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WO2007119391A1 - Composition de resist a travail negatif par rayonnement d'energie actinique et produit durci correspondant - Google Patents

Composition de resist a travail negatif par rayonnement d'energie actinique et produit durci correspondant Download PDF

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Publication number
WO2007119391A1
WO2007119391A1 PCT/JP2007/055350 JP2007055350W WO2007119391A1 WO 2007119391 A1 WO2007119391 A1 WO 2007119391A1 JP 2007055350 W JP2007055350 W JP 2007055350W WO 2007119391 A1 WO2007119391 A1 WO 2007119391A1
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group
active energy
formula
ether
photoresist composition
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Japanese (ja)
Inventor
Hideki Kimura
Masashi Date
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San Apro KK
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San Apro KK
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    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/038—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

Definitions

  • Active energy ray negative photoresist composition and cured product thereof Active energy ray negative photoresist composition and cured product thereof
  • the present invention uses a specific fluorinated alkyl fluorophosphate as an active energy ray cationic polymerization initiator, so that the thermal stability is good, the type of the solvent is not selected, and the strength is high. High-productivity, high resolution after development, a thick film, high aspect ratio resist pattern can be obtained, and active energy beam negative photo that can be used as a permanent pattern with high mechanical strength.
  • the present invention relates to a resist composition, a dry film resist, and a cured product obtained by patterning using the resist composition. Background art
  • MEMS micro electro mechanical systems
  • CMOS complementary metal-oxide-semiconductor
  • Semiconductor microfabrication technology is applied to the production of this system.
  • the production is performed by applying a photoresist to a substrate, patterning the coating film by photolithography technology, and using this as a mask for chemical etching. It is done by making full use of elect mouth forming technology such as electrolytic etching or electric plating.
  • the patterned film itself may become a permanent film and become a part of the system structure or parts.
  • Photoresist compositions used for semiconductor microfabrication are suitable for thin film pattern formation, but have thicknesses ranging from several tens to several hundreds / zm required for the production of precision parts used in MEMS, etc.
  • the film is not suitable for pattern formation with a high aspect ratio. This is because, in the case of a thick film where the transparency of the resist composition at the exposure wavelength is low, the light does not reach the lower layer of the resist film, resulting in poor resolution. This is due to factors such as poor drying and the inability to obtain a smooth coating film. Further, since the mechanical strength of the resulting resist pattern is low, the resistance to etching is low, and so-called “permanent pattern” (a pattern formed by resist is used permanently. There is a problem that it cannot be applied to the production of
  • the process for obtaining a resist film is provided with a step of heating (pre-beta step) in order to volatilize the solvent component contained after the resist composition is applied to a substrate.
  • pre-beta step a step of heating
  • the thicker the resist film after coating the more the solvent component in the composition evaporates, and as a result, when the tack (adhesiveness) remains in the coating film, The resist film adheres to the mask used during exposure, and the mechanical strength and resolution of the resist film after the exposure process and the development process are deteriorated.
  • the thermal stability of the resist composition will be low, resulting in partial polymerization and sufficient contrast between the exposed and unexposed areas during development.
  • the resolution is lowered. This is because the active energy ray cation polymerization initiator (mainly OH-SbF salt) contained in the composition decomposes partly at high temperatures, so that the resin in the unexposed part
  • Patent Document 1 where cyclopentanone is used as a solvent.
  • the lower the boiling point of the solvent used the more difficult it is to control the drying property of the coating film. Accordingly, there has been a demand for a resist composition that has excellent thermal stability of the resist composition, high productivity, and excellent resolution after development.
  • the thermal stability of the resist composition increases, the life of the composition itself as a product becomes longer, which is also meaningful in terms of quality control.
  • Patent Document 1 US2005Z0147918
  • Patent Document 2 US2005Z ⁇ 260522
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-250067
  • Patent Document 4 Japanese Patent Laid-Open No. 10-62991
  • Patent Document 5 Patent No. 3033549
  • Patent Document 6 US-2002/0076651 ⁇ -Disclosure of Invention
  • an object of the present invention is to provide an active energy ray negative photoresist composition having good thermal stability.
  • a further object of the present invention is to provide an active energy ray negative photoresist composition having good thermal stability and excellent resolution after development.
  • a still further object of the present invention is to provide an active energy ray negative photoresist composition suitable for obtaining a resist pattern having a thick film and a high aspect ratio.
  • a still further object of the present invention is to provide an active energy ray negative photoresist composition that has good thermal stability and provides strong mechanical strength after development.
  • a still further object of the present invention is to provide a dry film photoresist obtained from the above composition and a cured product obtained by patterning using the same.
  • the present inventors have found that when a compound in the form of a salt of a fluorinated alkyl fluorophosphate cation is used as an active energy ray cationic polymerization initiator, the active sensitivity suitable for the above-mentioned purpose is obtained.
  • the present inventors have found that an energy beam negative photoresist composition can be obtained, and further studied and completed the present invention. That is, the present invention provides the following.
  • An active energy ray negative photoresist composition comprising an active energy ray cationic polymerization initiator (1), a cationic polymerizable compound (2), and a solvent (3).
  • the active energy ray cationic polymerization initiator (1) has the following formula (4),
  • A represents an element of valence m of Group VIA or VIIA (CAS notation)
  • m is 1 or 2
  • n is an integer of 0 to 3
  • R represents an organic group bonded to A, and a plurality of R may be the same or different from each other! /
  • D may be represented by the following formula (5),
  • E represents a divalent group
  • G represents —O—, —S—, —SO—, —SO—, —NH—
  • Rf represents an alkyl group having 1 to 8 carbon atoms in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and b is an integer of 1 to 5.
  • Equation (4) D is the following group:
  • Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms
  • b is 2 or 3, the above 1! Type photoresist composition.
  • the cation polymerizable compound (2) is a bisphenol A novolac resin or a bisphenol F novolac resin having at least two epoxy groups in one molecule, 1 or 6 or 6 of the active energy ray negative photoresist composition.
  • Solvent (3) is at least one selected from the group consisting of methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma-butyral rataton, and propylene glycol monomethyl ether acetate. 7.
  • a positive-sensitive negative-line photoresist composition is at least one selected from the group consisting of methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma-butyral rataton, and propylene glycol monomethyl ether acetate. 7.
  • any of the active energy ray negative photoresist compositions or the dried active energy ray negative photoresist composition of the dry film resist described in 9 above are cured. Become a cured product.
  • an active energy ray negative photoresist composition having good thermal stability can be obtained. Therefore, the pre-beta temperature of the resist film after being applied to the substrate can be increased as compared with the prior art, and the solvent can be volatilized more quickly and reliably, thereby improving the productivity of the resist film.
  • the resist composition of the present invention has high thermal stability, hardly undergoes thermal polymerization during the pre-beta process, and can reliably remove the solvent, thereby improving the resolution when developed. To help.
  • the pre-beta temperature can be increased as compared with the conventional one, which makes it easier to produce a thicker resist film than the conventional one, which helps to obtain a resist pattern with a high aspect ratio.
  • the resist composition of the present invention can be used to obtain a permanent pattern because the cured product has high mechanical strength.
  • the resist composition of the present invention does not contain poisonous metals such as antimony arsenic and is therefore safe to handle and / or the environment.
  • A represents an element of group VIA to VIIA (CAS notation), organic group R and structure Combined with D to form oum [ ⁇ "].
  • S, I and Se which are excellent in force thione polymerization initiation ability, and particularly preferred is thermal. It is an excellent S.
