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WO2015146053A1 - Composé sulfonate imide, générateur de photoacide, et composition de résine pour photolithographie - Google Patents

Composé sulfonate imide, générateur de photoacide, et composition de résine pour photolithographie Download PDF

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Publication number
WO2015146053A1
WO2015146053A1 PCT/JP2015/001406 JP2015001406W WO2015146053A1 WO 2015146053 A1 WO2015146053 A1 WO 2015146053A1 JP 2015001406 W JP2015001406 W JP 2015001406W WO 2015146053 A1 WO2015146053 A1 WO 2015146053A1
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Prior art keywords
group
carbon atoms
represented
photoacid generator
nmr
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Japanese (ja)
Inventor
昌明 岡
秀基 木村
卓也 池田
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San Apro KK
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San Apro KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D223/18—Dibenzazepines; Hydrogenated dibenzazepines
    • 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
    • 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
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition

Definitions

  • the present invention relates to an imide sulfonate compound, a photoacid generator, and a resin composition for photolithography. More specifically, the present invention relates to a nonionic photoacid generator suitable for generating a strong acid by the action of ultraviolet rays (i rays), and a photolithographic resin composition containing the nonionic photoacid generator.
  • a nonionic photoacid generator suitable for generating a strong acid by the action of ultraviolet rays (i rays)
  • a photolithographic resin composition containing the nonionic photoacid generator containing the nonionic photoacid generator.
  • a photolithography process using i-line having a wavelength of 365 nm as exposure light has been widely used.
  • a resist material used in the photolithography process for example, a resin composition containing a polymer having a tert-butyl ester group of carboxylic acid or a tert-butyl carbonate group of phenol and a photoacid generator is used. Yes.
  • Nonionic photoacid generators such as triarylsulfonium salts (Patent Document 1), phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2), and acid generators having an oxime sulfonate structure (Patent Documents) 3)
  • Nonionic acid generators such as acid generators having a sulfonyldiazomethane structure (Patent Document 4) are known.
  • the photoacid generator is decomposed to generate a strong acid.
  • the tert-butyl ester group or tert-butyl carbonate group in the polymer is dissociated by the strong acid to form a carboxylic acid or a phenolic hydroxyl group. It becomes readily soluble in an alkaline developer. Pattern formation is performed using this phenomenon.
  • ionic photoacid generators lack compatibility with hydrophobic materials containing alicyclic skeletons, fluorine-containing skeletons, etc., they can exhibit sufficient resist performance due to phase separation in resist materials. Therefore, there is a problem that the pattern cannot be formed.
  • nonionic photoacid generators have good compatibility with hydrophobic materials, but the problem of insufficient sensitivity to i-line and the lack of heat resistance stability cause decomposition by post-exposure heating (PEB), and allowance. There is a narrow problem.
  • nonionic photoacid generator having high photosensitivity to i-line, excellent heat resistance stability, and excellent solubility in hydrophobic materials.
  • this invention is an imidosulfonate compound represented by General formula (1).
  • R1 to R8 are independently of each other a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms or a fluoroalkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, carbon An alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl group, a silyl group, a nitro group, a cyano group, an amino group, an alkoxy group or an aryloxy group represented by R 11 O—, R 12 An alkylthio group or an arylthio group represented by S—, a sulfinyl group represented by R 13 SO—, a sulfonyl group represented by R 14 SO 2 —, an alkylcarbonyl group or an arylcarbonyl group represented by R 15 CO—, R 16 COO - carbony
  • the imide sulfonate compound of the present invention and the nonionic photoacid generator (A) containing the imidesulfonate compound are nonionic and are more compatible with hydrophobic materials than ionic acid generators. Moreover, since it has a biphenyl structure in which benzene rings are twisted and is difficult to crystallize, it has excellent solubility in a solvent. Moreover, since it has an imide skeleton which is an absorption site for i-line, the non-ionic photoacid generator (A) can be easily decomposed by irradiating i-line, and sulfonic acid which is a strong acid can be generated. Furthermore, since the nonionic photoacid generator (A) has an imide skeleton, it has excellent heat stability.
  • the resin composition for photolithography (Q) containing the nonionic photoacid generator (A) of the present invention is highly sensitive to i-line and has an allowance in post-exposure heating (PEB). Excellent workability because it is wide.
  • the imide sulfonate compound of the present invention is represented by the general formula (1).
  • examples of the halogen atom represented by R1 to R8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 18 carbon atoms of R1 to R8 examples include linear alkyl groups having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl).
  • branched chain alkyl groups having 1 to 18 carbon atoms isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl) , Isohexyl and isooctadecyl
  • cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decylcyclohexyl).
  • C1-C18 linear or branched fluoroalkyl group (trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoro Propyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl, heptafluoropropyl, 2,2,3,3,4,4 , 4-heptafluorobutyl, perfluorobutyl, nonafluoro-tert-butyl, 1H, 1H-nonafluoropentyl, perfluoropentyl, 1H, 1H-tridecafluorohexyl, perfluorohexyl, 1H, 1H-pentadecafluorooctyl , Perfluorooctyl, groups, etc.).
  • alkenyl group having 2 to 18 carbon atoms of R1 to R8 examples include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, and 1-methyl.
  • alkynyl group having 2 to 18 carbon atoms represented by R1 to R8 examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, -Methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1,2-dimethyl-2-propynyl, 1-decynyl, 2-decynyl, Examples thereof include linear or branched ones such as 8-decynyl, 1-dodecynyl, 2-dodecynyl and 10-dodecynyl.
