WO2007046442A1 - Nouveau composé, générateur d'acide, composition de vernis photorésistant de type à amplification chimique, stratifié ayant une couche de réserve et procédé de formation d'une impression de réserve - Google Patents

Nouveau composé, générateur d'acide, composition de vernis photorésistant de type à amplification chimique, stratifié ayant une couche de réserve et procédé de formation d'une impression de réserve Download PDF

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Publication number
WO2007046442A1
WO2007046442A1 PCT/JP2006/320779 JP2006320779W WO2007046442A1 WO 2007046442 A1 WO2007046442 A1 WO 2007046442A1 JP 2006320779 W JP2006320779 W JP 2006320779W WO 2007046442 A1 WO2007046442 A1 WO 2007046442A1
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WIPO (PCT)
Prior art keywords
group
photoresist composition
aromatic ring
resist layer
acid
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PCT/JP2006/320779
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English (en)
Japanese (ja)
Inventor
Koji Saito
Hideo Hada
Yasushi Washio
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Tokyo Ohka Kogyo Co., Ltd.
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Priority claimed from JP2005304123A external-priority patent/JP4828201B2/ja
Priority claimed from JP2005303926A external-priority patent/JP4823640B2/ja
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2007046442A1 publication Critical patent/WO2007046442A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • 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
    • 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
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • the present invention relates to a novel compound, an acid generator, a chemically amplified photoresist composition, a resist layer laminate, and a resist pattern forming method.
  • Photophoto application is the application of a photosensitive resin composition such as photoresist to the surface of a workpiece to form a coating film, which is a photolithography technology.
  • This is a generic term for technologies for manufacturing various precision parts such as semiconductor packages by patterning the coating film by using the mask as a mask and performing chemical etching, electrolytic etching, and elect mouth forming mainly consisting of Z or electrical plating. .
  • connection terminals for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts that connect the rewiring extending from the peripheral terminals on the wafer and the mounting terminals. are placed on the board with high accuracy.
  • connection terminals are formed by, for example, forming a resist layer made of a photoresist on a support, exposing through a predetermined mask pattern, developing, and selectively removing (peeling off) portions where connection terminals are to be formed. After the resist pattern is formed, a conductor such as copper is buried in the removed portion (non-resist portion) by plating, and the surrounding resist pattern is removed.
  • the resist pattern is mainly formed using a photopolymerizable photosensitive resin composition as described in Patent Documents 1 to 3, for example, as a photoresist. It is performed using light in a long wavelength region, for example, light in the ultraviolet region such as g-line (436 nm), h-line (405 nm), i-line (365 nm).
  • the feature of chemically amplified photoresist is that the acid generator absorbs the irradiated radiation to generate an acid, and the acid generated from the acid generator causes an acid-catalyzed reaction to the base resin in the photoresist. , Changing its alkali solubility. Chemically amplified photoresists are classified into positive types that are alkali-insoluble when exposed to radiation and negative types that are alkali-insoluble when alkali-soluble.
  • Acid generators used in chemically amplified photoresists include sulfo-acid salt acid generators, onium salt-based acid generators such as iodine salt-based acid generators, oxime sulfonate-based acid generators, Various proposals such as imidosulfonate acid generators have been made.
  • onium salt-based acid generators use photons with wavelengths shorter than those of i-line, such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm). It is currently most commonly used because of its high sensitivity in lithography.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-207057
  • Patent Document 2 JP 2000-39709 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2000-66386
  • the form salt acid generator hardly absorbs in a long wavelength region of 365 nm or more. Therefore, in photo-applications in the long wavelength region of 365 nm or more, the present situation is that chemically amplified photoresists using an acid salt-based acid generator have low sensitivity and cannot be practically used.
  • a highly hydrophobic cation such as trisulfolsulfum is generally used, but an onium having a strong cation.
  • the salt-based acid generator also has a problem of low solubility in an organic solvent (resist solvent) used for dissolving various components of the resist. Such low solubility in a resist solvent reduces the temporal stability of the resist, and accordingly causes a bad pattern pattern.
  • the present situation is that chemically amplified photoresists using an acid salt-based acid generator as an acid generator cannot be used practically for photo applications in the long wavelength region of 365 nm or more.
  • the present invention has been made in view of the above circumstances, and exhibits high absorption in a long wavelength region of 365 nm or more and excellent solubility in an organic solvent having high sensitivity in a long wavelength region of 365 nm or more. It is an object to provide a compound, an acid generator comprising the compound, a chemically amplified photoresist composition containing the acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a method for forming a resist pattern. And
  • the present invention also includes a sulfo salt salt acid generator as an acid generator and high sensitivity in a long wavelength region of 365 nm or more, a chemically amplified photoresist composition, and the chemically amplified photoresist composition. It is another object of the present invention to provide a resist layer laminate and a resist pattern forming method using the above.
  • the first aspect of the present invention is a compound represented by the following general formula (B1).
  • R ⁇ R 2 and R 3 are each independently a group represented by the following general formula (Bla), an alkyl group, or a group obtained by removing one hydrogen atom from an aromatic ring.
  • the aromatic ring may have a substituent, and at least one of R 2 and R 3 is a group represented by the following general formula (Bla); ]
  • Y is a group obtained by removing two hydrogen atoms from an aromatic ring, and the aromatic ring may have a substituent; Z is a group obtained by removing one hydrogen atom from the aromatic ring.
  • the aromatic ring may have a substituent; the aromatic ring in at least one of Y and Z has at least one alkoxy group.
  • the second aspect of the present invention is the acid generator having the compound power of the first aspect.