  • m in formula (4) is 1 or 2 which is equal to the valence of element A.
  • R in the above formula (4) is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
  • substituents are alkyl, hydroxy, alkoxy, alkylcarbonyl, aryloylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylothiocarbonyl, acyloxy, arylothio, alkylthio, aryl, heterocyclic ring, May be substituted with at least one selected from the group consisting of aryloxy, alkylsulfiel, arylsulfiel, alkylsulfol, arylsulfol, alkyleneoxy, amide-containing nitro-containing groups and halogen power Good.
  • the number of R is m + n (m— 1) + 1, and the plurality of R may be the same or different from each other. Also, two or more R's can be directly or — 0—, — S—, — SO—, —SO—, — N
  • a ring structure containing element A may be formed by bonding via H, 1 NR, 1, CO, 1 COO, 1 CONH, an ananylene having 1 to 3 carbon atoms, or a phenol group.
  • R is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as a phenol group and naphthyl, anthracel, phenanthryl, pyrel, chrysal, naphthacenyl, Examples thereof include condensed polycyclic aryl groups such as benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone and anthraquinone.
  • examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, and a plurality of heteroatoms are the same.
  • Specific examples that may or may not be monocyclic heterocyclic groups such as chael, furanyl, biranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, birazinyl, and indolyl, benzofuranyl, isobenzo Furanyl, benzocenyl, isobenzothenyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, atalidinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl
  • the alkyl group having 1 to 30 carbon atoms includes a straight chain alkyl group such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and okudadecyl.
  • Branched alkyl groups such as isopropyl, isobutyl, sec butyl, tert butyl, isopentyl, neopentyl, tert pentyl, isohexyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, naphthylmethyl, anthra
  • Examples include aralkyl groups such as senylmethyl, 1-phenylethyl and 2-phenylethyl.
  • the alkenyl group having 2 to 30 carbon atoms includes val, allyl, 1-probe, iso-probe, 1-buturule, 2-butulyl, 3-butenyl, 1-methyl-1-propenyl, 1-Methyl-2-propenyl, 2-Methanol 1-Provenole, 2-Methylanol 2-Probenole, 1-Pentenole, 2-Pentenole, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-2 butyr, 1,2 dimethyl-1-probe, 1-decenyl, 2-decenyl, 8 decenyl, 1 Linear or branched, such as dodecenyl, 2 dodecenyl, 10 dodecenyl, cycloalkyl groups such as 2 cyclohexyl, 3 cyclohexenyl, or arylalkyl groups such as styryl and c
  • alkyl groups having 2 to 30 carbon atoms include: Etul, 1-Provure, 2-Propininole, 1 Butyninole, 2 Butininore, 3 Butyninole, 1-Methinore 2 Propininole ⁇ 1, 1-Dimethyl-2 Propiel, 1-Pentyl -2, 2, 3, 4, 1, 2, 8, 1, 2, 10, 10 And a straight-chain or branched-chain group such as, or an arylalkyl group such as a ferrule.
  • the ru group may have at least one substituent.
  • substituents are straight chain alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, okudadecyl; isopropyl, isobutyl, sec Branched alkyl groups having 1 to 18 carbon atoms such as butynole, tert butinole, isopentinole, neopentinole, tert pentinole and isohexyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; hydroxy Groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec butoxy, tert-butoxy, hexyloxy, de
  • An alkyleneoxy group represented by the above formula (7) (Q represents a hydrogen atom or a methyl group, k is an integer of 1 to 5); an unsubstituted amino group, an alkyl having 1 to 5 carbon atoms, and Z Or an amino group monosubstituted or disubstituted by aryl having 6 to 10 carbon atoms (specific examples of alkyl groups having 1 to 5 carbon atoms are straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl; isopropyl; Branched alkyl groups such as isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, etc.
  • cycloalkyl groups such as cyclopropyl, cyclopropyl, cyclopentyl, etc.
  • aryl groups having 6 to 10 carbon atoms examples include phenyl, naphthyl, etc.); cyano group; nitro group; fluorine , Halogens such as chlorine, bromine and iodine.
  • two or more R's may be directly or — 0—, — S—, — SO—, —SO—, — NH
  • -, -NR '-(R, is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • Specific examples of the alkyl group having 1 to 5 carbon atoms are methyl, ethyl, propyl, butyl And straight chain alkyl groups such as pentyl, etc., branched alkyl groups such as isopropyl, isobutyl, sec butyl, tert-butyl, isopentyl, neopentyl, tert pentyl, etc., and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, etc.
  • aryl groups of ⁇ 10 include phenol, naphthyl, etc.), —CO—, —COO—, —CONH, bonded via an alkylene or phenylene group having 1 to 3 carbon atoms.
  • ring structures containing element A are as follows:
  • A is an element of VIA group to VIIA group (CAS notation)
  • L is —O—, —S—, —SO—, —SO 1, NH—, —NR ′ one, CO 1, COO, or one CONH.
  • R is an element of VIA group to VIIA group (CAS notation)
  • L is —O—, —S—, —SO—, —SO 1, NH—, —NR ′ one, CO 1, COO, or one CONH.
  • E is a divalent group, and is a linear, branched or cyclic alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene; phenylene, xylylene, naphthylene, biphenylene, 6-20 carbon arylene groups such as anthracene; dibenzofurandyl, dibenzothiopheneyl, xanthenezyl, phenoxathiyl, thianthrene dil, bitiofensyl, biflangyl, thixanthone diyl, xanthone diyl, carbazole diyl Represents a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, such as atalidine diyl, phenothiazine diyl, and phenazine diyl.
  • a divalent group of a heterocyclic compound is a divalent group formed by removing one hydrogen atom in each of two ring
  • the divalent group of the alkylene group, arylene group or heterocyclic compound may have at least one substituent.
  • substituent may include methyl, ethyl, propyl, butyl, pentyl, octyl.
  • a linear alkyl group having 1 to 8 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, etc .; a branched alkyl group having 1 to 8 carbon atoms; cyclopropyl, cyclohexyl and the like having 3 to 8 carbon atoms Alkyl groups; alkoxy groups having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, etc .; 6-carbon atoms such as phenol and naphthyl: LO aryl group; hydroxy group; cyano group; nitro group or Examples include halogens such as fluorine, chlorine, fluorine, and iodine.
  • G in the above formula (5) is —O—, —S—, —SO—, —SO—, —NH—, —NR, — (R,
  • a is an integer of 0 to 5.
  • a + 1 E may be the same or different, and a G may be the same or different.
  • n in the formula (4) represents the number of repetitions of [D—A + R 1] units, and is an integer of 0 to 3, preferably 0 or 1.
  • Preferable examples of the atom ion [A +] in the formula (4) are sulfone, odonium, and selenium. Typical examples include the following.
  • sulfone ions include triphenyl sulfone, tri-p-tolyl sulfone, tri-o-tolyl sulfone, tris (4-methoxyphenol) sulfone, 1-naphthyl diphenol.