  • Examples of the aryl group having 6 to 18 carbon atoms of R1 to R8 include phenyl, tolyl, dimethylphenyl, naphthyl, anthracenyl, biphenyl, pentafluorophenyl, and the like.
  • Examples of the silyl group of R1 to R8 include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl.
  • tricarbylsilyl groups such as a tert-butyldimethylsilyl group, a methyldi-tert-butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.
  • the amino group of R1 to R8 includes an amino group (—NH2) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n -Propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino and Isopropylphenylamino and the like).
  • a substituted amino group having 1 to 15 carbon atoms methylamino, dimethylamino, ethylamino, methylethylamin
  • Examples of the alkoxy group represented by R 11 O— of R1 to R8 include linear or branched alkoxy groups having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert -Linear or branched fluoroalkyl groups having 1 to 18 carbon atoms (trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trimethyl, etc.) such as butoxy, hexyloxy, decyloxy, dodecyloxy and octadecyloxy Fluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoro-2- Propyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl
  • alkylthio group represented by R 12 S— of R1 to R8 examples include a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio and the like.
  • an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2 -Bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxy Phenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4-
  • Examples of the sulfinyl group represented by R 13 SO— in R1 to R8 include a linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, etc.), arylsulfinyl groups having 6 to 10 carbon atoms (phenylsulfinyl, toly
  • Examples of the sulfonyl group represented by R 14 SO 2 — in R1 to R8 include linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutyl) Sulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl and octadecylsulfonyl), arylsulfonyl groups having 6 to 10 carbon atoms ⁇ phenylsulfonyl, toly
  • the alkylcarbonyl group represented by R 15 CO— in R1 to R8 is a linear or branched alkylcarbonyl group having 2 to 18 carbon atoms (including carbonyl carbon) (acetyl, propionyl, butanoyl, 2-methylpropionyl). , Heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl and octadecanoyl).
  • Examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (including carbonyl carbon) (such as benzoyl and naphthoyl).
  • Examples of the carbonyloxy group represented by R 16 COO— of R1 to R8 include a linear or branched acyloxy group having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy Aryl having 6 to 18 carbon atoms, such as isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, hexylcarbonyloxy, 2-ethylhexylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy and octadecylcarbonyloxy) C1-C8 linear or branched fluoroalkyl groups (trifluoromethyl) such as carbonyloxy groups (benzoyloxy, naphthoyloxy, pentafluorobenzoyloxy, etc.) 2,2-difluor
  • Examples of the oxycarbonyl group represented by R 17 OCO— of R1 to R8 include straight or branched alkoxycarbonyl groups having 2 to 19 carbon atoms (including carbonyl carbon) (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, iso Propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.), aryloxy having 7 to 11 carbon atoms (including carbonyl carbon) Examples include carbonyl groups (phenoxycarbonyl, naphthoxycarbonyl, etc.) and the like.
  • R 18 carbonate group represented by -OCOO- R 18 of ⁇ R8, straight-chain alkyl groups (methyl of 1 to 18 carbon atoms, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl , N-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), a branched alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, etc.) , Tert-pentyl, isohexyl and isooctadecyl), and a cycloalkyl group having 3 to 18 carbon atoms (such as cyclopropyl, cyclobut
  • the urethane group represented by has a substituent (T) Good.
  • substituent (T) examples include an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, Examples thereof include an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a halogen atom.
  • the substituent (T) may be one type or two or more types.
  • At least two of R1 to R8 may be bonded to each other to form a ring structure.
  • a ring structure it is preferable that two adjacent ones form an aromatic ring.
  • the ring may contain a hetero atom or an oxo group.
  • you may have a substituent (T).
  • all of R1 to R8 are hydrogen atoms, or at least one of R1 to R8 is independently of each other a halogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon number.
  • One in which two are bonded to each other and two adjacent to each other form an aromatic ring is preferable.
  • R1 to R8 are a hydrogen atom or at least any two of R1 to R8 are the same functional group, and the functional group includes a halogen atom, a carbon number An alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl group, R An alkoxy group or aryloxy group represented by 11 O—, an alkylcarbonyl group or arylcarbonyl group represented by R 15 CO—, a carbonyloxy group represented by R 16 COO—, or an oxycarbonyl group represented by R 17 OCO— A certain one, or at least two of R1 to R8 are bonded to each other and two adjacent to each other
  • R9 which is an essential functional group for decomposing the sulfonic acid ester moiety by ultraviolet irradiation, is an optionally substituted hydrocarbon group having 1 to 18 carbon atoms (a part or all of hydrogen is substituted with fluorine). It may be).
  • substituent those exemplified as the substituent (T) can be used.
  • the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an aryl group, and a heterocyclic hydrocarbon group.
  • alkyl group examples include linear alkyl groups having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n- Hexadecyl, n-octadecyl, etc.), branched alkyl groups having 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and isooctadecyl), and 3 carbon atoms -18 cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decylcyclohexyl, 10-
  • aryl group examples include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, naphthyl, and pentafluorophenyl).
  • the heterocyclic hydrocarbon group includes a heterocyclic hydrocarbon group having 4 to 18 carbon atoms (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl.
  • Examples of the group in which part or all of the hydrogen atoms of the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent are substituted with fluorine include CxFy having a high electron-withdrawing property.
  • CxFy in the nonionic acid generator (A) may be used singly or in combination of two or more.
  • CxFy examples include a linear alkyl group (RF1), a branched alkyl group (RF2), a cycloalkyl group (RF3), and an aryl group (RF4) in which hydrogen atoms are substituted with fluorine atoms.