  • a third aspect of the present invention is a chemically amplified photoresist composition
  • a chemically amplified photoresist composition comprising (a) a resin whose alkali solubility is changed by an acid, and (b) a compound which generates an acid upon irradiation.
  • the (b) compound capable of generating an acid upon irradiation contains the acid generator according to the second aspect, which is a chemically amplified photoresist composition.
  • a fourth aspect of the present invention is a resist layer laminate characterized in that a resist layer comprising the chemically amplified photoresist composition of the third aspect is laminated on a support. is there.
  • a fifth aspect of the present invention includes a laminating step of laminating a resist layer having a chemically amplified photoresist composition on a support to obtain a resist layer laminate of the fourth aspect, and the resist layer
  • a resist pattern forming method comprising: an exposure step of selectively irradiating a laminate with radiation; and a development step of developing after the exposure step to obtain a resist pattern.
  • a sixth aspect of the present invention includes (a) a resin whose alkali solubility is changed by an acid, (b) a compound that generates an acid upon irradiation, and (c) the following general formula (C1 )
  • a chemically amplified photoresist composition characterized in that the compound (b) that generates an acid upon irradiation with radiation contains a sulfonium salt-based acid generator (b-1). .
  • a resist characterized in that a resist layer comprising the chemically amplified photoresist composition of the sixth aspect is laminated on a support. Layer stack.
  • An eighth aspect of the present invention includes a laminating step of laminating a resist layer comprising a chemically amplified photoresist composition on a support to obtain a resist layer laminate of the seventh aspect, and the resist
  • a resist pattern forming method comprising: an exposure step of selectively irradiating a layer stack with radiation; and a development step of obtaining a resist pattern by imaging after the exposure step.
  • a compound exhibiting high absorption in a long wavelength region of 365 nm or more, high sensitivity in a long wavelength region of 365 nm or more, and excellent solubility in an organic solvent, an acid comprising the compound It is possible to provide a generator, a chemically amplified photoresist composition containing the acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a method for forming a resist pattern.
  • a chemically amplified photoresist composition containing a sulfo salt salt acid generator as an acid generator and having high sensitivity in a long wavelength region of 365 nm or more, A resist layer laminate using the chemically amplified photoresist composition and a method for forming a resist pattern can be provided.
  • compound (B1) The compound of the first aspect of the present invention (hereinafter sometimes referred to as compound (B1)) is represented by the above general formula (B1).
  • R 2 and R 3 each independently represent a group represented by the above general formula (Bla), an alkyl group, or a group obtained by removing one hydrogen atom from an aromatic ring.
  • the aromatic ring may have a substituent.
  • At least one of R 2 and R 3 needs to be a group represented by the above general formula (Bla).
  • the compound (B1) exhibits sufficient absorption for use as an acid generator in a long wavelength region of 365 nm or longer.
  • the aromatic ring in Y and Z is not particularly limited, and examples thereof include aromatic rings having a carbon number of S6-18, such as benzene and naphthalene.
  • the alkoxy group is represented by R—O— [R is a linear, branched or cyclic alkyl group].
  • R is not particularly limited, but is preferably a linear alkyl group, preferably a linear or branched alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-4. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • the number of alkoxy groups bonded to the aromatic ring is not particularly limited, but for the effect of the present invention, 1 to 3 is preferable, and 1 is particularly preferable.
  • the aromatic ring in Y and Z may have a substituent other than an alkoxy group.
  • substituent other than the alkoxy group include an alkyl group and a hydroxyl group.
  • the alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
  • ⁇ ⁇ Is not particularly limited as an "alkyl group", for example, a straight chain having 1 to 12 carbon atoms And a branched or cyclic alkyl group. Specifically, methyl group, ethyl group
  • N-propyl group isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, and weak group.
  • the aromatic ring in the “group obtained by removing one hydrogen atom from an aromatic ring” is not particularly limited, and examples thereof include aromatic rings having 6 to 18 carbon atoms such as benzene, naphthalene, and anthracene.
  • the aromatic ring in ⁇ to may have a substituent such as an alkoxy group, an alkyl group, or a hydroxyl group, like the aromatic rings in X and Y above.
  • Aromatic ring strength in the “groups in which one hydrogen atom has been removed from an aromatic ring” in ⁇ ⁇ is more preferable. More preferably, it is a group.
  • X— is not particularly limited, and is any one of those conventionally used in chemically amplified resist compositions and proposed as a key-on in known acid generators! Yo! /
  • X— is a fluorinated alkyl sulfonate ion in which at least one of the hydrogen atoms of the alkyl group is substituted with a fluorine atom.
  • X— is a fluorinated alkyl sulfonate ion in which at least one of the hydrogen atoms of the alkyl group is substituted with a fluorine atom.
  • all of these are perfluoroalkyl sulfonate ions substituted with fluorine atoms.
  • the number of carbon atoms of the alkyl group of the fluorinated alkyl sulfonate ion is not particularly limited, but 1 to 12 is preferable and 1 to 4 is more preferable in terms of the bulk of the acid generated and the diffusion length of the acid.
  • R 4 and R 5 are each independently an alkyl group, a phenyl group or a naphthyl group; R 6 and R 7 are each independently an alkoxy group; Is on.
  • R 4 and R 5 are each independently an alkyl group, a phenyl group or a naphthyl group; R 6 and R 7 are each independently an alkoxy group; Is on.
  • alkyl group for R 4 and R 5 examples of the alkyl group in ⁇ ⁇ are the same as those described above.
  • the phenol group or naphthyl group of R 4 and R 5 may or may not have a substituent such as an alkoxy group, an alkyl group, or a hydroxyl group.
  • alkoxy group for R 6 and R 7 are the same as the alkoxy groups mentioned as the substituents for the aromatic ring in Y and Z.
