WO2016031580A1 - 層間絶縁膜形成用感光性樹脂組成物、層間絶縁膜及び層間絶縁膜の形成方法 - Google Patents
層間絶縁膜形成用感光性樹脂組成物、層間絶縁膜及び層間絶縁膜の形成方法 Download PDFInfo
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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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
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- 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
- G03F7/022—Quinonediazides
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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
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- 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
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- 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
- G03F7/075—Silicon-containing compounds
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a photosensitive resin composition for forming an interlayer insulating film, an interlayer insulating film, and a method for forming an interlayer insulating film.
- This application claims priority based on Japanese Patent Application No. 2014-173129 for which it applied to Japan on August 27, 2014, and uses the content here.
- Polyimide resin hereinafter referred to as “PI”
- PBO polybenzoxazole
- PI and PBO have photosensitive characteristics.
- the use of the provided photosensitive PI and photosensitive PBO is being studied.
- the photosensitive resins are used, there is an advantage that a pattern forming process is simplified and a complicated manufacturing process can be shortened.
- the photosensitive resin is effective as the interlayer insulating film because it has higher heat resistance and insulation resistance than a vinyl-based photosensitive resin that can be alkali developed by introducing a conventional carboxyl group (for example, (See Patent Documents 1 and 2).
- photosensitive PI and photosensitive PBO require baking at a high temperature (350 to 400 ° C.), are not stable over time, have a large film thickness reduction, and have low solvent solubility. There was a problem such as.
- Patent Document 3 an interlayer insulating film using a photosensitive acrylic resin having high heat resistance and good handleability has been proposed.
- Patent Document 3 there is still room for improvement in various lithography characteristics of the interlayer insulating film using the photosensitive acrylic resin.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition capable of forming an interlayer insulating film having good lithography characteristics.
- 1st aspect of this invention contains alkali-soluble resin (A), a photosensitizer (B), the thermal acid generator (T) which generate
- a photosensitive resin composition for forming an interlayer insulating film wherein the alkali-soluble resin (A) is a structural unit (A1) represented by general formula (a-1) or an alicyclic epoxy group-containing unit (A3). And a photosensitive resin composition for forming an interlayer insulating film.
- a second aspect of the present invention is an interlayer insulating film using the photosensitive resin composition for forming an interlayer insulating film according to the first aspect.
- a third aspect of the present invention includes a step of forming a photosensitive resin composition layer on a support using the photosensitive resin composition for forming an interlayer insulating film according to the first aspect, and the photosensitive resin composition
- An interlayer insulating film comprising: exposing a physical layer; developing the exposed photosensitive resin composition layer to form an interlayer insulating film pattern; and heating and curing the interlayer insulating film pattern It is the formation method.
- the photosensitive resin composition for forming an interlayer insulating film of the present embodiment (hereinafter also simply referred to as “photosensitive resin composition”) generates an acid by heating with an alkali-soluble resin (A), a photosensitive agent (B), and the like.
- the alkali-soluble resin (A) (hereinafter sometimes referred to as “copolymer (A)”) is a structural unit (A1) represented by the following general formula (a-1) or an alicyclic epoxy group. It has a content unit (A3).
- the structural unit (A1) is represented by the following general formula (a-1).
- R represents a hydrogen atom or a methyl group
- Ra 01 represents a hydrogen atom or an organic group having a hydroxyl group.
- R represents a hydrogen atom or a methyl group.
- Ra 01 is a hydrogen atom or an organic group having a hydroxyl group.
- examples of the organic group include a branched, linear, or cyclic alkyl group, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, and a substituent.
- aralkyl group which may have, or a substituent can be exemplified good heteroaralkyl group optionally having, Ra 01 has at least one hydroxyl group in its structure.
- the organic group preferably has 1 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. A large carbon number is preferable in terms of storage stability and low dielectric constant of the interlayer insulating layer, and a small carbon number is excellent in resolution.
- Ra 01 is a hydrogen atom, that is, selecting methacrylic acid or acrylic acid is effective in enhancing the alkali developability of the copolymer. From the viewpoint, it is preferable to employ the above organic group having a hydroxyl group as Ra 01 as the structural unit (A1).
- Preferred examples of the structural unit (A1) include structural units represented by the following general formula (a-1-1).