  • Rusulfol 2 naphthyl diphenyl sulfone, Tris (4 fluorophenol) sulfone, Tri-1-naphthyl sulfone, Tri-2-naphthyl sulfone, Tris (4- Hydroxyphenyl) sulfol, 4-(phenylthio) phenyl diphenylsulfur, 4- (p-tolylthio) phenyl p-tolylsulfol, 4 (4-methoxyphenylthio) phenol (4-Methoxyphenol) sulfo 4- (phenylthio) phenenolebis (4-funoleolophenol) sulfo 4- (phenylthio) phenol Bis (4-methoxyphenol) ) Sulfome, 4-(Fuerthio) Ferrite p Tolyl Sulfol, Bis [4 (Diphenylsulfo-) phenol] sulf
  • the iodine ions include diphenyl rhododonium, di-tritriordonium, bis (4-dodecylphenol) jordonium, bis (4-methoxyphenol) jordanium, (4- (Cutyloxy) Fuel rhodonum, Bis (4 decyloxyfel) rhodonum, 4— (2 Hydroxytetradecyloxy) fuerol rhodonium, 4— Examples thereof include isopropylphenol (p-tolyl) ododonium, isobutylphenol (p-tolyl) ododome, and the like. Macromolecules, 10, 1307 (1977), JP-A-6-184170, US Pat.
  • selenium ions include triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenol) selenium, 1-naphthyldiphenyl selenium, tris (4 fluorophenol) selenium.
  • Triaryl selenium such as diphenyl phenacyl selenium, diphenyl benzene selenium, diphenyl selenium such as diphenyl methyl selenium; phenol methylbenzyl selenium, 4-hydroxyphenol methylbenzyl selenium , Phenylmethylphenacyl selenium, 4-hydride Monoaryl selenium such as roxyphenyl methylphenacyl selenium, 4-methoxymethoxymethyl phenacyl selenium; dimethyl phenyl selenium, phenacyl tetrahydroselenophyl, dimethylbenzyl selenium, benzyltetrahydroselen
  • sulfonium and ododonium preferred are triphenyl sulfone, tri-p-tolyl sulfone, 4- (phenolic) Rudiphenyl sulfone, bis [4- (diphenylsulfo) phenol] sulfide, bis [4- ⁇ bis [4 (2-hydroxyethoxy) phenol] sulfo ⁇ phenol ] Sulfide, Bis ⁇ 4 [Bis (4 fluorophenol) sulfo] phenol ⁇ sulfide, 4 (4-Benzolinole-2—Black-mouthed Fe-Noretio) Fe-Norebis (4-Hunoleo-Headed-Nore ) Snorephonium, 4— (4-Benzylphenol-thiol) phenoldisulfol, 7—Isopropyl-1, 9-oxo-1, Thia-1,9,10 Dihydroanthracene, 2-
  • X- is a pair.
  • X— is a fluorinated alkyl fluorophosphate-one represented by the formula (6), and n + 1 X— may be the same or different from each other.
  • the resist composition of the present invention further contains some amount of other ions unless the object of the present invention is impaired. Any other conventionally known ion can be used, for example, halogen ions such as F-, Cl-, Br-, I-; OH-; CIO-; FSO-, C1SO ⁇ , C
  • Sulfonic acid ions such as H 2 SO—, CH 2 SO—, CF 2 SO—; sulfuric acid such as HSO—, SO 2
  • Acid ions Fluorophosphate ions such as PF— and PF OH—; BF—, B (C F) —, B (C H
  • Fluoroantimonate ions such as bF OH—, or fluorine such as AsF— or AsF OH—
  • Rf is a fluorine atom. It represents an alkyl group substituted with a elementary atom, preferably having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclobutyl.
  • the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. .
  • the fluorine atom substitution rate is less than 80%, the cationic polymerization initiating ability of the salt of the present invention and the salt of the transition metal complex is lowered.
  • Rf is a linear or branched alkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%.
  • Specific examples include CF, CF CF, (CF) CF, CF CF CF
  • the number b of Rf is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.
  • b Rf may be the same or different.
  • the fluorinated alkyl fluorophosphates of the present invention and the transition metal complex may be used alone as a force thione polymerization initiator, or two or more of them may be used alone. May be used together. Moreover, you may use together with another conventionally well-known cationic polymerization initiator.
  • Other powers Thion initiators include, for example, ionic ions such as sulfoyuum, odonium, selenium, ammonium and phospho- um, or transition metal complex ions and various ionic salts. Examples include halogen ions such as F-, Cl-, Br-, I-; OH-; CIO-
  • Sulfonic acid ions such as FSO-, C1SO-, CH SO-, C H SO-, CF SO-; HSO
  • Phosphate ions such as PO 3 ; Fluorophosphate ions such as PF-, PF OH-;
  • Borate ions such as B (C F) —, B (C H CF) —; AlCl—; BiF—; SbF—, SbF OH—
  • Fluoroantimonate ions such as 6 5 4 6 4 3 4 4 6 6 5; Fluoroarsenate ions such as AsF- and AsF OH-
  • fluoroantimonate ions and fluoroarsenate ions are not preferable because they contain toxic elements.
  • ammonia ions examples include tetramethyl ammonium, ethyltrimethyl ammonium, jetyldimethyl ammonium, triethylmethyl ammonium, tetraethyl ammonium, trimethylpropyl ammonium.
  • N Dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N, N Pyrrolidinum such as Jetylpyrrolidinum; N, N '— Dimethinoyl imidazolinum, N, N' — Getinoreyl imidazolinum, N ethyl N '— Methylimidazolium, 1, 2, 3 Trimethyl imida
  • Patent No. 4069055 Patent Publication No. 2519480, JP-A-5-222111, JP-A-5-222111, JP-A-5-262813, JP-A-5-255256, JP-A-5-255256. 7-109303, JP-A-10-101718, JP-A-2-268173, JP-A-9-32 8507, JP-A-5-132461, JP-A-9-221652, JP-A-7-43854, JP 7-43901, JP-A-5-262813, JP-A-4-327574, JP-A-2-433202, JP-A-60-203628, JP-A-57-209931, JP-A-9-221652, etc. Are listed.
  • Examples of the above phosphonium ions include tetraphenyl phosphonium, tetra p-tolyl phosphonium, tetrakis (2-methoxyphenol) phosphonium, and tetrakis (3-methoxyphenyl) phosphones.
  • Tetralinole phosphomes such as -um, tetrakis (4-methoxyphenol) phosphomume; triphenyl pendyl phosphome, triphenylphenacyl phosphine, triphenylmethylphosphome, triphenyl butylphospho Triarinorephosphomumes such as rum; triethylbenzylphosphome, tributylbenzylphosphome, tetraethylphosphome, tetrabutylphosphome, tetrahexylphosphome, Examples thereof include tetraalkylphosphonium such as triethylphenacylphosphome and tributylphenacylphosphome. These are described in JP-A-6-157624, JP-A-5-105692, JP-A-7-82283, JP-A-9 202873, and the like.
  • the amounts of each other The ratio is arbitrary and not limited.
  • the quantity ratio to the fluorinated alkyl fluorophosphate of formula (4) may be arbitrary, but usually the fluorinated alkyl fluoride of formula (4).
  • the other cationic polymerization initiator is 10 to 900 parts by mass, preferably 25 to 400 parts by mass with respect to 100 parts by mass of the olophosphate (in the following description, parts represent parts by mass).
  • arabic tanning solvents are used as the active energy ray cationic polymerization initiator (1). You may use what was dissolved in.
  • solvents include alcohols such as methanol, ethanol, n -propyl alcohol, isopropyl alcohol, n-butanol, and isobutanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, and methyl.