  • the alkoxy group of R 6 and the alkoxy group of R 7 may be the same or different.
  • a preferred example of the compound (B1) of the present invention is a compound represented by the following formula () 3).
  • the compound (B1) of the present invention is suitably used as an acid generator for a chemically amplified photoresist composition, particularly a chemically amplified photoresist composition for radiation having a wavelength of 365 nm or more.
  • the acid generator of the second aspect of the present embodiment (hereinafter sometimes referred to as the acid generator (bl)) is also the compound (B1) of the first aspect.
  • the acid generator (bl) may be composed of one kind of the compound (B1) or a mixture of two or more kinds of the compound (B1).
  • the chemically amplified photoresist composition of the third aspect of the present invention comprises (a) a resin whose alkali solubility is changed by an acid (hereinafter sometimes referred to as (a) component), and (b) an acid upon irradiation.
  • the component (b) contains the acid generator (bl) of the present invention. It can be negative or positive! /.
  • component (a) is a resin whose alkali solubility is lowered by acid, and is generally used as a base resin for negative chemically amplified photoresists. If it is fat, it will not specifically limit, According to the light source used for exposure, it can select and use arbitrarily from a conventionally well-known thing. For example, those containing a novolac resin as a main component are generally widely used because of their good characteristics.
  • Particularly preferable examples of the component (a) include those composed of (i) novolac resin, and (one) one or more kinds of resin that also have a polymer power having a hydroxystyrene constituent unit. This is because it is easy to control the coating property and the development speed.
  • Novolak rosin (hereinafter referred to as (i) component and! /, U) includes, for example, aromatic compounds having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and aldehydes. Can be obtained by addition-condensation in the presence of an acid catalyst.
  • the phenols used include, for example, phenol, o-cresol, m-cresol monole, p-creso mono nore, o-ethino leuenore, m-ethino leuenore, p-echi Rufenol, o-Butylphenol, m-Butinolenoenole, p-Butinolenoenore, 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 —trimethylphenol, p-phenol Examples include lufenol, resorcinol, hydroquinone, hydroquinone monomethylol ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid,
  • aldehydes examples include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetoaldehyde.
  • the catalyst for the addition condensation reaction is not particularly limited.
  • hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.
  • the novolac coconut resin preferably has a mass average molecular weight of 00000 to 10,000, preferably 6000 to 900, and more preferably 7000 to 8000.
  • the mass average molecular weight is 300,000 or more, the tendency of the film to decrease (thinner) after development can be sufficiently suppressed, and when the mass average molecular weight is 10,000 or less, residues can be prevented from remaining after development. preferable.
  • (Mouth) Polymers having a hydroxystyrene structural unit are, for example, hydroxystyrene such as ⁇ -hydroxystyrene, ⁇ -methylhydroxystyrene, ⁇ -ethyl
  • hydroxystyrene such as ⁇ -hydroxystyrene, ⁇ -methylhydroxystyrene, ⁇ -ethyl
  • examples thereof include a radical polymer or an ionic polymer in which only a hydroxystyrene structural unit such as a-alkylhydroxystyrene such as hydroxystyrene is effective, and a copolymer having the above hydroxystyrene structural unit and other structural units.
  • Ratio of hydroxystyrene constituent unit in the polymer is preferably 1 mass 0/0 or more, more preferably 10 to 30 wt%. This is because when the proportion of the hydroxystyrene structural unit is 10% by mass or more, the developability and resolution tend to be excellent.
  • the mass average molecular weight of the (mouth) component is preferably 5000 or less, more preferably 20000 or more and 4000 or less. This is because if the mass average molecular weight is 5000 or less, the resolution tends to be excellent.
  • V is preferred as a monomer that forms a structural unit other than the hydroxystyrene structural unit.
  • the monomer V is a monomer obtained by substituting the hydroxyl group of the hydroxystyrene structural unit with another group or an ⁇ , ⁇ unsaturated double bond. And the like.
  • an alkali dissolution inhibiting group that is not dissociated by an acid is used.
  • Alkali dissolution inhibiting groups that are not dissociated by acid include substituted or unsubstituted benzenesulfoxy groups, substituted or unsubstituted naphthalenesulfoxy groups, substituted or unsubstituted benzenecarboxoxy groups, substituted or unsubstituted groups.
  • Naphthalenecarboxoxy group, etc. and specific examples of the substituted or unsubstituted benzenesulfonyloxy group include benzenesulfoloxy group, black benzenesulfoloxy group, methylbenzenesulfoloxy group, Ethylbenzenesulfoloxy group, propylbenzenesulfuroxy group, methoxybenzenesulfuroxy group, ethoxybenzenesulfuroxy group, propoxybenzenesulfuroxy group, acetoaminobenzenesulfuroxy group, etc.
  • naphthalenesulfo-loxy examples include naphthalenesulfuroxy group, chloronaphthalenesulfuroxy group, methylnaphthalenesulfuroxy group, ethylnaphthalenesulfuroxy group, propylnaphthalenesulfuroxy group, methoxynaphthalenesulfuroxy group, ethoxynaphthalenesulfol group.
  • -Luoxy group, propoxynaphthalene sulfo-loxy group, acetoamino naphthalene sulfo-loxy group and the like are preferable.
  • examples of the substituted or unsubstituted benzencarboxoxy group and the substituted or unsubstituted naphthalenecarboxoxy group include those in which the substituted or unsubstituted sulfo-oxy group is replaced with a carbo-oxy group. Among them, acetaminobenzene sulfo-oxy group or anacetoamino naphthalene sulfo-oxy group is preferred.