- Ra 001 represents an alkyl group having 1 to 5 carbon atoms
- a represents 1 to 5 B represents 0 or an integer of 1 to 4
- a + b is 5 or less.
- these Ra 001 may mutually differ or may be the same.
- R represents a hydrogen atom or a methyl group, and is preferably a methyl group.
- Ya 01 represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, an isopentylene group, and a neopentylene group. Among these, a single bond, a methylene group, and an ethylene group are preferable.
- Ya 01 is preferably a single bond because it can improve alkali solubility and further improve the heat resistance when used as an interlayer insulating film.
- a represents an integer of 1 to 5, and a is preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
- the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to Ya 01 is the reference (first position).
- Ra 001 is a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Among these, a methyl group or an ethyl group is preferable from the viewpoint of easy production.
- b represents 0 or an integer of 1 to 4, but b is preferably 0 from the viewpoint of the effects of the present invention and the ease of production.
- o-hydroxyphenyl (meth) acrylate m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl (meth) acrylate, o-hydroxybenzyl (meth) acrylate, m -Derived from hydroxybenzyl (meth) acrylate, p-hydroxybenzyl (meth) acrylate, o-hydroxyphenylethyl (meth) acrylate, m-hydroxyphenylethyl (meth) acrylate, p-hydroxyphenylethyl (meth) acrylate, etc.
- those derived from p-hydroxyphenyl (meth) acrylate or p-hydroxybenzyl (meth) acrylate are preferred, particularly those derived from p-hydroxyphenyl (meth) acrylate. It is preferred.
- the content ratio of the structural unit (A1) in the copolymer (A) is preferably 10 to 70 mol% with respect to the total of all the structural units constituting the copolymer (A). Further, it is preferably 15 to 60 mol%, and most preferably 20 to 50 mol%.
- the alicyclic epoxy group-containing unit (A3) is not particularly limited as long as it is a structural unit derived from a compound having an alicyclic epoxy group in the structure and having an ethylenic double bond.
- the alicyclic group of the alicyclic epoxy group preferably has about 5 to 10 carbon atoms.
- alicyclic epoxy group-containing unit (A3) examples include those derived from alicyclic epoxy group-containing polymerizable unsaturated compounds represented by the following general formulas (1) to (31), respectively. It is done.
- R 4 represents a hydrogen atom or a methyl group
- R 5 represents a divalent hydrocarbon group having 1 to 8 carbon atoms
- R 6 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
- R 4 , R 5 and R 6 may be the same or different
- w represents an integer of 0 to 10.
- those represented by the general formulas (1) to (6), (14), (16), (18), (21), (23) to (25) or (30) are preferable. More preferably, those represented by the general formulas (1) to (6), respectively.
- the content ratio of the alicyclic epoxy group-containing unit (A3) in the copolymer (A) is preferably 5 to 40 mol% with respect to the total of all the structural units constituting the copolymer (A). . Further, it is preferably 10 to 30 mol%, and most preferably 15 to 25 mol%. If the content ratio is 10 mol% or more, the heat resistance and adhesion of the interlayer insulating film can be improved, and if it is less than 40 mol%, the dielectric constant of the interlayer insulating film can be kept low.
- the copolymer (A) preferably has a structural unit (A2) represented by the following general formula (a-2).
- R represents a hydrogen atom or a methyl group
- Rb represents a hydrocarbon group
- Examples of the hydrocarbon group for Rb include a branched, linear, or cyclic alkyl group, an aryl group that may have a substituent, or an aralkyl group that may have a substituent. Can do.
- the hydrocarbon group preferably has 1 to 20 carbon atoms.
- the branched or straight chain alkyl group preferably has 1 to 12 carbon atoms, and most preferably 1 to 6 carbon atoms.
- the cyclic alkyl group preferably has 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms.
- the aryl group which may have a substituent or the aralkyl group which may have a substituent preferably has 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms. Alkali resolution is sufficient if the carbon number is 20 or less, and it is preferable if the carbon number is 1 or more because the dielectric constant of the interlayer insulating film can be reduced.
- the structural unit (A2) include linear or branched alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, and t-octyl acrylate; cyclohexyl Examples thereof include alicyclic alkyl acrylates such as acrylate, dicyclopentanyl acrylate, 2-methylcyclohexyl acrylate, and isobornyl acrylate; those derived from benzyl acrylate, aryl acrylate (eg, phenyl acrylate), and the like.