  • Ketones such as n-propyl ketone, cyclopentanone and cyclohexanone; ethers such as jetyl ether, tert-butyl ether, tetrahydrofuran, 1,3 dioxane, 1,4 dioxane; propylene carbonate, ethylene carbonate, 1, 2 —Carbonates such as butylene carbonate, dimethylolate carbonate, and jetinole carbonate; ethyl acetate, lactyl acetate, butyl acetate sorb acetate, carbinol acetate, ⁇ -propiolatathone, j8-butyrolol T, y butyrolatataton, ⁇ valerolatataton, ⁇ -force prolatataton and other esters; ethylene glycol monomethyl etherate, ethylene glycol monoethanolateolate, propylene glycolenolemonomethinoretel, propylene glycol norenomethin
  • the use ratio is usually 15 to L000 parts, preferably 100 parts by weight with respect to 100 parts of the active energy-linear cationic polymerization initiator of (1) of the present invention. Is between 30 and 500cm.
  • Examples of the cationically polymerizable compound (2) in the composition of the present invention include cyclic ether compounds such as epoxide oxetanes, ethylenically unsaturated compounds such as butyl ethers and styrene, and Bicycloorthoesters, spiroorthocarbonates, spiroorthoesters and the like can be mentioned.
  • Examples of the epoxide include conventionally known epoxides, and examples of the aromatic epoxide include monovalent and polyvalent phenols having at least one aromatic ring, such as phenol, tare zonole, xylenol, biphenol, bisphenol.
  • A bisphenol f, triphenol methane, trisole methane, biphenol, tetramethylbiphenol, dihydroxynaphthalene, binaphthol, bis (4-hydroxyphenol) diphenol methane, phenol novolak, xylylene novolak, cresolol novolak, xylenol novolak , Bifuenol novolak, bisphenol A novolak, bisphenol F novolak, triphenol Glycidyl ether of rumethane novolak, dicyclopentadiene phenol novolak, terpene phenol nopolac and brominated compounds thereof or compounds further added with alkylene oxide, and glycidyl monovalent and polyvalent carboxylic acid having at least one aromatic ring Esters such as diglycidyl phthalate, diglycidyl
  • alicyclic epoxide a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent, for example, 3, 4-epoxycyclohexylmethyl-3, 4 —Epoxycyclohexanecarboxylate, 3, 4 Epoxy 1-methylcyclohexylene 3,4 Epoxy 1-methylhexanecarboxylate, 6-Methyl-3,4 Epoxycyclohexyl Methyl-6-methyl-3,4-Epoxycyclohexane Carboxylate, 3, 4 Epoxy 3-Methylcyclohexylmethyl- 3, 4-Epoxy 3-methylcyclohexane force Ruboxylate, 3, 4 Epoxy-5-Methylcyclohexylmethyl- 3, 4-Epoxy 5-methylcyclohexanecarboxylate, 2- (3,4 epoxy cyclohexyl -5, 5-spir
  • oxetanes conventionally known ones such as, for example, 3-ethyl-3-hydroxymethyl oxetane, (3-ethyl-3-oxeta-methoxy) methylbenzene, [1- (3-ethyl-3-oxeta-methoxy) ethyl] phenol ether , Isobutoxymethyl (3-ethyl 3-oxeta-methyl) ether, isobornyl oxychetyl (3-ethyl 3-oxeta-methyl) ether, isobornyl (3-ethyl 3-oxetamethyl) ether, 2-ethyl Xylyl (3ethyl 3-oxeta-methyl) ether, Ethyl diethylene glycol (3-ethyl-3-alkyl ether), Dicyclopentyl (3-ethyl-3-oxeta-methyl) ether, Dicyclopentenyl (3-ethyl)
  • Examples of the ethylenically unsaturated compound include conventionally known cationically polymerizable compounds such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutino levino reetenole, cyclohexino levino reetenole, 2-chloroethinorevinino ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl butyl ether, 2-acetoxetyl butyl ether, diethylene glycol noremonobi-norethenore, 2-ethinorehexino levi Aliphatic monovinyl ethers such as 2-noreatenore, dodecinorebi-noreether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyl oxychetyl butyl ether, 2-ataryl leuoxy schit
  • bicycloorthoesters examples include 1-phenyl 4-ethyl 2, 6, 7 trioxa bicyclo [2. 2. 2] octane, 1-ethyl 4-hydroxymethyl-2, 6, 7 trioxabi cyclo [2. 2. 2] Octane and so on.
  • Spiro orthocarbonates include 1, 5, 7, 11-tetraoxaspiro [5.5] undecane, 3, 9-dibenzyl-1, 5, 7, 11-tetraoxaspiro [5.5] undecane And so on.
  • Spiro orthoesters include 1, 4, 6 trioxaspiro [4. 4] nonane, 2-methyl
  • aromatic epoxides having excellent etching resistance, resistance to plating, and mechanical strength of the resist after pattern formation are preferred.
  • Functionality of epoxy groups in one molecule Bisphenol A novolak or bisphenol F novolac resin having a radix of 2 or more is particularly preferred.
  • These cationically polymerizable compounds may be used alone or in combination of two or more.
  • the active energy-sensitive linear cationic polymerization initiator (1) is used in an amount of usually 0.05 to 30 parts per 100 parts of the cationic polymerizable compound (2) relative to the cationic polymerizable compound (2). However, it is preferably 0.1 to 15 parts. Appropriate use ratios are the properties of the cationic polymerizable compound, the type and irradiation amount of active energy rays, temperature, curing time, humidity, coating thickness, etc. Determined by considering various factors.
  • the proportion of the active energy-sensitive cationic polymerization initiator is less than 0.05 parts, the polymerization of the cationic polymerizable compound is insufficient, and if it is more than 30 parts, it is cured by an unreacted cationic polymerization initiator or its decomposition product.
  • the properties of the product may deteriorate, or the amount of active energy rays absorbed by the cationic polymerization initiator itself may increase, so the curability at the deep part of the coating film may decrease.
  • the solvent (3) is suitable for dissolving the active energy-sensitive cationic polymerization initiator (1) and the cationic polymerizable compound (2) and applying them to the substrate.
  • Liquidity As long as it is possible to obtain a uniform and smooth coating film in the pre-beta (solvent component removal step) and it does not remain in the resist coating film, it may be any material.
  • examples of such a solvent include the same solvents described above as solvents that can be used when dissolving the active energy ray cationic polymerization initiator (1). Also, these solvents can be used alone, or one of them can be used alone, or two or more can be used together.
  • methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma butyrolatatane, or propylene glycol monomethyl ether acetate which can provide fluidity of the composition and a uniform coating film, is preferable.
  • solvents (3) methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma butyrolatatane, or propylene glycol monomethyl ether acetate
  • the use ratio of the solvent (3) is usually 5 to 300 parts, preferably 10 to L00 parts with respect to 100 parts of the cationically polymerizable compound (2).
  • the resist composition of the present invention includes a sensitizer, a pigment, a filler, an antistatic agent, a flame retardant, an antifoaming agent, a flow regulator, a light stabilizer, a solvent, a non-reactive soot as necessary.
  • Additives such as fats and radical polymerizable compounds can be used.
  • a conventionally known sensitizer can be used in combination with the resist composition of the present invention, particularly those cured by irradiation with active energy rays, if necessary. Examples of such sensitizers are described in JP-A-11 279212 and JP-A-09-183960.
  • the use ratio is usually 0.005 to 20 parts, preferably 0.01 to 10 parts, per 100 parts of the resist composition of the present invention.
  • These sensitizers can be used alone, or one of them can be used alone, or two or more can be used together.
  • Examples of the pigment include conventionally known pigments, for example, inorganic pigments such as titanium oxide, iron oxide, and carbon black, and organic pigments such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments. .