  • monomers having ex and ⁇ unsaturated double bonds include styrene monomers such as styrene, chlorostyrene, chloromethyl styrene, butyltoluene, and monomethylol styrene, methyl acrylate, and methacrylic acid.
  • styrene monomers such as styrene, chlorostyrene, chloromethyl styrene, butyltoluene, and monomethylol styrene, methyl acrylate, and methacrylic acid.
  • acrylic acid monomers such as methyl acid and methacrylic acid vinyl
  • butyl acetate monomers such as vinyl acetate and benzoic acid butyl, among which styrene is preferable.
  • component (a) can contain other resin components for the purpose of appropriately controlling physical and chemical properties.
  • component (c) acrylic resin (hereinafter referred to as component (c)), (2) vinyl resin (hereinafter referred to as component (2)).
  • the component (c) acrylic resin is not particularly limited as long as it is an alkali-soluble acrylic resin, and in particular, a structural unit derived from a polymerizable compound having an ether bond (st ructural unit). , And a constituent unit derived from a polymerizable compound having a carboxyl group.
  • polymerizable compounds having an ether bond examples include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate.
  • examples include (meth) acrylic acid derivatives having ether bonds and ester bonds such as acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
  • polymerizable compounds having a carboxyl group examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxychetyl succinate.
  • monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid
  • dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid
  • 2-methacryloyloxychetyl succinate examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid
  • dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid
  • 2-methacryloyloxychetyl succinate examples include 2-methacryloyloxychetyl succinate.
  • Illustrative compounds such as acid, 2-methacryloyloxychetylmaleic acid,
  • the component (2), butter resin, is poly (bule lower alkyl ether) and is obtained by polymerizing a single or a mixture of two or more vinyl lower alkyl ethers represented by the following general formula (I). (Co) polymer power
  • R 6 represents a linear or branched alkyl group having 1 to 5 carbon atoms.
  • examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n propyl group, an i propyl group, and an n butyl group. I-butyl group, n-pentyl group, i-pentyl group and the like. Of these alkyl groups, a methyl group, an ethyl group, and an i-butyl group are preferable, and a methyl group and an ethyl group are particularly preferable.
  • particularly preferred poly (vinyl lower alkyl ethers) are poly (butymethyl ether) and poly (butyethyl ether).
  • component (a) is made of a mixed resin containing the component (i) and the component (mouth), the sum of the component (i) and the component (port) is 100 parts by mass.
  • Component is 50 to 98 parts by mass, preferably 55 to 95 parts by mass, and (mouth) component is 50 to 2 parts by mass, preferably 45 to 5 parts by mass.
  • the component (b) needs to contain the acid generator (bl) of the present invention.
  • the acid generator (bl) may be used alone or in combination of two or more. Good.
  • the ratio of the acid generator (bl) is preferably 50% by mass or more, more preferably 80 to L00% by mass, and most preferably 100% by mass for the effect of the present invention. %.
  • the chemically amplified photoresist composition includes, in addition to the acid generator (bl), a known acid generator (hereinafter referred to as an acid generator (hereinafter referred to as "acid generator”)) used in conventional chemically amplified resist compositions.
  • b2) t may be contained).
  • the acid generator (b2) is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light and is not included in the acid generator (bl). Specifically, 2, 4 —bis (trichloromethyl) 6— [2— (2 furyl) etul] — s triazine, 2, 4 bis (trichloromethyl) —6— [2— (5-methyl-2) Frills) etul] —s triadine, 2 , 4 -Bis (trichloromethyl) 6- [2- (5-ethyl 2-furyl) ether] s Triazine, 2, 4 Bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ether
  • R 4 represents a monovalent to trivalent organic group
  • R 5 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group
  • n is 1 It indicates a natural number of ⁇ 3.
  • the aromatic compound group refers to a group of a compound exhibiting physical 'chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon such as a phenyl group or a naphthyl group.
  • Groups, and heterocyclic groups such as a furyl group and a chenyl group, which have one or more suitable substituents on the ring, such as a neurogen atom, an alkyl group, an alkoxy group, and a nitro group. Even Good.
  • R 5 includes a methyl group, an ethyl group, a propyl group, and a butyl group, in which an alkyl group having 1 to 4 carbon atoms is particularly preferred. Particularly preferred are compounds wherein R 4 is an aromatic compound group and R 5 is a lower alkyl group.
  • P-Toluenesulfonic acid 2 Nitrobenzyl, p Toluenesulfonic acid 2, 6 Dinitrobenzyl, Nitrobenzinoretosylate, Di-Trobenzinoretosylate, Nitrobenzinoresnolefonate, Nitrobenze -Trobenzyl derivatives such as lucarbonate and dinitrobenzyl carbonate; pyrogallo monoretrimesylate, pyrgarol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfo-luoxysuccinimide, N-trichloromethyl sulfone -Luoxy succinimide Sulfonic acid esters such as N-phenylsulfo-loxymaleimide and N-methylsulfo-loxyphthalimide; Trifluoromethane sulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; Saflu
  • these compounds may be used alone or in combination of two or more.
  • the content of the component (b) is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (a). -10 mass parts is more preferable, and 1-5 mass parts is still more preferable.
  • the content of the component (b) is 0.1 parts by mass or more, high sensitivity can be obtained and sufficient image formation can be performed.
  • the amount is 20 parts by mass or less, the resist film has a high residual film ratio after image formation and excellent developability.
  • a crosslinking agent is further included in addition to the above-mentioned components (a) and (b).
  • the cross-linking agent used in the present invention can be appropriately selected from cross-linking agents used in any known chemically amplified negative photoresist composition without particular limitation.
  • cross-linking agents used in any known chemically amplified negative photoresist composition without particular limitation.