- linear or branched alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate,
- linear or branched alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate; cyclohexyl methacrylate, Alicyclic alkyl methacrylates such as dicyclopentanyl methacrylate, 2-methylcyclohexyl methacrylate, and isobornyl methacrylate; those derived from benzyl methacrylate, aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.) It is done.
- benzyl methacrylate aryl methacrylate (eg, phenyl me
- the dissolution speed of the copolymer can be adjusted.
- the structural unit (A2) those derived from a monomer having an alicyclic group are particularly preferred from the viewpoint of reducing the dielectric constant of the interlayer insulating film.
- the content ratio of the structural unit (A2) in the copolymer (A) is preferably 5 to 50 mol% with respect to the total of all the structural units constituting the copolymer (A).
- the copolymer (A) may have a structural unit (A4) other than the structural units (A1) to (A3) as long as the object of the present invention is not violated.
- the structural unit (A4) is not particularly limited as long as it is a structural unit derived from a compound having an ethylenic double bond. Examples of the structural unit (A4) include structural units derived from compounds selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like.
- acrylamides include acrylamide, N-alkylacrylamide (the alkyl group preferably has 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, Octyl group, cyclohexyl group and the like), N-arylacrylamide (aryl groups include, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group and the like), N, N-dialkylacrylamide (The alkyl group preferably has 1 to 10 carbon atoms), N, N-arylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N— Methylacrylamide, N-2-acetamidoethyl-N Acetyl acrylamide.
- N-alkylacrylamide the alkyl group preferably has 1
- methacrylamides include methacrylamide, N-alkylmethacrylamide (the alkyl group preferably has 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, Cyclohexyl group and the like), N-aryl methacrylamide (the aryl group includes a phenyl group), N, N-dialkyl methacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, and the like).
- N-alkylmethacrylamide the alkyl group preferably has 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, Cyclohexyl group and the like
- N-aryl methacrylamide the aryl group includes a phenyl group
- N, N-diarylmethacrylamide (an aryl group includes a phenyl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl- N-phenylmethacrylamide may be mentioned.
- allyl compounds include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) And allyloxyethanol.
- allyl esters eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.
- vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, Vinyl Phenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl vinyl
- vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl Examples include butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl- ⁇ -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.
- styrenes include styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloro.
- alkyl styrene for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexy
- Methyl styrene trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogen styrene (eg chloro styrene, dichloro styrene, etc.) Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, Li-fluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.). Also included are acrylonitrile, methacrylonitrile and the
- a copolymer (A) consists of the said structural unit (A1), (A2), and (A3).
- the copolymer (A) has a mass average molecular weight (Mw: measured value in terms of polystyrene by gel permeation chromatography (GPC)) of preferably 2000 to 50000, and more preferably 5000 to 30000.
- Mw mass average molecular weight
- GPC gel permeation chromatography
- the copolymer (A) can be produced by known radical polymerization. That is, it can be produced by dissolving the polymerizable monomer for inducing the structural units (A1) to (A3) and the like and a known radical polymerization initiator in a polymerization solvent, and then stirring with heating.
- the alkali-soluble resin (A) may contain one or more other copolymers in addition to the copolymer containing the structural units (A1) to (A3).
- This copolymer is preferably 0 to 50 parts by mass, and more preferably 0 to 30 parts by mass with respect to 100 parts by mass of the copolymer (A).
- the weight average molecular weight of this copolymer (Mw: measured value in terms of polystyrene by gel permeation chromatography (GPC)) is preferably 2000 to 50000, and more preferably 5000 to 30000.
- Photosensitive agent (B) Although it will not specifically limit if it is a compound which can be used as a photosensitive component as a photosensitizer (B), A quinonediazide group containing compound is mentioned as a preferable example.
- quinonediazide group-containing compound examples include completely esterified products and partially esterified products of a phenol compound (also referred to as a phenolic hydroxyl group-containing compound) and a naphthoquinonediazide sulfonic acid compound.
- the phenol compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone; tris (4-hydroxyphenyl) methane, Bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl) -4- Roxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylme
- Linear type 3 such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol and 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol
- naphthoquinone diazide sulfonic acid compound examples include naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid.
- quinonediazide group-containing compounds such as orthobenzoquinonediazide, orthonaphthoquinonediazide, orthoanthraquinonediazide, or orthonaphthoquinonediazidesulfonic acid esters and the like can be mentioned.