  • RF1 linear alkyl group
  • RF2 branched alkyl group
  • RF3 cycloalkyl group
  • RF4 aryl group
  • linear alkyl group (RF1) in which a hydrogen atom is substituted with a fluorine atom
  • CxFy having a high electron-withdrawing property is preferable.
  • a linear alkyl group (RF1), a branched chain is preferable.
  • Preferred examples of the imide sulfonate compound represented by the general formula (1) include, but are not limited to, the following from the viewpoints of ease of synthesis, adjustment of the absorption wavelength region, and heat stability.
  • the method for synthesizing the imide sulfonate compound of the present invention is not particularly limited as long as the target product can be synthesized.
  • sulfonic acid anhydrides represented by N-hydroxyimide compound (P1) and (R9-SO 2 ) 2 O as precursors
  • a reaction of a salt of the N-hydroxyimide compound (P1) with a sulfonic acid chloride represented by R9-SO 2 Cl represented by R9-SO 2 Cl.
  • the nonionic photoacid generator (A) of the present invention contains the imide sulfonate compound.
  • the nonionic photoacid generator (A) of the present invention may be dissolved in advance in a solvent that does not inhibit the reaction in order to facilitate dissolution in the resist material.
  • Solvents include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.); esters (ethyl acetate, ethyl lactate, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -Valerolactone and ⁇ -caprolactone, etc.); ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and ether esters ( Ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate And diethylene glycol monobutyl ether acetate, etc.) and the like.
  • the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, with respect to 100 parts by weight of the nonionic photoacid generator of the present invention.
  • the resin composition for photolithography (Q) of the present invention contains the nonionic photoacid generator (A) as an essential component, the exposed portion and the unexposed portion are exposed by performing ultraviolet irradiation and post-exposure heating (PEB). Difference in solubility in the developer of the part.
  • a nonionic photoacid generator (A) can be used individually by 1 type or in combination of 2 or more types.
  • Examples of the resin composition (Q) for photolithography include a mixture of a negative chemical amplification resin (QN) and a nonionic photoacid generator (A); and a positive chemical amplification resin (QP) and a nonionic photoacid.
  • QN negative chemical amplification resin
  • QP positive chemical amplification resin
  • a mixture with a generator (A) is mentioned.
  • the negative chemical amplification resin (QN) is composed of a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).
  • the phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it contains a phenolic hydroxyl group.
  • a novolak resin a polyhydroxystyrene, a copolymer of hydroxystyrene, a copolymer of hydroxystyrene and styrene Copolymer, copolymer of hydroxystyrene, styrene and (meth) acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, polyimide containing phenolic hydroxyl group, polyamic acid containing phenolic hydroxyl group Phenol-dicyclopentadiene condensation resin is used.
  • novolak resins polyhydroxystyrene, copolymers of polyhydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth) acrylic acid derivatives, phenol-xylylene glycol Condensed resins are preferred.
  • these phenolic hydroxyl group containing resin (QN1) may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.
  • phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples include trimethylphenol, catechol, resorcinol, pyrogallol, ⁇ -naphthol, ⁇ -naphthol and the like.
  • aldehydes include formaldehyde, paraformaldehyde, ace
  • novolak resin examples include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.
  • the phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low molecular weight compound as a part of the component.
  • the phenolic low molecular weight compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1 -Methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4 -[1- (4-hydroxyphenyl) -1- [4
  • the content ratio of the phenolic low molecular weight compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by weight or less, more preferably, based on 100% by weight of the phenolic hydroxyl group-containing resin (QN1). 1 to 30% by weight.
  • the weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, more preferably 2000 from the viewpoint of the resolution, thermal shock resistance, heat resistance, residual film ratio, etc. of the obtained insulating film. About 20,000.
  • the content of the phenolic hydroxyl group-containing resin (QN1) in the negative chemically amplified resin (QN) is 30 to 90% by weight when the total composition excluding the solvent is 100% by weight. Is more preferable, and 40 to 80% by weight is more preferable.
  • the content of the phenolic hydroxyl group-containing resin (QN1) is 30 to 90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability with an alkaline aqueous solution. Therefore, it is preferable.
  • the crosslinking agent (QN2) is not particularly limited as long as it is a compound that can crosslink the phenolic hydroxyl group-containing resin (QN1) with a strong acid generated from the nonionic photoacid generator (A).
  • crosslinking agent (QN2) examples include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds, poly (hydroxystyrene) epoxy compounds, and oxetanes.
  • methylol group-containing phenol compounds methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds and acetoxymethyl group-containing phenol compounds
  • methoxymethyl group-containing melamine compounds for example, hexamethoxymethyl melamine
  • methoxymethyl group-containing glycoluril compounds methoxymethyl group-containing urea compounds
  • the methoxymethyl group-containing melamine compound is a trade name such as CYMEL300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Cyanamid Co., Ltd.), and the methoxymethyl group-containing glycoluril compound is a trade name such as CYMEL1174 (manufactured by Mitsui Cyanamid Co., Ltd.). Further, the methoxymethyl group-containing urea compound is commercially available under a trade name such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).
  • the content of the crosslinking agent (QN2) is usually 5 to 5 with respect to all acidic functional groups in the phenolic hydroxyl group-containing resin (QN1) from the viewpoints of reduction of the remaining film ratio, pattern meandering and swelling, and developability.
  • the amount is 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%.
  • a positive chemical amplification resin As a positive chemical amplification resin (QP), a part of hydrogen atoms of acidic functional groups in an alkali-soluble resin (QP1) containing one or more acidic functional groups such as phenolic hydroxyl group, carboxyl group, or sulfonyl group Or the protecting group introduction
  • transduction resin which substituted all by the acid dissociable group is mentioned.