  • Alkoxymethyl-aminoamino resin such as fluorinated urea resin can be suitably used.
  • the alkoxymethyl-aminoamino resin is obtained by converting a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution to a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, or isopropyl alcohol. It can be produced by etherifying with a kind and then cooling and precipitating the reaction liquid with.
  • alkoxymethyl-aminoamino resin examples include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylethylamine resin, Examples thereof include ethoxymethyl iurea resin, propoxymethylated urea resin, butoxymethyl iurea resin.
  • the alkoxymethylamino amino coffin can be used alone or in combination of two or more.
  • alkoxymethylated melamine rosin is preferable because it can form a stable resist pattern with a small amount of dimensional change of the resist pattern with respect to a change in radiation dose.
  • methoxymethylated melamine, ethoxymethylated melamine, propoxymethyl melamine and butoxymethylated melamine are preferred.
  • the crosslinking agent is preferably contained in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the component (a).
  • the cross-linking agent is 1 part by mass or more, the resist pattern shape formed with high adhesion resistance, chemical resistance and adhesion of the obtained film is good. If the amount is 30 parts by mass or less, development defects are unlikely to occur during development.
  • an organic solvent can be blended in order to dissolve the above components.
  • Any organic solvent can be used as long as it can dissolve each component used to form a uniform solution.
  • one or two of the known solvents for chemically amplified resists can be used. Select and use as appropriate. Togashi.
  • organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol mono-monoacetate, diethylene glycol, diethylene glycol mono-monoacetate.
  • Polyhydric alcohols such as propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl etherate, monopropyl ether, monobutyl ether or monophenyl ether and their derivatives; Cyclic ethers such as dioxane; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropiate Methyl phosphate, can be mentioned esters such as ethoxypropionate Echiru. These may be used alone or in admixture of two or more.
  • propylene glycol monomethyl ether which is preferred for polyhydric alcohols and derivatives thereof, is more preferred.
  • the organic solvent is usually used in an amount such that the solid content concentration in the chemically amplified photoresist composition is in the range of 1 to 65% by mass.
  • a spin-coating method is used to obtain a thick resist layer having a thickness of, for example, 5 m or more.
  • An amount such that the solid content concentration in the photoresist composition is in the range of 30 to 65% by mass is preferable.
  • the solid content concentration is 30% by mass or more, it is easy to obtain a thick film suitable for manufacturing connection terminals.
  • the composition has good fluidity and is easy to handle. Furthermore, it is easy to obtain a uniform resist film by spin coating.
  • an additive having a miscibility for example, an additional resin for improving the performance of the resist film, as long as it does not impair the essential characteristics.
  • Conventional materials such as plasticizers, adhesion assistants, stabilizers, colorants, and surfactants can be added and contained.
  • the component (b) and the organic solvent are the same as in the case of the negative type, but the component (a) is a resin whose alkali solubility is increased by an acid.
  • the component (a) is not particularly limited as long as it is a resin generally used as a base resin for a positive chemically amplified photoresist, and it is not limited to those conventionally known depending on the light source used for exposure. It can be arbitrarily selected and used.
  • acryl resin is the main component, and at least part of its hydroxyl group is substituted with an alkali dissolution inhibiting group dissociated by an acid, or a polymer having a hydroxyl styrene structural unit as a main component.
  • a group in which at least a part of the group is replaced with an alkali dissolution inhibiting group dissociated by an acid is preferable.
  • the particularly preferred component (a) is composed of a polymer having a (mouth) hydroxystyrene structural unit similar to the negative type described above, and (c) one or more types of resin selected from acrylic resin, and the hydroxyl group Examples thereof include those substituted at least with an alkali dissolution inhibiting group dissociated by an acid S and an acid. This is because it is easy to control coating properties and development speed.
  • Alkali dissolution inhibiting groups dissociated by the action of an acid include tertiary alkyloxy groups such as tert-ptyloxy group and tert-amyloxy group; cyclic acetaloxy groups such as tetrahydrobiraloxy group and tetrahydrofuranyloxy group ; Chain acetaloxy group such as ethoxyethyloxy group, methoxypropyloxy group; cycloalkyloxy group such as cyclohexyloxy group, cyclopentyloxy group; 1-methylcyclohexyloxy group, 1 ethyl; 1-alkyl cycloalkyloxy group such as cycloalkyloxy group; 1-alkyl-polycycloalkyloxy group such as 1-methyladamantyloxy group and 1-ethyladamantyloxy group At least one of the above is preferred.
  • the component (a) can contain other rosin components for the purpose of appropriately controlling physical and chemical properties.
  • rosin components for example, (i) novolak resin and (2) vinyl resin similar to the negative type described above can be mentioned.
  • the crosslinking agent and the component (a) are excluded.
  • the component (b), the organic solvent, and other components can be the same.
  • the chemically amplified photoresist composition of the present invention can be used to form a resist layer on a support.
  • the chemically amplified photoresist composition of the present invention has a high sensitivity to radiation of 365 nm or more, and a resist solution having a high solid content concentration in which the acid generator (bl) is highly soluble in an organic solvent (resist solvent). Therefore, a thick resist layer having a film thickness of 5 m or more can be easily formed. Therefore, as described later, it is suitably used for manufacturing connection terminals.
  • the resist layer laminate of the present invention is obtained by laminating a resist layer made of the chemically amplified photoresist composition on a support.
  • the support is not particularly limited, and a conventionally known one can be used.
  • a substrate for an electronic component or a substrate on which a predetermined wiring pattern is formed can be exemplified. .
  • the substrate examples include a metal substrate such as silicon, silicon nitride, titanium, tantalum, noradium, titanium tungsten, copper, chromium, iron, and aluminum, and a glass substrate.
