hexane were added to a reaction vessel and stirred. 0.7 g of tert-butanol was gradually added thereto. Then, the mixture was reacted at room temperature for 5 hours, and 10 mL of water was added. The organic layer and the aqueous layer were separated by a separation operation. The obtained aqueous layer was extracted twice with 10 mL of diisopropyl ether, and the obtained organic layer was combined and washed three times with 10 mL of water.
• Example 7 In a reaction vessel, 4.5 g of 1-adamantanemethyloxycarbonyl-1-fluoro-1-(pentafluorosulfanyl)-methanesulfonyl chloride and 1.7 g of N-hydroxyphthalimide were added and dissolved in 50 mL of chloroform. This was cooled to 0°C, and 1.1 g of triethylamine was slowly added dropwise while stirring. After that, the temperature was raised and the mixture was stirred at 50°C for 8 hours, and then 50 mL of chloroform and 50 mL of water were added to the reaction liquid and stirred for 1 hour.
• Example 8 The same procedure as in Example 7 was repeated, except that 1.7 g of N-hydroxyphthalimide was replaced with 1.8 g of 4-methoxybenzoyl cyanide oxime, and 3.4 g of a pale yellow solid was obtained (yield 58%). From 1 H-NMR and 19 F-NMR, the pale yellow solid was identified as N-[1-adamantanemethyloxycarbonyl-1-fluoro-1-(pentafluorosulfanyl)-methanesulfonyloxy]-4-methoxybenzimidoyl cyanide.
• Example 9 1.3 g of N-methylhydroxylammonium hydrochloride was added to a reaction vessel, dissolved in 10 mL of methanol, and 15 mL of a 10% solution of potassium hydroxide in methanol was added dropwise while stirring at 0°C. Furthermore, 2.4 g of 8-methoxycoumarin-3-carboxylic acid chloride dissolved in 10 mL of THF was added and stirred for 1 hour. The reaction solution was returned to room temperature and stirred for another 1 hour, after which the reaction solution was distilled off under reduced pressure.
• Example 7 The same procedure as in Example 7 was carried out except that 1.7 g of N-hydroxyphthalimide was replaced with 2.5 g of compound (F-11), and 3.6 g of a pale yellow solid was obtained (yield 54%). From 1 H-NMR and 19 F-NMR, the pale yellow solid was identified as N-methyl-N-[1-adamantanemethyloxycarbonyl-1-fluoro-1-(pentafluorosulfanyl)-methanesulfonyloxy]-8-methoxycoumarin-3-carbonylamide.
• Example 10 3.0 g of 5-bromopyridin-2-yltetrafluoro- ⁇ 6 -sulfanyl chloride, 200 mL of acetonitrile, 10 g of sodium dithionite, and 0.25 g of benzoyl peroxide were added to a reaction vessel, and the mixture was reacted at 85° C. for 65 hours.
• the solvent was distilled off under reduced pressure, and 20 mL of water and 20 mL of toluene were added thereto, and the mixture was stirred for 1 hour and allowed to stand.
• the aqueous layer was separated, and 100 mL of saturated saline was added thereto, and the precipitated solid was filtered.
• Example 11 2.6 g of 4-chlorophenyltetrafluoro- ⁇ 6 -sulfanyl chloride, 200 mL of acetonitrile, 10 g of sodium dithionite, and 0.25 g of benzoyl peroxide were added to a reaction vessel and reacted at 85°C for 65 hours. The solvent was distilled off under reduced pressure, and 20 mL of water and 20 mL of toluene were added thereto, stirred for 1 hour, and allowed to stand. The aqueous layer was separated, and 100 mL of saturated saline was added thereto, and the precipitated solid was filtered.
• Example 12 2.3 g of 4-fluorophenyltetrafluoro- ⁇ 6 -sulfanyl chloride, 200 mL of acetonitrile, 10 g of sodium dithionite, and 0.25 g of benzoyl peroxide were added to a reaction vessel and reacted at 85°C for 65 hours.