  • the acid dissociable group is a group that can be dissociated in the presence of a strong acid generated from the nonionic photoacid generator (A).
  • the protecting group-introduced resin (QP2) is itself insoluble in alkali or hardly soluble in alkali.
  • alkali-soluble resin examples include a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), and a sulfonic acid group-containing resin (QP13).
  • the phenolic hydroxyl group-containing resin (QP11) the same phenolic hydroxyl group-containing resin (QN1) can be used.
  • the carboxyl group-containing resin (QP12) is not particularly limited as long as it is a polymer having a carboxyl group.
  • vinyl polymerization of a carboxyl group-containing vinyl monomer (Ba) and, if necessary, a hydrophobic group-containing vinyl monomer (Bb) is vinyl-polymerized. It is obtained by doing.
  • carboxyl group-containing vinyl monomer (Ba) examples include unsaturated monocarboxylic acids [(meth) acrylic acid, crotonic acid, cinnamic acid, etc.], unsaturated polyvalent (2- to 4-valent) carboxylic acids [(anhydrous) maleic acid, and the like. Acid, itaconic acid, fumaric acid, citraconic acid and the like], unsaturated polyvalent carboxylic acid alkyl (alkyl group having 1 to 10 carbon atoms) ester [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester, etc.
  • salts thereof [alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), amine salts, ammonium salts, etc.].
  • unsaturated monocarboxylic acids are preferred from the viewpoint of polymerizability and availability, and (meth) acrylic acid is more preferred.
  • hydrophobic group-containing vinyl monomer (Bb) examples include (meth) acrylic acid ester (Bb1) and aromatic hydrocarbon monomer (Bb2).
  • Examples of the (meth) acrylic acid ester (Bb1) include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.] and alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, Sidiclopentenyl (meth) acrylate, isobornyl (meth) acrylate, etc.].
  • alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group for example, methyl (meth) acrylate, ethyl (meth)
  • aromatic hydrocarbon monomer (Bb2) examples include hydrocarbon monomers having a styrene skeleton [for example, styrene, ⁇ -methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene. Cyclohexyl styrene and benzyl styrene] and vinyl naphthalene.
  • hydrocarbon monomers having a styrene skeleton for example, styrene, ⁇ -methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene. Cyclohexyl styrene and benz
  • the charged monomer molar ratio of (Ba) / (Bb) in the carboxyl group-containing resin (QP12) is usually from 10 to 100/0 to 90, preferably from 10 to 80/20 to 90, more preferably from the viewpoint of developability. 25-85 / 15-75.
  • the sulfonic acid group-containing resin (QP13) is not particularly limited as long as it is a polymer having a sulfonic acid group.
  • a sulfonic acid group-containing vinyl monomer (Bc) and, if necessary, a hydrophobic group-containing vinyl monomer (Bb) are used. Obtained by vinyl polymerization.
  • the hydrophobic group-containing vinyl monomer (Bb) the same ones as described above can be used.
  • Examples of the sulfonic acid group-containing vinyl monomer (Bc) include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, ⁇ -methyl styrene sulfonic acid, 2- (meth) acryloylamide-2-methylpropane sulfonic acid. And salts thereof.
  • Examples of the salt include alkali metal (such as sodium and potassium) salts, alkaline earth metal (such as calcium and magnesium) salts, primary to tertiary amine salts, ammonium salts and quaternary ammonium salts.
  • the charged monomer molar ratio of (Bc) / (Bb) is usually 10 to 100/0 to 90, preferably 10 to 80/20 to 90, more preferably from the viewpoint of developability. Is 25 to 85/15 to 75.
  • the preferred range of the HLB value of the alkali-soluble resin (QP1) varies depending on the resin skeleton of the alkali-soluble resin (QP1), but is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 17.
  • the HLB value is 4 or more, developability is further improved when developing, and when it is 19 or less, the water resistance of the cured product is further improved.
  • the HLB in the present invention is an HLB value according to the Oda method, which is a hydrophilic-hydrophobic balance value, and can be calculated from the ratio between the organic value and the inorganic value of the organic compound.
  • HLB ⁇ 10 ⁇ Inorganic / Organic
  • the inorganic value and the organic value are described in the document “Surfactant Synthesis and Applications” (published by Tsuji Shoten, Oda, Teramura), page 501; It is described in detail on page 198 of “Introduction to New Surfactants” (Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd.).
  • Examples of the acid dissociable group in the protecting group-introduced resin (QP2) include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid.
  • Examples include a dissociable group. These may be used alone or in combination of two or more.
  • Examples of the 1-substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphena Sil group, methylthiophenacyl group, ⁇ -methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl Group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert-
  • Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl.
  • Examples of the 1-branched alkyl group include i-propyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. it can.
  • silyl group examples include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, tert-butyl.
  • examples thereof include tricarbylsilyl groups such as dimethylsilyl group, methyldi-tert-butylsilyl group, tri-tert-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, and triphenylsilyl group.
  • germyl group examples include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldi-i-propylgermyl group, and tri-i-propylgel.
  • Tricarbylgermyl groups such as mil group, tert-butyldimethylgermyl group, methyldi-tert-butylgermyl group, tri-tert-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. Can be mentioned.
  • alkoxycarbonyl group examples include methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, tert-butoxycarbonyl group and the like.
  • Acyl groups include, for example, acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl Group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group, benzoyl group , Phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group
  • cyclic acid dissociable group examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiofuranyl group.