  • a metal substrate such as silicon, silicon nitride, titanium, tantalum, noradium, titanium tungsten, copper, chromium, iron, and aluminum
  • a glass substrate As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.
  • the portion of the support that is in contact with copper is used.
  • the power of the chemically amplified photoresist is obstructed by copper, and there is a problem of substrate dependency such as development failure such as soldering at that part.
  • the acid generator (bl) of the present invention is used as a component. By using it, the substrate dependency is reduced. Therefore, a resist pattern having an excellent shape can be formed.
  • the chemically amplified photoresist composition of the present invention can be prepared, for example, by mixing and stirring the above-described components by a usual method, as necessary.
  • a dissolver, a homogenizer, a three-neck roll mill (a triple roll mill) ) Or the like may be used for dispersion and mixing. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.
  • the resist layer laminate of the present invention can be produced, for example, as follows. sand That is, a solution of the chemically amplified photoresist composition prepared as described above is applied onto a substrate, and the solvent is removed by heating to form a desired coating film (resist layer).
  • a coating method on the substrate to be processed methods such as a spin coating method, a roll coating method, a screen printing method, and an applicator method can be employed.
  • the prebeta conditions for the coating film of the composition of the present invention are different forces depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc. Usually 70 to 130 ° C, preferably 80 to 120 ° C. 2-60 minutes.
  • the thickness of the resist layer is not particularly limited.
  • the resist layer when the resist layer is a thick film resist layer having a film thickness of 5 m or more, it can be suitably used for production of connection terminals.
  • the lower limit of the thickness of the thick resist layer is more preferably 20 m / z m or more, more preferably 30 m or more, and even more preferably 55 m or more.
  • the upper limit is not particularly limited, but 1000 m or less force S is preferable, 500 m or less is more preferable, 150 / zm or less is more preferable, 120 m or less is more preferable, and 75 m or less is more preferable. Further preferred.
  • the resist pattern forming method of the present invention comprises a laminating step of obtaining a resist layer laminate of the present invention by laminating a resist layer having a chemical amplification type photoresist composition force of the present invention on a support; It includes an exposure step of selectively irradiating radiation, and a development step of obtaining a resist pattern by forming an image after the exposure step.
  • the lamination step can be performed in the same manner as in the production of the resist layer laminate.
  • radiation for example, ultraviolet rays having a wavelength of 300 to 500 nm or visible light is selected through a mask having a predetermined pattern on the obtained photoresist layer.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal lamp, a ride lamp, an argon gas laser, or the like can be used.
  • radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like.
  • the present invention is particularly suitable for an exposure process using radiation in a long wavelength region of 365 nm or more.
  • the amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, and the film thickness of the coating film.
  • ultra-high pressure mercury lamp g-line (436nm), h-line (405nm), i-line (365nm) Including No
  • it is 100 ⁇ 2000mjZcm 2.
  • the development step can be performed, for example, by using a predetermined alkaline aqueous solution as a developer, and an unnecessary portion is dissolved and removed by the developer to obtain a predetermined resist pattern.
  • an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide can be used.
  • an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution is used as a developer.
  • the development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition. Power is usually 1 to 30 minutes, and the development method is liquid deposition, dating, paddle, spray development, etc. Either of these is acceptable. After development, wash with running water for 30 to 90 seconds and dry using an air gun or oven.
  • the treatment method is not particularly limited, and various methods known in the art can be employed.
  • the plating solution solder plating and copper plating solution are particularly preferably used.
  • the remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.
  • the compound (B1) of the present invention has sufficient absorption to function as an acid generator in a long wavelength region of 365 nm or more, and exposure using radiation having a wavelength of 365 nm or more. Also, a sufficient amount of acid is generated for forming a resist pattern. Also, the solubility in organic solvents used in resists is high. Therefore, the acid generator (bl) composed of the compound (B1) is suitably used for a chemically amplified photoresist composition, particularly a chemically amplified photoresist composition for radiation having a wavelength of 365 nm or more, and the acid generator (bl) The chemical amplification type photoresist composition containing the compound has high sensitivity.
  • the chemically amplified photoresist composition of the present invention can form a resist pattern excellent in shape and accuracy regardless of the type of substrate used, which has low substrate dependency.
  • substrate dependency such as development failure (such as film loss in the case of negative, adhesion failure in the case of positive), but as a component (b) from the compound (B1) of the present invention.
  • substrate dependency is reduced by using the acid generator (bl). The effect of reducing the substrate dependency is presumed to be because the compound (B1) of the present invention has a group that easily reacts with a metal such as copper, such as CN.
  • the chemically amplified photoresist composition of the present invention can increase the solid content concentration of the organic solvent solution of the resist, so that the film thickness is 5 Suitable for forming a thick resist layer of m or more.
  • the chemically amplified photoresist composition of the present invention is also excellent in storage stability as a resist solution in a bottle. It is expected. Along with this, it is presumed that a decrease in sensitivity and a deterioration in resist pattern shape due to deterioration of performance over time can be prevented.
  • the chemically amplified photoresist composition according to the sixth aspect of the present invention comprises (a) a resin whose alkali solubility is changed by an acid (hereinafter sometimes referred to as (a) component), and (b) by irradiation with radiation.
  • a compound that generates an acid hereinafter also referred to as component (b)
  • component (c) a compound represented by the following general formula (C1) (hereinafter also referred to as component (c))
  • the component (b) includes a sulfonium salt-based acid generator (b-1), and may be negative or positive.
  • the component (a) is the same as the component (a) in the first embodiment, and the description thereof is omitted.
  • the component (b) is a sulfo-um salt-based acid generator (b-1) (hereinafter referred to as an acid generator). (b-1) may be contained).