- orthoquinonediazidesulfonyl chloride and a compound having a hydroxyl group or an amino group for example, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3
- a reaction product with dimethyl ether, gallic acid, gallic acid esterified or etherified with some hydroxyl groups remaining, aniline, p-aminodiphenylamine, etc. can also be used. You may use these individually or in combination of 2 or more types.
- quinonediazide group-containing compounds include, for example, a trisphenol type compound and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazido-4-sulfonyl chloride in a suitable solvent such as dioxane.
- a suitable solvent such as dioxane.
- an alkali such as triethanolamine, alkali carbonate, alkali hydrogen carbonate and the like, and can be produced by complete esterification or partial esterification.
- the component (B) it is preferable to use a non-benzophenone-based quinonediazide group-containing compound, and it is preferable to use a polynuclear branched compound.
- the phenolic hydroxyl group-containing compound preferably has a gram extinction coefficient of 1 or less at a wavelength of 350 nm. Thereby, in the photosensitive resin composition, higher sensitivity can be obtained, and the transmittance (transparency) when an interlayer insulating film is formed can be improved.
- the phenolic hydroxyl group-containing compound preferably has a decomposition temperature of 300 ° C. or higher. Thereby, the transparency of the interlayer insulating film can be ensured.
- a quinonediazide group-containing compound is preferable, and a naphthoquinonediazidesulfonic acid ester is particularly preferable.
- a naphthoquinonediazidesulfonic acid ester is particularly preferable.
- a naphthoquinone diazide sulfonate esterified product such as 1-bis (4-hydroxyphenyl) ethyl] benzene can be preferably used.
- the content of the component (B) is preferably 10 to 40% by mass, more preferably 15 to 30% by mass, based on the total solid content of the photosensitive resin composition of the present embodiment.
- the content of the component (B) is preferably 10 to 40% by mass, more preferably 15 to 30% by mass, based on the total solid content of the photosensitive resin composition of the present embodiment.
- the photosensitive resin composition for forming an interlayer insulating film of this embodiment contains a thermal acid generator (T). Since the photosensitive resin composition for forming an interlayer insulating film according to this embodiment contains a thermal acid generator (T), a polymerization reaction in the photosensitive resin film is caused by the action of an acid generated by heat during the thermosetting process. (In particular, polymerization with an epoxy group in an alkali-soluble resin) is further promoted, and the film density is considered to be improved.
- the thermal acid generator (T) may be appropriately selected from known ones, such as trifluoromethanesulfonate, boron trifluoride etherate, hexafluorophosphate, perfluorobutanesulfonic acid, three Cationic or protonic acid catalysts such as boron fluoride can be used.
- trifluoromethanesulfonate such as trifluoromethanesulfonate
- boron trifluoride etherate such as boron trifluoride etherate
- hexafluorophosphate, perfluorobutanesulfonic acid are preferable
- trifluoromethanesulfonic acid is more preferable.
- aromatic onium salts that are also used as acid generators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators.
- Sun Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110L, SI-145, I-150, SI-160 SI-180L, SI-B3, SI-B3A manufactured by Sanshin Chemical Industry Co., Ltd.
- CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2623, CI-2039 (manufactured by Nippon Soda Co., Ltd.), CP-66, CP-77 ((shares) ADEKA), FC-520 (manufactured by 3M) K-PURE TAG-2396, TAG-2713S, TAG-2713, TAG-2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG- 2678, TAG-2681, TAG-2679, TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC-1613, CX C-1739, CXC-1751, CXC-1766, CX
- the acid generation temperature of the thermal acid generator (T) is preferably equal to or higher than the pre-baking temperature, specifically 110 ° C. or higher, and preferably 130 ° C. or higher. More preferred. If the acid generation temperature of the thermal acid generator (T) is lower than the pre-baking temperature, acid is generated from the thermal acid generator (T) during pre-baking, and polymerization proceeds in the photosensitive resin film. The alkali solubility in the exposed area is lowered, and a good pattern cannot be formed. On the other hand, when the acid generation temperature of the thermal acid generator (T) is in the above range, the polymerization in the photosensitive resin film can be promoted during the thermosetting process after the formation of the photosensitive resin film. It is thought that it can contribute to the improvement of the film density without hindering.