  • tert-butyl group benzyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tetrahydropyranyl group, A tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrofuranyl group, and the like are preferable.
  • Introduction rate of acid-dissociable groups in protecting group-introducing resin (QP2) ⁇ Ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in protecting group-introducing resin (QP2) ⁇ Cannot be generally defined by the type of acid-dissociable group or the alkali-soluble resin into which the group is introduced, but is preferably 10 to 100%, more preferably 15 to 100%.
  • the polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the protecting group-introduced resin (QP2) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 3, 000 to 100,000.
  • the ratio (Mw / Mn) of the Mw of the protecting group-introduced resin (QP2) and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 To 10, preferably 1 to 5.
  • the content of the nonionic photoacid generator (A) based on the weight of the solid content of the resin composition for photolithography (Q) is preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight. %, Particularly preferably 0.05 to 7% by weight. If it is 0.001% by weight or more, the sensitivity to ultraviolet rays can be exhibited more satisfactorily, and if it is 20% by weight or less, the physical properties of the insoluble part in the alkali developer can be exhibited more satisfactorily.
  • the resist using the resin composition for photolithography (Q) of the present invention is prepared by, for example, applying a resin solution dissolved in a predetermined organic solvent (dissolved and dispersed when inorganic fine particles are included) to a spin coat, curtain coat, roll It can be formed by drying the solvent by heating or hot air blowing after applying to the substrate using a known method such as coating, spray coating or screen printing.
  • the organic solvent for dissolving the resin composition for photolithography (Q) is particularly limited as long as the resin composition can be dissolved and the resin solution can be adjusted to physical properties (viscosity, etc.) applicable to spin coating or the like.
  • known solvents such as N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone and xylene Can be used.
  • solvents those having a boiling point of 200 ° C. or less (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone and xylene) from the viewpoint of drying temperature and the like are preferable, and can be used alone or in combination of two or more.
  • the amount of the solvent is not particularly limited, but is usually preferably 30 to 1,000% by weight, more preferably based on the weight of the solid content of the resin composition for photolithography (Q). It is 40 to 900% by weight, particularly preferably 50 to 800% by weight.
  • the drying condition of the resin solution after coating varies depending on the solvent used, but is preferably carried out at 50 to 200 ° C. for 2 to 30 minutes, and the residual solvent amount of the resin composition for photolithography (Q) after drying ( Weight%) and the like.
  • the wiring pattern shape is irradiated with light. Then, after performing post-exposure heating (PEB), alkali development is performed to form a wiring pattern.
  • PEB post-exposure heating
  • Examples of the light irradiation method include a method of exposing the resist with actinic rays through a photomask having a wiring pattern.
  • the actinic ray used for the light irradiation is not particularly limited as long as the nonionic photoacid generator (A) in the resin composition for photolithography (Q) of the present invention can be decomposed.
  • Actinic rays include low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halogen lamp, electron beam irradiation device, X-ray irradiation device, laser (argon laser, dye laser, nitrogen laser, LED, helium Cadmium laser). Of these, high pressure mercury lamps and ultrahigh pressure mercury lamps are preferred.
  • the post-exposure heating (PEB) temperature is usually 40 to 200 ° C., preferably 500 to 190 ° C., more preferably 60 to 180 ° C. If the temperature is lower than 40 ° C., the deprotection reaction or the crosslinking reaction cannot be sufficiently performed. Therefore, there is not enough difference in solubility between the ultraviolet irradiated portion and the ultraviolet unirradiated portion, and a pattern cannot be formed. There is.
  • the heating time is usually 0.5 to 120 minutes, preferably 1 to 90 minutes, and more preferably 2 to 90 minutes. If it is less than 0.5 minutes, it is difficult to control the time and temperature, and if it is more than 120 minutes, there is a problem that productivity is lowered.
  • Examples of the alkali developing method include a method of dissolving and removing the wiring pattern shape using an alkali developer.
  • the alkali developer is not particularly limited as long as the solubility of the ultraviolet-irradiated part and the ultraviolet-irradiated part of the resin composition for photolithography (Q) can be varied.
  • Examples of the alkali developer include a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, sodium hydrogen carbonate, and a tetramethylammonium salt aqueous solution.
  • These alkaline developers may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N-methylpyrrolidone and the like.
  • a developing method there are a dip method, a shower method, and a spray method using an alkali developer.
  • the temperature of the developer is preferably 25 to 40 ° C.
  • the development time is appropriately determined according to the resist thickness.
  • the reaction solution was added while stirring 1N hydrochloric acid (100 mL) placed in a beaker, and the precipitated solid was collected by filtration.
  • the obtained solid was dissolved in acetic anhydride (30 g) and reacted under reflux conditions for 2 hours, and then the pressure was reduced to distill off acetic anhydride.
  • Pyridine (10 g) was added to the residue for dissolution, and hydroxylamine hydrochloride (4.9 g) was further added, followed by stirring at 100 ° C. for 10 hours. After cooling to room temperature, the reaction mixture was poured into 1N hydrochloric acid (300 mL), and the precipitate was collected by filtration to give the title compound [Intermediate (3)].
  • Example 1 Synthesis of N-trifluoromethanesulfonyloxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-1)] [Intermediate (1)] (3.0 g) obtained in Production Example 1 was dissolved in pyridine (20 ml), and trifluoromethanesulfonic anhydride (12.3 g) was added dropwise with stirring at 0 ° C. . After stirring at 25 ° C. for 8 hours, the reaction mixture was extracted with dichloromethane-water, and the organic layer was removed under reduced pressure to give an orange oil. Further, the title compound [nonionic photoacid generator (A-1)] was obtained by recrystallization from methanol.