  • the acid generator (b-1) can be arbitrarily selected from the sulfo salt-based acid generators proposed for use in chemically amplified resist compositions.
  • the “sulfo salt-based acid generator” is a compound having a sulfone ion as a force thione part and generating an acid upon irradiation with radiation. Examples of the sulfo-um ion include those represented by the following general formula (IX).
  • R ′′ to R ′′ each independently represents an aryl group or an alkyl group.
  • R U to R 13 out of it is preferred instrument R U to R 13 at least Tsu is Ariru group, 2 or more, all it is more preferred instrument R "to R 13 is a Ariru group Most preferred is an aryl group.
  • aryl group of R U to R 13 for example, a group represented by the general formula (Bla) described later, or an aryl group having 6 to 20 carbon atoms, which is substituted with an alkyl group, a halogen atom, or the like. Examples thereof include a fluorine group and a naphthyl group which may be omitted.
  • the alkyl group which may be substituted on the aryl group is not particularly limited, and examples thereof include a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the halogen atom that may be substituted on the aryl group include a chlorine atom, a fluorine atom, an iodine atom, and a bromine atom.
  • Examples of the alkyl group of R U to R 13 include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • the acid generator (b-1) contains a compound represented by the general formula (B1) (hereinafter sometimes referred to as the compound (B1)). .
  • B1 a compound represented by the general formula (B1)
  • This further improves the sensitivity in a long wavelength region of 365 ⁇ m or more.
  • the compound (Bl) is the same as the compound (Bl) in the first embodiment, and thus the description thereof is omitted.
  • the acid generator (b-1) may be used alone or in combination of two or more.
  • the ratio of the acid generator (b-1) is preferably 50% by mass or more, more preferably 80 to L00% by mass, and most preferably 100 for the effect of the present invention. % By mass.
  • the chemically amplified photoresist composition comprises an acid generator (b) as component (b).
  • the acid generator (b-2) may contain a known acid generator (hereinafter sometimes referred to as acid generator (b-2)) used in conventional chemically amplified resist compositions.
  • acid generator (b-2) is the same as the acid generator (b2) in the first embodiment, description thereof is omitted.
  • Component (c) is a compound represented by the general formula (C1).
  • the chemically amplified photoresist composition of the present invention contains the sulfo-acid salt generator (b-1) as the component (b)! /, However, it has high sensitivity to radiation in the long wavelength region of 365 nm or more.
  • R 1 and R 2 are an ethyl group or an n-butyl group because of the excellent effects of the present invention.
  • the ratio of the component (c) to the component (b) is preferably within the range of 5 to 30% by mass, more preferably 10 to 25% by mass. Preferred 15 to 20% by mass is more preferred.
  • the content is 5% by mass or more, high sensitivity can be obtained and sufficient image formation can be performed. In addition, if it is 30% by mass or less, the sensitivity is not adversely affected.
  • a crosslinking agent is further contained.
  • the cross-linking agent is the same as the cross-linking agent in the first aspect, and the description thereof is omitted.
  • the organic solvent is the same as the cross-linking agent in the first embodiment, and the description thereof is omitted.
  • resist layer laminate As described above, and thus description thereof is omitted.
  • the chemically amplified photoresist composition of the present invention containing the sulfo-acid salt acid generator (b-1) and the component (c) has high sensitivity. This is because the component (c) has a function as a sensitizer of the sulfur salt-based acid generator (b-1).
  • the chemically amplified photoresist composition of the present invention can form a resist pattern excellent in shape and accuracy regardless of the type of substrate used, which has low substrate dependency.
  • the use of the compound (B 1) as the sulfo-salt salt acid generator (b-1) is particularly excellent in the above effects.
  • compound (B1) has sufficient absorption to function as an acid generator in the long wavelength region of 365 nm or more, and is sufficient to form a resist pattern even by exposure using radiation having a wavelength of 365 nm or more. This is because a large amount of acid is generated.
  • the compound (B1) since the compound (B1) has high solubility in the organic solvent used in the resist, the solid content concentration of the organic solvent solution of the resist can be increased. Therefore, the chemically amplified photoresist composition of the present invention can be used as a film.
  • the compound (B1) has high solubility in an organic solvent, it is expected that the chemically amplified photoresist composition is excellent in bottle aging stability. Along with this, it is presumed that a decrease in sensitivity and a deterioration in resist pattern shape due to deterioration in performance over time can be prevented.
  • m-Talesol and p-Talesol were mixed at a mass ratio of 60:40, and formalin was added thereto, followed by condensation by a conventional method using a oxalic acid catalyst to obtain a cresol novolac coconut resin. A fractionation treatment was applied to this rosin, and the low molecular region was cut to obtain a novolac rosin having a mass average molecular weight of 8,000. This oil is called (A-1).
  • Example 2 instead of 3 parts by mass of the acid generator (B-1), the same procedure as in Example 1 was carried out except that 3 parts by mass of triphenylsulfo-trifluoromethanesulfonate (acid generator (B-2)) was used. Thus, a chemically amplified negative photoresist composition was prepared.
  • the concentration of propylene glycol monomethyl ether acetate in each acid generator was adjusted by changing the concentration in increments of 1% by mass from 5% by mass to 1% by mass. After the adjustment, each solution was stirred to measure the concentration at which each acid generator was completely dissolved.
  • composition of the present invention has high sensitivity to i-line (365 nm), and i-line The same effect was obtained with single exposure (365 nm).
  • the shape of the formed resist pattern was observed using an optical microscope or an electron microscope, and judged according to the following evaluation criteria.