  • inorganic pigments such as titanium oxide, iron oxide, and carbon black
  • organic pigments such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments.
  • the ratio of these pigments to be used is generally 0.1 to 300 parts, preferably 1 to 200 parts, per 100 parts of the resist composition of the present invention.
  • these pigments may be used alone or in combination of two or more.
  • filler conventionally known ones such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, slag, talc, calcium silicate, lithium aluminum silicate, etc. Is mentioned.
  • the amount used is usually 10 to 300 parts, preferably 30 to 200 parts, per 100 parts of the resist composition of the present invention.
  • these fillers may be used alone or in combination of two or more.
  • Antistatic agents are conventionally known, for example, glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, ⁇ , ⁇ ⁇ bis (2-hydroxyethyl) alkylamine, polyoxyethylene alkyl.
  • Nonionic type such as amine, polyoxyethylene alkylamine fatty acid ester, alkyldiethanolamide; Alon type such as alkyl sulfonate, alkylbenzene sulfonate, alkyl phosphate; Tetraalkyl ammonia Cation-type salts such as salt, trialkylbenzil ammonium salt; alkylbetaine, alkylimidazole Amphoteric type such as umbetaine; quaternary ammonium group-containing styrene mono (meth) tarylate copolymer, quaternary ammonium group-containing styrene-acrylonitrile-maleimide copolymer and polyethylene oxide, Examples include ionic and nonionic polymer types such as polyether ester amide, polyether amide imide, ethylene oxide-epoxychlorohydrin copolymer, and methoxypolyethylene glycol (meth) acrylate copolymer. It is done.
  • the use ratio is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the resist composition of the present invention. Also, these antistatic agents may be used alone or in combination of two or more.
  • flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide aluminum Inorganic compounds such as magnesium hydroxide and calcium aluminate; bromines such as tetrabromophthalic anhydride, hexabromobenzene and decabromobiphenyl ether; phosphate esters such as tris (tribromophenol) phosphate Things.
  • the use ratio is usually 0.1 to 20 parts, preferably 0.5 to LO parts, with respect to 100 parts of the resist composition of the present invention.
  • These flame retardants may be used alone or in combination of two or more.
  • Conventionally known antifoaming agents for example, alcohols such as isopropanol, n-butanol, octethyl alcohol, hexadecyl alcohol; metal stalagmites such as calcium stearate and aluminum stearate; Phosphate esters such as tributyl phosphate; Fatty acid esters such as glycerin monolaurate; Polyethers such as polyalkylene glycol; Silicones such as dimethyl silicone oil and silica 'silicone compound; Mineral in which silica powder is dispersed Oils.
  • alcohols such as isopropanol, n-butanol, octethyl alcohol, hexadecyl alcohol
  • metal stalagmites such as calcium stearate and aluminum stearate
  • Phosphate esters such as tributyl phosphate
  • Fatty acid esters such as glycerin monolaurate
  • Polyethers such
  • the amount used is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the resist composition of the present invention.
  • These antifoaming agents may be used alone or in combination of two or more.
  • the flow regulator conventionally known ones such as hydrogenated castor oil, acid-polyester are used. Examples thereof include lens, organic bentonites, colloidal silica, amide waxes, metal stannic acids, and acrylate polymers.
  • the amount used is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the resist composition of the present invention.
  • these flow regulators may be used alone or in combination of two or more.
  • ultraviolet absorption types such as benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof
  • radical scavenging types represented by hindered amines
  • nickel Examples include quenching types such as complexes.
  • the use ratio is usually 0.005 to 40 parts, preferably 0.01 to 20 parts, relative to 100 parts of the resist composition of the present invention.
  • these photostabilizers may be used alone or in combination of two or more.
  • the active energy-sensitive negative resist composition of the present invention has a polyfunctional OH group-containing compound, a crosslinking agent, non- A reactive resin or radical polymerizable compound can be added.
  • polyfunctional OH-containing compounds include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3 butanediol, 1, 4 -Butanediol, 1,6 hexanediol, 1,2,4 butanetriol, 1,2 cyclohexanediol, 1,3 cyclohexanediol, 1,4-cyclohexanediol, 1,2 cyclohexanedi Methanol, 1,4-cyclohexanedimethanol, 1,3,5-cyclohexane trimethanol, 1,2 cyclopentanediol,
  • crosslinking agent examples include conventionally known amino compounds such as melamine resin, urea resin, guanamine resin, glycoluril formaldehyde resin, succinamide-formaldehyde resin, ethylene urea-formaldehyde resin.
  • methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethyliurea resin, ethoxymethylated urea resin, propoxymethyliurea Resins, alkoxymethylated melamines such as butoxymethyl iurea resins, and the like can be suitably used.
  • non-reactive resin examples include polyester, polyacetate butyl, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polybutyl ether, polybutyl propylal, polybutene, hydrogenated styrene butadiene block copolymer, ( Examples thereof include a copolymer of (meth) acrylic acid ester and polyurethane.
  • the number average molecular weight of these coconut resins is 1000 to 500000, preferably 5000 to 100000 (the number average molecular weight is measured by a general method such as GPC).
  • radical polymerizable compounds are “Photopolymer Handbook” (1989, Industrial Research Committee) edited by Photopolymer Social Meeting, “UV'EB Curing Technology” (1982, General Technology). Surgery Center), Radtech Study Group “UV'EB Curing Materials” (1992, CM1), Technical Information Association “UV Curing Failure Inhibition Causes and Countermeasures” (2003, Technical Information Association) It is described in.
  • the use ratio is usually 1 to: 100 parts per 100 parts of the composition of the present invention. Parts, preferably 5 to 50 parts. Further, any one of these polyfunctional OH group-containing compounds, crosslinking agents, non-reactive resins, and radical polymerizable compounds may be used alone or in combination of two or more. Well, ...
  • radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight thereof by radical polymerization.
  • radical polymerization initiators include conventionally known ones.
  • thermal radical polymerization initiator examples include organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 2 , 2-bis (te rt butylperoxy) butane, peroxyketals such as 1, 1 bis (tert butylperoxy) cyclohexane, tert butyl hydride peroxide, cumene hydride peroxide, etc.
  • organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 2 , 2-bis (te rt butylperoxy) butane, peroxyketals such as 1, 1 bis (tert butylperoxy) cyclohexane, tert butyl hydride peroxide, cumene hydride peroxide, etc.
  • Dialkyl peroxides such as oxides, disilver oxides such as isobutyryl peroxide, lauroyl peroxide, and benzoyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, tert butylperoxyiso Peroxyesters such as thiolate, 2,5 dimethyl-2,5 di (benzoylperoxy) hexane, and azo compounds such as 1,1, -azobis (cyclohexane—one strength rubonitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4 dimethyl-4-methoxyvalero-tolyl), 2,2,1azobis (2-methylpropionamidine) dihydride chloride, 2, 2, -azobis [2-methyl-N- (2-probe) propionamidine] dihydrochloride, 2,2, -azobis (2-methylpropionamide), 2, 2, -azobis [2-methyl-N- ( 2-hydroxyethyl
  • Photo radical polymerization initiators include acetophenone, p-tert butyltrichloroacetophenone, 2, 2-diethoxyacetophenone.
  • Acetophenone compounds such as benzophenone, o Benzophenone compounds such as methyl benzoylbenzoate, 4 benzoyl 4, 4-methyldiphenylsulfide, 4, 4, bis (dimethylamino) benzophenone, 4, 4, 1bis (jetylamino) benzophenone, etc.