  • Example 2 Synthesis of N-trifluoromethanesulfonyloxy-4-methoxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-1)] obtained in Production Example 1 [Intermediate (1)] (3.0 g) was changed to [Intermediate (2)] (3.4 g) obtained in Production Example 2, and the title compound [nonionic photoacid generator] was obtained in the same manner as in Example 1. (A-2)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 3 Synthesis of N-trifluoromethanesulfonyloxy-5,5′-difluorobiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-3)] [Intermediate ( 1)] (3.0 g) in the same manner as in Example 1 except that [Intermediate (3)] (3.5 g) obtained in Preparation Example 3 was used. Acid generator (A-3)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 4 Synthesis of N-trifluoromethanesulfonyloxy-4,4′-dimethylbiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-4)] [Intermediate ( 1)] (3.0 g) in the same manner as in Example 1 except that [Intermediate (4)] (3.4 g) obtained in Preparation Example 4 was used. Acid generator (A-4)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 5 Synthesis of N-trifluoromethanesulfonyloxy-6,6′-dimethylbiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-5)] obtained in Production Example 1 [Intermediate ( 1)] (3.0 g) in the same manner as in Example 1, except that [Intermediate (5)] (3.4 g) obtained in Preparation Example 5 was used. Acid generator (A-5)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 6 Synthesis of N-trifluoromethanesulfonyloxy-4,4′-dimethoxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-6)] [Intermediate ( 1)] (3.0 g) in the same manner as in Example 1 except that [Intermediate (6)] (3.8 g) obtained in Preparation Example 6 was used. Acid generator (A-6)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 7 Synthesis of N-trifluoromethanesulfonyloxy-4,4′-dicarboxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-7)] obtained in Production Example 1 [Intermediate] (1)] (3.0 g) was changed to [Intermediate (7)] (4.1 g) obtained in Production Example 7 in the same manner as in Example 1 except that the title compound [Nonionic System] Photoacid generator (A-7)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 8 Synthesis of N-trifluoromethanesulfonyloxy-4,4 ′, 5,5′-tetramethoxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-8)]
  • the obtained [Intermediate (1)] (3.0 g) was changed to [Intermediate (8)] (3.8 g) obtained in Production Example 8 in the same manner as in Example 1, except that Compound [Nonionic photoacid generator (A-8)] was obtained.
  • the product was identified by 1 H-NMR and 19 F-NMR.
  • Example 9 Synthesis of N-trifluoromethanesulfonyloxy-1,1′-binaphthalene-2,2′-dicarboximide [nonionic photoacid generator (A-9)] [Intermediate (1 )] (3.0 g) in the same manner as in Example 1 except that [Intermediate (9)] (4.3 g) obtained in Preparation Example 9 was used. Generator (A-9)] was obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 10 Synthesis of N-trifluoromethanesulfonyloxy-4,4′-dicarbonyloxymethylbiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-10)] obtained in Example 7 [ Nonionic photoacid generator (A-7)] (4.6 g) was dissolved in thionyl chloride (30 g), reacted at 60 ° C. for 1 hour, and reduced in pressure at 60 ° C. to generate thionyl chloride. Hydrogen chloride was distilled off.
  • Example 11 Synthesis of N-trifluoromethanesulfonyloxy-4,4′-dihydroxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-11)] obtained in Example 6 [nonionic Photoacid generator (A-6)] (4.3 g) was dissolved in dichloromethane (20 mL) under a nitrogen atmosphere, cooled to ⁇ 78 ° C., and boron tribromide (12.5 g) was added dropwise with stirring. And allowed to react for 6 hours. The reaction mixture was poured into a saturated aqueous ammonium chloride solution (100 mL) and extracted with methylene chloride (50 mL).
  • Example 12 Synthesis of N-trifluoromethanesulfonyloxy-4,4′-dibutyroyloxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-12)] obtained in Example 11 [non- Ionic photoacid generator (A-11)] (4.0 g) was dissolved in acetonitrile (15 mL), butyroyl chloride (2.7 g) was added, and pyridine (2.5 g) was cooled in an ice bath. ) was added dropwise over 30 minutes and reacted at room temperature (25 ° C.) for 3 hours.
  • the reaction solution was added while stirring water (150 mL) in a beaker, and the precipitated white solid was collected by filtration and washed to obtain the title compound [nonionic photoacid generator (A-12)]. .
  • the product was identified by 1 H-NMR and 19 F-NMR.
  • Example 13 Synthesis of N-pentafluorobenzenesulfonyloxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-13)] Trifluoromethanesulfonic anhydride (12.3 g) was converted to pentafluorobenzenesulfonyl chloride. The title compound [Nonionic Photoacid Generator (A-13)] was obtained in the same manner as in Example 1, except that the amount was changed to (11.4 g). The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 14 Synthesis of N-pentafluorobenzenesulfonyloxy-6,6′-dimethylbiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-14)] Trifluoromethanesulfonic anhydride (12.3 g) ) was changed to pentafluorobenzenesulfonyl chloride (11.4 g) in the same manner as in Example 5 to obtain the title compound [nonionic photoacid generator (A-14)]. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 15 Synthesis of N-pentafluorobenzenesulfonyloxy-4,4′-dimethoxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-15)] Trifluoromethanesulfonic anhydride (12.3 g) ) was changed to pentafluorobenzenesulfonyl chloride (11.4 g) in the same manner as in Example 6 to obtain the title compound [nonionic photoacid generator (A-15)]. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 16 Synthesis of N-pentafluorobenzenesulfonyloxy-4,4 ′, 5,5′-tetramethoxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-16)] Trifluoromethanesulfonic acid
  • the title compound [nonionic photoacid generator (A-16)] was prepared in the same manner as in Example 8 except that the anhydride (12.3 g) was changed to pentafluorobenzenesulfonyl chloride (11.4 g). Obtained. The product was identified by 1 H-NMR and 19 F-NMR.