- the content of the thermal acid generator (T) is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 0%, based on the total solid content of the photosensitive resin composition. 0.8 mass%, most preferably 0.1-0.4 mass%.
- a solvent for example, PGMEA, PGME, N-methylpyrrolidone (NMP), etc.
- an acid hydrofluoric acid, etc.
- an alkali TMAH, etc.
- the photosensitive resin composition for interlayer insulation film formation of this embodiment contains a silane coupling agent (C).
- the photosensitive resin composition for forming an interlayer insulating film of the present embodiment can improve the adhesion between the film formed of the photosensitive resin composition and the substrate by containing the silane coupling agent (C), The property of the film formed by the photosensitive resin composition can be adjusted.
- Specific examples of the silane coupling agent (C) include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, and ⁇ -glycidoxypropylalkyl.
- ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
- the content of the silane coupling agent (C) is preferably 0.01 to 10% by mass, more preferably 0.1 to 2% by mass, based on the total solid content of the photosensitive resin composition of the present embodiment. Most preferably, it is 0.2 to 1.5% by mass. When included in the above range, the adhesion between the pattern formed from the photosensitive resin composition of the present embodiment and the substrate is preferably improved.
- the photosensitive resin composition for forming an interlayer insulating film of the present embodiment further contains a crosslinking agent (D).
- a crosslinking agent (D) it is more preferable that it is at least 1 sort (s) selected from the group which consists of an oxetane containing compound, an epoxy group containing compound, and a block isocyanate compound.
- the compound having an oxetane group or an epoxy group include styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamate, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl.
- Examples include ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.), oxetane alcohol and the like.
- the oxetane-containing compound Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
- epoxy group-containing compound epoxy resin EXA4850-150 and epoxy resin EXA4850-1000 (both manufactured by DIC Corporation) can be used.
- the blocked isocyanate compound is inactive at room temperature, and is a compound that regenerates the isocyanate group by dissociating the blocking agent such as oximes, diketones, phenols, caprolactams, etc. when heated.
- a block isocyanate compound can be used individually by 1 type, or can use 2 or more types together.
- isocyanate compound known compounds can be used.
- aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, Alicyclic diisocyanates such as hydrogenated xylylene diisocyanate and hydrogenated tolylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p- Aromatic diisocyanates such as phenylene diisocyanate and naphthylene diisocyanate Sulfonates, Kishirume
- aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate
- alicyclic diisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate
- aromas such as tolylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and naphthylene diisocyanate
- an adduct is an adduct of aliphatic diisocyanate and trimethylolpropane
- a biuret is a reaction product of hexamethylene diisocyanate and water or a tertiary alcohol
- an isocyanurate is a trimer of hexamethylene diisocyanate. Is preferred.
- a blocking agent is a compound that is added to a polyisocyanate group and is stable at room temperature but is liberated to generate an isocyanate group when heated to a temperature higher than the dissociation temperature.
- the blocking agent include lactam compounds such as ⁇ -butyrolactam, ⁇ -caprolactam, ⁇ -valerolactam, propiolactam, methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamide oxime Oxime compounds such as acetooxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, monocyclic phenol compounds such as phenol, cresol, catechol, nitrophenol, polycyclic phenol compounds such as 1-naphthol, methyl alcohol, ethyl alcohol, isopropyl Alcohol compounds such as alcohol, tert-butyl alcohol, trimethylolpropan
- a blocked isocyanate compound can be produced by reacting an isocyanate compound with a blocking agent.
- the reaction between the isocyanate compound and the blocking agent is carried out, for example, by heating at about 50 to 100 ° C. in a solvent having no active hydrogen (1,4-dioxane, cellosolve acetate, etc.) and if necessary, the presence of a blocking catalyst. Done below.
- the use ratio of the isocyanate compound and the blocking agent is not particularly limited, but is preferably 0.95: 1.0 to 1.1: 1.0 as an equivalent ratio of the isocyanate group to the blocking agent in the isocyanate compound. More preferably 1: 1.05 to 1: 1.15.
- Known blocking catalysts can be used, for example, metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate and potassium methylate, and tetraalkylammonium such as tetramethylammonium, tetraethylammonium and tetrabutylammonium.
- metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate and potassium methylate
- tetraalkylammonium such as tetramethylammonium, tetraethylammonium and tetrabutylammonium.