  • Michler's ketone compounds such as benzoin and benzoin methyl ether
  • benzoin compounds such as benzoin and benzoin methyl ether
  • thixanthone 2-methylthioxanthone, 2-ethylthioxanthone, 2 cyclothioxanthone, 2 isopropinoretioxanthone, 2,4 jetinorexanthone Thioxanthone compounds
  • isacylphosphine compounds such as monoacylphosphine oxide and bisacylphosphine oxide.
  • radical polymerization initiators is usually 0.01 to 20 parts, preferably 0.1 to L0 parts with respect to 100 parts of the radical polymerizable compound.
  • radical polymerization initiators may be used alone or in combination of two or more.
  • the preparation of the active energy-sensitive negative resist composition of the present invention can be performed by mixing and stirring by a usual method, and using a disperser such as a dissolver, a homogenizer, or a three-roll mill. You may mix. You may heat as needed. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.
  • a disperser such as a dissolver, a homogenizer, or a three-roll mill. You may mix. You may heat as needed. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.
  • a resist film is formed by applying the active energy ray negative resist composition of the present invention to a substrate, and heating and drying (pre-beta) the substrate coated with the resist composition.
  • a step of selectively exposing the obtained resist film in accordance with a desired pattern using active energy rays, a step of improving the contrast by heat-treating the exposed resist film (PEB), and a heat treatment A good pattern can be formed by developing the subsequent resist film and dissolving and removing the unexposed resist material to obtain a pattern layer. Especially, a pattern with a thick film and a high aspect ratio can be obtained. It is possible.
  • the resist composition of the present invention is applied to a substrate.
  • a substrate There are no particular restrictions on the coating method. Screen coating methods such as curtain coating, blade coating, spin coating, spray coating, dip coating, and slit coating can be applied. Since the resist composition of the present invention can be made into a high concentration resist solution, it can be applied to a thick film by a simple method such as spin coating.
  • the support substrate to which the resist composition of the present invention is applied and the surface state thereof are not particularly limited. Examples of the supporting substrate include silicon, glass, metal, ceramic, and organic polymer. These supporting base materials can also be subjected to pretreatment of the base material for the purpose of improving adhesiveness. For example, improvement of adhesiveness can be expected by performing silane treatment.
  • (B) Drying of coating film The substrate coated with the resist composition of the present invention in the above step is dried by heating (pre-beta) to obtain a resist film.
  • the temperature varies depending on the type and proportion of each component in the composition of the present invention, the coating film thickness, etc. Preferred to do ,. Usually, it is 60 to 160 ° C, preferably 70 to 140 ° C for about 1 minute to 5 hours. If the drying temperature is too high, the composition may cause a thermal reaction, which may cause defects in pattern formation.
  • the thickness of the resist film is not particularly limited, and is usually about several to zm to several mm. Even a thick film of 50 / zm or more can be processed with high accuracy in the subsequent steps. A particularly preferred film thickness is 50 m to 2 mm.
  • (C) Active energy ray irradiation The resist film obtained in the above step is selectively exposed to an active energy ray in accordance with a desired pattern.
  • the active energy line used for the exposure is not particularly limited. Examples of these active energy rays include ultraviolet rays, visible rays, far ultraviolet rays, near ultraviolet rays, X-rays, electron beams, and the like.
  • As a source of these active energy lines low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressures, etc.
  • Active energy rays in the ultraviolet to visible light region (about 100 to about 800 nm) obtained from the above are used.
  • the amount of active energy ray irradiation varies depending on the type of each component in the composition, the blending amount, and the film thickness of the coating film. For example, when using an ultrahigh pressure mercury lamp, it is 100 to 5000 miZcm2.
  • This heat treatment step is performed at a temperature within a range where the unexposed portion of the resist does not cause a thermal reaction and becomes insoluble in the developer. And need to be done in time.
  • a preferred temperature is 70 to 170 ° C, more preferably 80 to 150 ° C, and a preferred time is 0.5 minutes to 5 hours. If the temperature is too low or the time is too short, the contrast will be insufficient, and if the temperature is too high or if the time is too long, problems such as insolubilization of unexposed areas in the developer will occur.
  • a pattern layer is obtained by developing the resist film that has been heat-treated in the above-described step and dissolving and removing the resist material in the unexposed areas.
  • the developer is not particularly limited as long as it is a solvent that dissolves and removes the negative resist in the unexposed areas.
  • propylene glycol monoalkyl ether such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.
  • Lactic acid alkyl esters such as acetates, methyl lactate and ethyl lactate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ethylene glycol monomethino ethenole, ethylene glycol monoethanol Ethylene glycol monoalkyl ethers such as ethynole etherenole, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl etherenoate acetate, etc.
  • Glyconomonomonoalkyl ether acetates 2-heptanone, ⁇ -butyrolatatane, alkyl alkoxypropionates such as methyl methoxypropionate, ethyl ethoxypropionate, pyruvate alkyl esters such as methyl pyruvate, ethyl pyruvate, Examples thereof include ketones such as methyl ethyl ketone, cyclopentanone and cyclohexanone, ⁇ -methylpyrrolidone, ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylacetamide, dimethyl sulfoxide, propylene carbonate and diacetone alcohol.
  • alkaline aqueous solution developers include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, ⁇ -propylamine, jetylamine, — ⁇ —propylamine, triethylamine, methyljetylamine, dimethylethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5. 4.0 ] -7-Undecene, 1,5-Diazabicyclo [4. 3.
  • —5-Nonane and other alkaline aqueous solutions can be used.
  • an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the alkaline aqueous solution.
  • a caloric aqueous solution as a developer.
  • these developers ⁇ -petit-mouth rataton, propylene glycol monomethyl ether acetate, and the like are particularly preferable.
  • any of a spray method, a paddle method, an immersion method, and the like may be used, but the immersion method is preferable because there is little pattern destruction such as peeling of the pattern.
  • an ultrasonic wave etc. can also be irradiated as needed.
  • a rinsing step is preferably performed after development as necessary, the rinsing step, the rinsing liquid, and the rinsing method can be performed with known liquids and methods without particular limitations.
  • the resist pattern can be heated under known conditions to further advance the curing and thereby stabilize the pattern.
  • the resist composition can be applied by a simple method such as spin coating with high film thickness accuracy and high film thickness controllability, and exposure is performed according to the desired pattern accuracy.
  • a light source can be selected, batch exposure using a photomask or the like is possible, and a resist pattern having a high exposure accuracy with a short exposure time, high productivity, high turnability, and a high aspect ratio can be obtained.
  • the resist pattern obtained from the resist composition of the present invention can be a thick permanent film, it can also be used as a component such as an electronic component, an optical component, or a biochip. Of course, there are various uses because the pattern can be a non-thick film.
  • the resist pattern obtained by the pattern forming method can be used as a component such as MEMS.
  • the resist pattern can be used for an original application of a resist that forms another pattern via the resist pattern.
  • a wiring pattern can be formed.
  • the ability to etch the copper foil by contacting with a chemical solution such as acid is very stable against the chemical solution, so it has good resistance as an etching mask. Therefore, a wiring pattern can be formed.
  • the resist pattern obtained by the pattern forming method can be used as a solder mask.
  • an electronic component is connected to the obtained wiring board by soldering using a jet soldering method or a reflow soldering method. Is formed. Since the resist pattern formed according to the present invention is thermally stable and exhibits good resistance as a solder mask, an electronic circuit unit can be formed.