  • Example 17 Synthesis of N-(+)-10-camphorsulfonyloxy-biphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-17)] Trifluoromethanesulfonic anhydride (12.3 g) The title compound [Nonionic Photoacid Generator (A-17)] was obtained in the same manner as in Example 1 except for changing to (+)-10-camphorsulfonyl chloride (11.0 g). The product was identified by 1 H-NMR.
  • Example 18 Synthesis of N-(+)-10-camphorsulfonyloxy-6,6′-dimethylbiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-18)] Trifluoromethanesulfonic anhydride
  • the title compound [nonionic photoacid generator (A-18)] was obtained in the same manner as in Example 5 except that (12.3 g) was changed to (+)-10-camphorsulfonyl chloride (11.0 g).
  • the product was identified by 1 H-NMR.
  • Example 20 Synthesis of N-(+)-10-camphorsulfonyloxy-4,4 ′, 5,5′-tetramethoxybiphenyl-2,2′-dicarboximide [nonionic photoacid generator (A-20)]
  • the title compound [nonionic photoacid generation] was carried out in the same manner as in Example 8, except that trifluoromethanesulfonic anhydride (12.3 g) was changed to (+)-10-camphorsulfonyl chloride (11.0 g). Agent (A-20)] was obtained.
  • the product was identified by 1 H-NMR.
  • Comparative Example 4 ⁇ Synthesis of Ionic Photoacid Generator (A'-4)> An ionic photoacid generator (A′-4) was obtained in the same manner as in Comparative Example 2 except that the potassium trifluoromethanesulfonate solution was changed to a potassium pentafluorobenzenesulfonate solution.
  • Comparative Example 6 Synthesis of Ionic Photoacid Generator (A'-6)> An ionic photoacid generator (A′-6) was obtained in the same manner as in Comparative Example 2, except that the aqueous potassium trifluoromethanesulfonate solution was changed to a (+)-10-camphorsulfonic acid potassium aqueous solution.
  • ⁇ Performance evaluation> As performance evaluation of the photoacid generator, the obtained nonionic photoacid generators (A-1) to (A20), nonionic photoacid generators (A′-1), (A′-3), Molar absorption coefficient, resist curability, thermal decomposition temperature, and solvent solubility of (A′-5), ionic acid generators (A′-2), (A′-4) and (A′-6), The amine resistance was evaluated by the following method.
  • PGMEA resin solution of acetate
  • This resist was irradiated with ultraviolet rays (HMW-661F-01, manufactured by Oak Manufacturing Co., Ltd.), and ultraviolet light whose wavelength was limited by a filter L-34 (manufactured by Kenko Optical Co., Ltd., which cuts light of less than 340 nm). A predetermined amount of light was exposed on the entire surface. The integrated exposure was measured at a wavelength of 365 nm. Subsequently, after performing post-exposure heating (PEB) for 10 minutes with a 120 ° C. normal air dryer, development was performed by immersing in a 0.5% potassium hydroxide solution for 30 seconds, followed by immediately washing with water and drying.
  • PEB post-exposure heating
  • the film thickness of this resist was measured using a shape measuring microscope (ultra-deep shape measuring microscope VK-8550, manufactured by Keyence Corporation).
  • the resist curability was evaluated according to the following criteria from the minimum exposure amount at which the change in resist film thickness before and after development was within 10%. ⁇ : minimum exposure amount 250 mJ / cm 2 or less ⁇ : Minimum exposure amount greater than 250mJ / cm 2, 500mJ / cm 2 or less ⁇ : Minimum exposure amount is greater than 500 mJ / cm 2
  • Thermal decomposition temperature Using the differential thermal / thermogravimetric simultaneous measurement device (TG / DTA6200, manufactured by SII), the synthesized photoacid generator was subjected to a change in weight under a nitrogen atmosphere from 30 ° C. to 500 ° C. under a temperature rising condition of 10 ° C./min. The point at which the weight decreased by 2% was defined as the thermal decomposition temperature.
  • ⁇ Amine resistance> The synthesized photoacid generator is diluted to 0.25 mmol / L with acetonitrile in which amine (pyridine, triethylamine) is dissolved at a concentration of 0.25 mmol / L, and the purity is calculated by HPLC analysis. This solution was stored at 25 ° C. under light-shielding conditions for 24 hours, and then the purity was calculated again by HPLC analysis, and the amine resistance was evaluated according to the following criteria from the rate of decrease in purity before and after storage.
  • ⁇ Purity reduction rate is 0.1% to less than 1.0%
  • Purity reduction rate is 1.0% to less than 10%
  • Nonionic photoacid generators (A-1) to (A20) of the present invention prepared in Examples, and nonionic photoacid generators (A′-1) for comparison prepared in Comparative Examples, (A '-3), (A'-5), molar extinction coefficient, thermal decomposition temperature, solvent solubility of ionic acid generators (A'-2), (A'-4) and (A'-6), Table 2 shows the results of measuring amine resistance by the method described above.