• the solvent was distilled off under reduced pressure, and 20 mL of water and 20 mL of toluene were added thereto, stirred for 1 hour, and allowed to stand.
• the aqueous layer was separated, and 100 mL of saturated saline was added thereto, and the precipitated solid was filtered.
• Examples 13 and 14 The compounds shown in the table were synthesized according to the method of Example 1.
• Example 15 The compounds shown in the table were synthesized according to the method of Example 7.
• Example 16 3.6 g of 3,3,4-trifluoro-4-(p-fluorophenyltetrafluoro- ⁇ 6 -sulfanyl)-1,2-oxathietane-2,2-dioxide and 15 mL of water were added to a reaction vessel and reacted for 60 hours at 60° C. The reaction vessel was thoroughly cooled in a salt ice bath and dried under reduced pressure to obtain a pale yellow solid. To the resulting pale yellow solid, 40 mL of dry methanol and 4.5 g of lithium hydroxide monohydrate were added at room temperature, and the mixture was stirred for 16 hours, and then reacted under reflux for 6 hours.
• the reaction vessel was thoroughly cooled in a salt ice bath and dried under reduced pressure to obtain a pale yellow solid.
• Examples 17-22 The compounds shown in the table were synthesized according to the method of Example 16.
• Preparation of photoresist 80 parts by weight of the acid-reactive compound obtained in Preparation Example 1 was mixed with 7.4 parts by weight of a compound of an Example, Comparative Example, or Reference Example, 1.1 parts by weight of tris[2-(methoxymethoxy)ethyl]amine, 896 parts by weight of PGMEA, and 364 parts by weight of cyclohexanone to obtain a mixture, and the obtained mixture was filtered through a 0.2 ⁇ m Teflon (registered trademark) filter to prepare a photoresist.
• Teflon registered trademark
• An anti-reflective coating solution (ARC-29A, manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon substrate and baked at 200° C. for 60 seconds to prepare an anti-reflective coating (78 nm thick).
• the photoresist prepared above was spin-coated on a substrate provided with an anti-reflective coating, and baked at 120° C. for 60 seconds using a hot plate to prepare a resist film with a thickness of 160 nm.
• the exposure dose at which 80 nm lines and spaces are resolved at 1:1 was defined as the optimum exposure dose (Eop, mJ/cm 2 ), and the minimum line width (nm) of the lines and spaces separated at this exposure dose was defined as the resolution.
• the shape of the pattern in the cross section of the resist was observed using a scanning electron microscope.
• the compounds of the present invention can generate sulfonic acids having higher acid strengths and can form patterns with higher resolution, as compared with the acid generators that have conventionally been used and are described in the Reference Examples and Comparative Examples. Therefore, it is evident that by using the compound of the present invention, semiconductor devices having high-resolution wiring patterns or circuit patterns can be manufactured with good yield.
• a compound which is a salt of an anion represented by formula (a-1) or (a-2) and a cation [2] A compound represented by formula (b-1) or (b-2): [3] A compound represented by formula (c-1) or (c-2): [4] A compound represented by formula (d-1) or (d-2): [5] An acid generator comprising the compound according to any one of [1] to [4]. [6] A photoresist comprising the acid generator according to [5] and an acid-reactive compound.
• a method for producing an electronic device or an optical device comprising a step of forming a pattern by photolithography using the photoresist according to [6].
• a photoresist comprising the compound according to any one of [1] to [4] and an acid-reactive compound.
• the compound of the present invention does not have a perfluoromethyl group or a perfluoromethylene group, and is therefore exempt from the PFAS regulations. Moreover, the compound is easily decomposed by irradiation with light to generate a sulfonic acid having a high acid strength.
• a photoresist containing the compound of the present invention By using a photoresist containing the compound of the present invention, a resist film having a high-resolution pattern with good accuracy can be produced.
• a semiconductor device having a high-resolution pattern can be produced with good yield.

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