- examples thereof include hydroxides, organic weak acid salts such as acetates thereof, octylates, myristates and benzoates, and alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylic acid and myristic acid.
- the blocked catalyst can be used alone or in combination of two or more
- a commercial item can also be used as a block isocyanate compound.
- Specific examples of commercially available products include TPA-B80E (trade name, manufactured by Asahi Kasei Corporation, isocyanurate type), 17B-60P (trade name, manufactured by Asahi Kasei Corporation, biuret type), E402-B80B (trade name, Asahi Kasei Corporation) Company-made, adduct type).
- the content of the blocked isocyanate compound is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 10 to 40% by mass with respect to the total solid content of the photosensitive resin composition of the present embodiment. is there.
- a blocked isocyanate compound as the crosslinking agent (D) from the viewpoint of improving the mechanical properties of the interlayer insulating film.
- a blocked isocyanate compound an adduct type blocked isocyanate compound is preferably employed.
- the content of the adduct type blocked isocyanate compound is preferably 10 to 40% by mass, more preferably 15%, based on the total solid content of the photosensitive resin composition of the present embodiment. To 25% by mass.
- the photosensitive resin composition according to the present embodiment preferably contains an organic solvent (S) in order to improve applicability or adjust the viscosity.
- Organic solvents (S) include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate (MA), 3-methoxybutanol (BM) ), 3-me 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene
- the amount of the organic solvent (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. Specifically, it is preferable to use the photosensitive resin composition so that the solid content concentration is in the range of 10 to 50% by mass, particularly 15 to 35% by mass.
- the photosensitive resin composition for forming an interlayer insulating film according to this embodiment may contain a surfactant (E).
- the surfactant (E) include silicone surfactants and fluorine surfactants. Specifically, BYK-Chemie's BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK are available as BYK-Chemie.
- BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355 BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, and the like can be used.
- Fluorosurfactants include DIC (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, and F-444.
- the surfactant (E) may be other than those described above, and examples thereof include anionic, cationic, and nonionic compounds. Specific examples include
- the content of the surfactant (E) is preferably 0.01 to 10% by mass based on the total solid content of the photosensitive resin composition of the present embodiment.
- the content is preferably 0.1 to 2% by mass, most preferably 0.05 to 1% by mass.
- the photosensitive resin composition which concerns on this embodiment may contain various additives, such as a sensitizer and an antifoamer.
- sensitizer those used in conventionally known positive resists can be used.
- a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less can be used.
- the antifoaming agent may be a conventionally known antifoaming agent, and examples thereof include silicone compounds and fluorine compounds.
- the (A) component, the (B) component, the (C) component, and the (D) component are mixed (dispersed and kneaded) with a stirrer such as a roll mill, a ball mill, or a sand mill. If necessary, it can be prepared by filtering with a filter such as a 5 ⁇ m membrane filter.
- the interlayer insulation film of this embodiment uses the said photosensitive resin composition for interlayer insulation film formation.
- the interlayer insulating film of this embodiment can be suitably used as an interlayer insulating film provided to insulate between wirings arranged in layers in electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements.
- the method for forming an interlayer insulating film according to this embodiment includes a step of forming a photosensitive resin composition layer on a support using the photosensitive resin composition for forming an interlayer insulating film, and the photosensitive resin composition layer. , Exposing the exposed photosensitive resin composition layer to form an interlayer insulating film pattern, and heat curing the interlayer insulating film pattern.
- a method for forming an interlayer insulating film using the photosensitive resin composition according to the present embodiment will be described.
- a photosensitive resin composition according to this embodiment is applied onto a support such as a substrate using a spinner, a roll coater, a spray coater, a slit coater, or the like, and dried to form a photosensitive resin composition layer.
- a support such as a substrate using a spinner, a roll coater, a spray coater, a slit coater, or the like
- the substrate include a glass plate that includes wiring such as a transparent conductive circuit, and includes a black matrix, a color filter, a polarizing plate, and the like as necessary.
- drying method examples include (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C. for 60 to 300 seconds, (2) a method of leaving at room temperature for several hours to several days, and (3) a temperature. Any method of removing the solvent by placing it in a wind heater or an infrared heater for several tens of minutes to several hours may be used.
- the film thickness of the photosensitive resin composition layer is not particularly limited, but is preferably about 1.0 to 5.0 ⁇ m.