  • the nonionic photoacid generators (A) of Examples 1 to 20 of the present invention have a sufficient molar extinction coefficient at i-line (365 nm) and have good resist curability. I know that there is. Moreover, it is excellent in the solubility with respect to a solvent, and it turns out that handling property is favorable when producing a resist. Moreover, the thermal decomposition temperature is 220 ° C. or higher, and it has sufficient stability. Moreover, since amine tolerance is high, it turns out that the choice of the amine which can be used as a quencher is wide when producing a resist.
  • Comparative Examples 2, 4, and 6 using conventionally known ionic acid generation have low sensitivity to i-line and the resist curability is not sufficient. Further, the nonionic photoacid generators of Comparative Examples 1, 3, and 5 are insufficient in solubility in a solvent. Further, the nonionic photoacid generators of Comparative Examples 1, 3, and 5 have insufficient amine resistance. When a resist having a relatively high pKa such as triethylamine is used, The acid generator may decompose and change over time.
  • the imide sulfonate compound of the present invention is suitable as a photoacid generator for use in positive resists, resist films, liquid resists, negative resists, MEMS resists, photosensitive materials, nanoimprint materials, micro stereolithography materials, and the like. Moreover, the resin composition (Q) for photolithography of this invention is suitable for said use.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne : un générateur de photoacide non-ionique comprenant un composé à base de sulfonate imide et présentant une haute sensibilité de lumière à une i-ligne, une excellente stabilité thermique, et une excellente solubilité dans un matériau hydrophobe; et une composition de résine pour photolithographie le comprenant. La présente invention est un composé sulfonate imide représenté par la formule générale (1). [Dans la formule (1), R1 à R8 sont chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe alkyle ayant 1 à 18 atomes de carbone, un groupe fluoroalkyle ayant 1 à 18 atomes de carbone, etc. Au moins deux de R1 à R8 peuvent être réunis de manière à former une structure cyclique. R9 est un groupe hydrocarboné ayant 1 à 18 atomes de carbone qui peut avoir un substituant (une partie ou la totalité de l'hydrogène peut être substituée par du fluor).]
PCT/JP2015/001406 2014-03-24 2015-03-13 Composé sulfonate imide, générateur de photoacide, et composition de résine pour photolithographie Ceased WO2015146053A1 (fr)

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CN112558409A (zh) * 2019-09-25 2021-03-26 常州强力先端电子材料有限公司 能够在i线高产酸的磺酰亚胺类光产酸剂

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JPH02100054A (ja) * 1988-10-07 1990-04-12 Fuji Photo Film Co Ltd モノマーの製造方法
JPH112901A (ja) * 1996-04-25 1999-01-06 Fuji Photo Film Co Ltd ポジ型感光性組成物
JP2004217748A (ja) * 2003-01-14 2004-08-05 Konica Minolta Holdings Inc 活性光線硬化型インク組成物、それを用いた画像形成方法及びインクジェット記録装置
JP2005314633A (ja) * 2003-09-26 2005-11-10 Dainippon Printing Co Ltd 光ラジカル発生剤、感光性樹脂組成物及び、物品
JP2008266495A (ja) * 2007-04-23 2008-11-06 Sanbo Chemical Ind Co Ltd 光酸発生剤、その製造方法及びフォトリソグラフィ用樹脂組成物
WO2011087011A1 (fr) * 2010-01-13 2011-07-21 株式会社Adeka Nouveau composé dérivé d'acide sulfonique et nouveau composé dérivé d'acide naphtalique
US20110229821A1 (en) * 2008-09-15 2011-09-22 Centre National De La Recherche Scientifique-Cnrs Method of Photochemical Hydrolysis-Polycondensation of Cross-Linkable Chromophores with Steric Hindrance, Catalysed by a Photogenerated Acid, and the Applications Thereof
JP2013001821A (ja) * 2011-06-17 2013-01-07 San Apro Kk 光酸発生剤及びフォトリソグラフィー用樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02100054A (ja) * 1988-10-07 1990-04-12 Fuji Photo Film Co Ltd モノマーの製造方法
JPH112901A (ja) * 1996-04-25 1999-01-06 Fuji Photo Film Co Ltd ポジ型感光性組成物
JP2004217748A (ja) * 2003-01-14 2004-08-05 Konica Minolta Holdings Inc 活性光線硬化型インク組成物、それを用いた画像形成方法及びインクジェット記録装置
JP2005314633A (ja) * 2003-09-26 2005-11-10 Dainippon Printing Co Ltd 光ラジカル発生剤、感光性樹脂組成物及び、物品
JP2008266495A (ja) * 2007-04-23 2008-11-06 Sanbo Chemical Ind Co Ltd 光酸発生剤、その製造方法及びフォトリソグラフィ用樹脂組成物
US20110229821A1 (en) * 2008-09-15 2011-09-22 Centre National De La Recherche Scientifique-Cnrs Method of Photochemical Hydrolysis-Polycondensation of Cross-Linkable Chromophores with Steric Hindrance, Catalysed by a Photogenerated Acid, and the Applications Thereof
WO2011087011A1 (fr) * 2010-01-13 2011-07-21 株式会社Adeka Nouveau composé dérivé d'acide sulfonique et nouveau composé dérivé d'acide naphtalique
JP2013001821A (ja) * 2011-06-17 2013-01-07 San Apro Kk 光酸発生剤及びフォトリソグラフィー用樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112558409A (zh) * 2019-09-25 2021-03-26 常州强力先端电子材料有限公司 能够在i线高产酸的磺酰亚胺类光产酸剂
CN112558409B (zh) * 2019-09-25 2022-05-20 常州强力先端电子材料有限公司 能够在i线高产酸的磺酰亚胺类光产酸剂

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