  • ⁇ The shape of the formed resist pattern is rectangular
  • the shape of the formed resist pattern is an inverted trapezoid (the number in parentheses represents the contact angle between the pattern and the substrate)
  • m-Talesol and p-Talesol were mixed at a mass ratio of 60:40, and formalin was added thereto, followed by condensation by a conventional method using a oxalic acid catalyst to obtain a cresol novolac resin. A fractionation treatment was applied to this rosin, and the low molecular region was cut to obtain a novolac rosin having a mass average molecular weight of 8,000.
  • This oil is designated as (A-11).
  • a chemically amplified negative photoresist composition was obtained in the same manner as in Example 2 except that the blending amount of 9,10-di (n-butoxy) anthracene was changed to 0.3 parts by mass.
  • a chemically amplified negative photoresist composition was obtained in the same manner as in Example 2 except that the blending amount of 9,10-di (n-butoxy) anthracene was changed to 0.5 parts by mass.
  • a chemically amplified negative photoresist composition was prepared in the same manner as in Example 2 except that 9,10-di (n-butoxy) anthracene was not added.
  • composition of the present invention is highly sensitive to i-line (365 nm). The same effect was obtained with single exposure (365 nm).
  • the present invention relates to a compound that exhibits high absorption in a long wavelength region of 365 nm or more, excellent absorption in an organic solvent having high sensitivity in a long wavelength region of 365 nm or more, and an excellent solubility in an organic solvent.
  • the present invention can be applied to an acid generator comprising the above, a chemically amplified photoresist composition containing the acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a method for forming a resist pattern.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un composé qui présente une absorption élevée dans la région des grandes longueurs d'onde supérieures ou égales à 365 nm et qui présente une sensibilité élevée dans la région des grandes longueurs d'onde supérieures ou égales à 365 nm, lequel excelle en termes de solubilité dans des solvants organiques ; un générateur d'acide constitué du composé ; une composition de vernis photorésistant de type à amplification chimique contenant le générateur d'acide ; et, faisant usage de la composition de vernis photorésistant de type à amplification chimique, un stratifié ayant une couche de réserve et un procédé de formation d'une impression de réserve. Le composé est n'importe lequel de ceux représentés par la formule générale (B1). Dans la formule (B1), au moins l'un de R1, R2 et R3 est l'un quelconque des groupes de formule (B1a). Dans la formule (B1a), Y est un groupe dérivé d'un cycle aromatique privé de deux atomes d'hydrogène, le cycle aromatique ayant facultativement un substituant ; Z est un groupe dérivé d'un cycle aromatique privé d'un atome d'hydrogène, le cycle aromatique ayant facultativement un substituant ; et le cycle aromatique d'au moins l'un de Y et de Z a au moins un alcoxy.
PCT/JP2006/320779 2005-10-19 2006-10-18 Nouveau composé, générateur d'acide, composition de vernis photorésistant de type à amplification chimique, stratifié ayant une couche de réserve et procédé de formation d'une impression de réserve WO2007046442A1 (fr)

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JP2005303926A JP4823640B2 (ja) 2005-10-19 2005-10-19 新規な酸発生剤、化学増幅型ホトレジスト組成物、レジスト層積層体およびレジストパターン形成方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007126066A1 (fr) * 2006-04-28 2007-11-08 Kawasaki Kasei Chemicals Ltd. Initiateur de photopolymerisation et composition photodurcissable
CN107935899A (zh) * 2016-10-12 2018-04-20 信越化学工业株式会社 锍化合物、抗蚀剂组合物及图案形成方法
JP2018193305A (ja) * 2017-05-12 2018-12-06 東洋合成工業株式会社 ヨードニウム塩化合物、それを含有する光酸発生剤及び組成物、並びに、デバイスの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH107649A (ja) * 1996-06-18 1998-01-13 Nippon Kayaku Co Ltd 光重合開始剤、これを含有するエネルギー線硬化性組成物及びその硬化物
WO2004029037A1 (fr) * 2002-09-25 2004-04-08 Asahi Denka Co.Ltd. Nouveau compose de sel de sulfonium aromatique, generateur photo-acide le comprenant et composition photopolymerisable le contenant, composition de resine pour la mise en forme tridimensionnelle optique et procede correspondant
JP2005187799A (ja) * 2003-11-04 2005-07-14 Natl Starch & Chem Investment Holding Corp スルホニウム塩光反応開始剤とその使用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH107649A (ja) * 1996-06-18 1998-01-13 Nippon Kayaku Co Ltd 光重合開始剤、これを含有するエネルギー線硬化性組成物及びその硬化物
WO2004029037A1 (fr) * 2002-09-25 2004-04-08 Asahi Denka Co.Ltd. Nouveau compose de sel de sulfonium aromatique, generateur photo-acide le comprenant et composition photopolymerisable le contenant, composition de resine pour la mise en forme tridimensionnelle optique et procede correspondant
JP2005187799A (ja) * 2003-11-04 2005-07-14 Natl Starch & Chem Investment Holding Corp スルホニウム塩光反応開始剤とその使用

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007126066A1 (fr) * 2006-04-28 2007-11-08 Kawasaki Kasei Chemicals Ltd. Initiateur de photopolymerisation et composition photodurcissable
CN107935899A (zh) * 2016-10-12 2018-04-20 信越化学工业株式会社 锍化合物、抗蚀剂组合物及图案形成方法
CN107935899B (zh) * 2016-10-12 2019-11-12 信越化学工业株式会社 锍化合物、抗蚀剂组合物及图案形成方法
JP2018193305A (ja) * 2017-05-12 2018-12-06 東洋合成工業株式会社 ヨードニウム塩化合物、それを含有する光酸発生剤及び組成物、並びに、デバイスの製造方法

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