  • the second pattern layer it is also possible to provide another material at least in the concave portion of the pattern layer formed by the above method to form the second pattern layer.
  • a metal is used as the other material, for example, if it is provided by a plating process, a composite structure of a resist pattern layer and a metal pattern layer can be obtained.
  • the method of the plating process is not particularly limited, but the electrolytic plating method is preferable.
  • a method of performing metal plating such as copper, nickel, silver, gold, solder, copper Z-nickel multilayer, or a composite system of these, known methods can be used. For example, “Surface Treatment Technology Overview” (Technical Data Center Co., Ltd., 1987Z12Z21 first edition, pages 281 to 422).
  • the electrolytic plating method it is preferable that the surface of the supporting substrate on which the active energy ray negative resist composition is applied is conductive because the electrolytic plating process can be easily performed.
  • a resin can be used as a material for forming the second pattern layer.
  • a light or thermosetting resin is provided by a casting method or a coating method, and then light or heat is used.
  • the second pattern layer is formed by curing the resin, the composite structure of the resist pattern layer and the resin pattern layer can be obtained.
  • the light or thermosetting resin is not particularly limited, but for example, the use of light or thermosetting PDMS (polydimethylsiloxane) is particularly preferable because it is easily cured by light or heat.
  • the composition of the present invention can also be used for forming a resist film (photosensitive layer) of a dry film resist.
  • a dry film resist is obtained by forming a resist film (photosensitive layer) on a support such as a polymer film as a base material.
  • the film thickness of the resist film formed using the composition of the present invention is not particularly limited and is usually several; zm to several mm. Even a thick film of 50 ⁇ m or more can be processed accurately in the subsequent steps. can do.
  • a particularly preferred film thickness is 50 / ⁇ ⁇ to 2 ⁇ .
  • polymer film used for the support examples include, for example, polyethylene terephthalate, polyester resin such as aliphatic polyester, Examples thereof include films made of polyolefin resin such as pyrene and low density polyethylene, and among these, films made of polyester and low density polyethylene are preferred. Further, since these polymer films need to be removed from the resist film (photosensitive layer) later, it is preferable that these polymer films can be easily removed from the resist film (photosensitive layer).
  • the thickness of these polymer films is usually 5 to: LOO ⁇ m, preferably 10 to 30 ⁇ m.
  • the dry film resist can be produced by a resist film (photosensitive layer) forming step in which the composition is applied onto a support and dried. Also, by providing a cover film on the formed resist film (photosensitive layer), a support, a photosensitive layer, and a cover film are sequentially laminated, and a dry film resist having films on both sides of the resist film (photosensitive layer). Can also be manufactured. Force Bar film is peeled off when using dry film resist. By using a cover film on the resist film (photosensitive layer) before use, the resist film (photosensitive layer) can be protected and has excellent pot life. It becomes a dry film resist.
  • the cover film may be the same as the polymer film used for the support described above, and the cover film and the support may be the same material or different materials, and the thickness may also be different. Even if they are the same, they can be different! / ⁇ .
  • a bonding step of bonding the resist film (photosensitive layer) of the dry film resist and the substrate is performed.
  • the cover film is peeled off to expose the resist film (photosensitive layer), and then brought into contact with the substrate.
  • the resist film (photosensitive layer) and the substrate are thermocompression bonded at about 40 to 120 ° C. using a pressure roller or the like, and the resist film (photosensitive layer) is laminated on the substrate.
  • the actinic light used for exposure, the developer, and the thermosetting process conditions of the resist film can be used in the same manner as described above.
  • tris (pentafluoroethyl) difluorophosphorane gas chromatographic purity 97%, yield 72%) was synthesized by electrofluorination of triethylphosphine.
  • Tris-heptafluoropropyl difluorophosphorane (gas chromatographic purity 89%, yield 52%) was synthesized by electrolytic fluorination of tris-n-propylphosphine according to US Pat. No. 6,264,818.
  • a reaction vessel was charged with 24.24 g of diphenylsulfoxide, 18.6 g of diphenylsulfide, and 86. Og of methanesulfonic acid, mixed uniformly, and then 15.8 g of acetic anhydride was added dropwise. After reacting at 40-50 ° C for 5 hours, it was cooled to room temperature. The reaction solution was added dropwise to entering a port was containers 20 mass 0/0 aqueous solution 249g of tri scan potassium (penta Full O Roe chill) Torifuruororin acid created in the Production Example 1, and stirred well for 1 hour at room temperature.
  • the yellowish slightly viscous oil Extraction was performed with 240 g of ethyl acetate, the aqueous layer was separated, and the organic layer was washed 3 times with 200 g of water. The solvent was distilled off from the organic layer, and 80 g of toluene was added to the resulting yellow residue to dissolve it. In order to remove impurities such as unreacted raw materials and by-products, 600 g of hexane was added to this toluene solution, and the mixture was allowed to stand after stirring well at 10 ° C for 1 hour. Since the solution was separated into two layers, the upper layer was removed by liquid separation.
  • Tris (penta Full O Roe chill) 20 Weight 0/0 aqueous solution of tris (hepta full O b propyl) potassium Torifuruororin acid except that 20 mass 0/0 aqueous solution 326g of potassium Torifuruororin acid in the same manner as in Preparation Example 3
  • 53.8 g of 4- (phenylthio) phenol disulfol sulfomutris (heptafluoropropyl) trifluorophosphate was obtained.
  • the compound was identified by 1 H, 13 C, 19 F and 31 P-NMR.
  • Each component was mixed in the ratio shown in Table 1 to prepare a uniform active energy-sensitive linear resist composition.
  • P—2 50% of a mixture of 4 (phenylthio) phenylsulfo-hexafluoroantimonate and Thioji P-phenylenebis (diphenylsulfo-um) bis (hexafluoroantimonate) Propylene carbonate solution [trade name: UVR-6974, manufactured by Dow Chemical Company]
  • the resist compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were applied on a silicon substrate under conditions such that the film thickness was 100 m using a spin coater. Dried on a 90 ° C and 150 ° C hot plate. Weigh the silicon substrate during drying at regular intervals, measure the time until the weight loss is eliminated, and judge according to the following evaluation criteria.
  • the active energy ray negative resist compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were applied on a silicon substrate by a spin coater, then dried on a hot plate at 90 ° C. for 110 minutes, and 100 m thick. A resist film was obtained. A resist film was obtained in the same manner by changing the drying temperature to 150 ° C and the drying time to 30 minutes. The coatability of the obtained resist film was visually observed and judged according to the following evaluation criteria.
  • the obtained coating film is uniform and uniform.
  • the obtained coating film has unevenness such as pinholes and repellency.
  • the resist films of Examples 1 and 2 and Comparative Examples 1 to 3 obtained in the above coating property test were irradiated through a mask using a high-pressure mercury lamp as a light source (exposure amount: 1000 miZcm2). Thereafter, heat treatment was performed on a hot plate at 100 ° C. for 10 minutes, followed by development by immersing in propylene glycol monomethyl ether acetate for 30 minutes to obtain a resist pattern. The obtained resist pattern was observed with an optical microscope and judged according to the following evaluation criteria.
  • ⁇ No pattern meandering or surface wrinkles due to swelling.
  • a pattern with a mask line width of 10 ⁇ m is resolved (aspect ratio 10).
  • the coating film was exposed with a high-pressure mercury lamp without using a mask, and then heat-treated on a 100 ° C hot plate for 10 minutes to form a cured coating film. Obtained. The surface of the coating film after rubbed the cured coating film 20 times with absorbent cotton soaked with methyl ethyl ketone was observed and judged according to the following evaluation criteria.
  • ⁇ The surface is glossy with scratches.
  • Viscosity change from initial viscosity is less than 2 times
  • Viscosity change from initial viscosity is 2 times or more
  • Table 2 shows the results of the above tests.
  • Comparative example 90 ⁇ o o ⁇ ⁇ X hole (S b) 1 1 50 ⁇ ⁇ ⁇ ⁇ ⁇
  • the resist composition of the present invention has a good resist pattern forming property even when the pre-beta temperature is high (150 ° C), and does not contain antimony.
  • the mechanical strength of the membrane is high. Furthermore, as a result of the high thermal stability of the resist composition, it is excellent in storage stability.
  • the present invention has good thermal stability, can increase the pre-beta temperature, improve the productivity of the resist film, and can improve the resolution of the pattern when developed, and a sensitive energy.
  • Useful as a line negative photoresist composition Useful as a line negative photoresist composition.
  • the present invention is also suitable for creating a permanent pattern because the strength of the cured product is high, and a pattern with a higher aspect ratio can be created by increasing the film thickness than in the past. It is also useful for producing optical parts, biochip parts and the like. In addition, since it does not contain toxic metals such as arsenic antimony, it has the advantage of being safe to handle and the environment.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une composition de résist à travail négatif par rayonnement d'énergie actinique qui est dépourvue de tout élément toxique, a une bonne stabilité thermique et a une excellente résolution. La composition comprend un sel d'onium fluoré d'acide alkylfluorophosphorique, en tant qu'initiateur de polymérisation cationique représenté par la formule (4), dans laquelle A représente un élément du groupe VIA ou VIIA (notation CAS) ayant une valence de m; m vaut de 1 à 2, n vaut de 0 à 3, R représente un groupe organique, D est représenté par la formule (5), E représente un groupe ayant un groupe divalent, G représente -O-, -S-, -SO-, -SO2-, -NH-, -NR'-, -CO-, -COO-, -CONH, un groupe alkylène ayant de 1 à 3 atomes de carbone ou un groupe phénylène, a vaut de 0 à 5, X- est représenté par la formule (6), Rf représente un groupe alkyle dans lequel pas moins de 80 % des atomes d'hydrogène ont été substitués par un atome de fluor, et b vaut de 1 à 5. La composition comprend en outre un composé polymérisable par polymérisation cationique et un solvant.
PCT/JP2007/055350 2006-03-22 2007-03-16 Composition de resist a travail negatif par rayonnement d'energie actinique et produit durci correspondant Ceased WO2007119391A1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008090768A1 (fr) * 2007-01-24 2008-07-31 Tokyo Ohka Kogyo Co., Ltd. Composition de résine photosensible et procédé destiné à former un motif à partir de celle-ci
JP2008180877A (ja) * 2007-01-24 2008-08-07 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物、及びこれを用いたパターン形成方法
JP2008180878A (ja) * 2007-01-24 2008-08-07 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物、及びこれを用いたパターン形成方法
WO2008152834A1 (fr) * 2007-06-14 2008-12-18 Omron Corporation Composition durcissable et dispositif optique obtenu à partir de celle-ci
JP2009075284A (ja) * 2007-09-20 2009-04-09 Jsr Corp 感放射線性樹脂組成物、液晶表示素子のスペーサーおよび保護膜ならびにそれらの形成方法
JP2009180949A (ja) * 2008-01-31 2009-08-13 Jsr Corp 着色層形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子
WO2009125677A1 (fr) * 2008-04-08 2009-10-15 コニカミノルタオプト株式会社 Procédé de fabrication d’une lentille de tranche et lentille de tranche
WO2010001919A1 (fr) * 2008-07-02 2010-01-07 日本化薬株式会社 Composition de résine photosensible pour des microsystèmes électromécaniques et son produit durci
JP2010008972A (ja) * 2008-06-30 2010-01-14 Jsr Corp メッキ造形物製造用ポジ型感放射線性樹脂組成物、転写フィルムおよびメッキ造形物の製造方法
JPWO2022018968A1 (fr) * 2020-07-23 2022-01-27
US20230041025A1 (en) * 2019-10-08 2023-02-09 Tokyo Ohka Kogyo Co., Ltd. Negative-working photosensitive resin composition, photosensitive resist film, pattern formation method, cured film, cured film production method, and rolled body

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JPH05188593A (ja) * 1991-07-15 1993-07-30 Internatl Business Mach Corp <Ibm> フォトイメージング用の改良された組成物
WO2005116038A1 (fr) * 2004-05-28 2005-12-08 San-Apro Limited Nouveau sel d'onium et de complexe de métal de transition d'un acide alkylfluorophosphorique fluoré

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JPH05188593A (ja) * 1991-07-15 1993-07-30 Internatl Business Mach Corp <Ibm> フォトイメージング用の改良された組成物
WO2005116038A1 (fr) * 2004-05-28 2005-12-08 San-Apro Limited Nouveau sel d'onium et de complexe de métal de transition d'un acide alkylfluorophosphorique fluoré

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8288078B2 (en) 2007-01-24 2012-10-16 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition, and pattern formation method using the same
JP2008180877A (ja) * 2007-01-24 2008-08-07 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物、及びこれを用いたパターン形成方法
JP2008180878A (ja) * 2007-01-24 2008-08-07 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物、及びこれを用いたパターン形成方法
WO2008090768A1 (fr) * 2007-01-24 2008-07-31 Tokyo Ohka Kogyo Co., Ltd. Composition de résine photosensible et procédé destiné à former un motif à partir de celle-ci
WO2008152834A1 (fr) * 2007-06-14 2008-12-18 Omron Corporation Composition durcissable et dispositif optique obtenu à partir de celle-ci
JP2008308589A (ja) * 2007-06-14 2008-12-25 Omron Corp 硬化性組成物およびこれを用いた光学デバイス
JP2009075284A (ja) * 2007-09-20 2009-04-09 Jsr Corp 感放射線性樹脂組成物、液晶表示素子のスペーサーおよび保護膜ならびにそれらの形成方法
JP2009180949A (ja) * 2008-01-31 2009-08-13 Jsr Corp 着色層形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子
WO2009125677A1 (fr) * 2008-04-08 2009-10-15 コニカミノルタオプト株式会社 Procédé de fabrication d’une lentille de tranche et lentille de tranche
JP2010008972A (ja) * 2008-06-30 2010-01-14 Jsr Corp メッキ造形物製造用ポジ型感放射線性樹脂組成物、転写フィルムおよびメッキ造形物の製造方法
WO2010001919A1 (fr) * 2008-07-02 2010-01-07 日本化薬株式会社 Composition de résine photosensible pour des microsystèmes électromécaniques et son produit durci
JP2010032991A (ja) * 2008-07-02 2010-02-12 Nippon Kayaku Co Ltd Ｍｅｍｓ用感光性樹脂組成物及びその硬化物
US20230041025A1 (en) * 2019-10-08 2023-02-09 Tokyo Ohka Kogyo Co., Ltd. Negative-working photosensitive resin composition, photosensitive resist film, pattern formation method, cured film, cured film production method, and rolled body
JPWO2022018968A1 (fr) * 2020-07-23 2022-01-27
WO2022018968A1 (fr) * 2020-07-23 2022-01-27 サンアプロ株式会社 Générateur de photoacide
JP7715713B2 (ja) 2020-07-23 2025-07-30 サンアプロ株式会社 光酸発生剤

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