- exposure is performed through a predetermined mask.
- This exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light.
- active energy rays such as ultraviolet rays and excimer laser light.
- the active energy ray light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, and an excimer laser generator.
- the energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, it may be, for example, about 30 to 2000 mJ / cm 2 .
- the exposed photosensitive resin composition layer is developed with a developer to form a pattern.
- the developer include an organic alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution or an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium metasilicate, and sodium phosphate.
- TMAH tetramethylammonium hydroxide
- an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium metasilicate, and sodium phosphate.
- an interlayer insulating film can be provided in a desired range.
- the pattern is cured by heating. This heat curing is preferably performed, for example, under conditions of 300 ° C. or lower, and more preferably performed under conditions of 250 ° C. or lower.
- the photosensitive resin film (interlayer insulating film) formed using the photosensitive resin composition for forming an interlayer insulating film of the present embodiment has lost the peak due to the epoxy group after the heat curing treatment. It was found that the polymerization reaction was accelerated. As a result of the acceleration of the polymerization reaction, a resin film having an improved film density was obtained, and it is considered that chemical resistance was also improved.
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Abstract
Description
本願は、2014年8月27日に日本に出願された、特願2014-173129号に基づき優先権を主張し、その内容をここに援用する。
本発明の第二の態様は、前記第一の態様の層間絶縁膜形成用感光性樹脂組成物を用いた層間絶縁膜である。
本発明の第三の態様は、支持体上に、前記第一の態様の層間絶縁膜形成用感光性樹脂組成物を用いて感光性樹脂組成物層を形成する工程と、前記感光性樹脂組成物層を露光する工程と、露光された前記感光性樹脂組成物層を現像して層間絶縁膜パターンを形成する工程と、前記層間絶縁膜パターンを加熱硬化する工程と、を有する、層間絶縁膜の形成方法である。
本実施形態の層間絶縁膜形成用感光性樹脂組成物(以下単に「感光性樹脂組成物」ともいう)は、アルカリ可溶性樹脂(A)と、感光剤(B)と、加熱により酸を発生する熱酸発生剤(T)と、シランカップリング剤(C)と、を含有する層間絶縁膜形成用感光性樹脂組成物であって、前記アルカリ可溶性樹脂(A)は、一般式(a-1)で表される構成単位(A1)又は脂環式エポキシ基含有単位(A3)を有する。
アルカリ可溶性樹脂(A)(以下、「共重合体(A)」と記載することがある。)は、下記一般式(a-1)で表される構成単位(A1)又は脂環式エポキシ基含有単位(A3)を有する。
構成単位(A1)は、下記一般式(a-1)で表される。
一般式(a-1)中、Ra01は水素原子、又は水酸基を有する有機基である。
ここで、有機基としては、例えば、分岐状、直鎖状若しくは環状のアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、置換基を有していてもよいアラルキル基、又は置換基を有していてもよいヘテロアラルキル基を挙げることができ、Ra01は、その構造中に少なくとも一つの水酸基を有する。前記有機基の炭素数は1~20であることが好ましく、6~12であることが更に好ましい。炭素数が大きいと保存安定性や層間絶縁層の低誘電率化の面で好ましく、炭素数が小さいと解像性に優れる。
また、Ya01は単結合又は炭素数1~5の直鎖状若しくは分岐状のアルキレン基を示す。具体的には、メチレン基、エチレン基、プロピレン基、イソプロピレン基、n-ブチレン基、イソブチレン基、tert-ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基等が挙げられる。中でも、単結合、メチレン基、エチレン基であることが好ましい。
Ya01は、アルカリ可溶性を向上させることができることと、更に層間絶縁膜としたときの耐熱性が向上することから、単結合であることが好ましい。
ここで、bは0又は1~4の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、bは0であることが好ましい。
脂環式エポキシ基含有単位(A3)としては、脂環式エポキシ基を構造中に有し、エチレン性二重結合を有する化合物から誘導される構成単位であれば、特に限定されない。脂環式エポキシ基の脂環式基の炭素数は、5~10程度が好ましい。共重合体(A)が脂環式エポキシ基含有単位(A3)を有することで、アウトガス発生の原因となる低分子量架橋成分を感光性樹脂組成物に添加せずとも、その耐熱性を向上することが可能となる。
また、上記共重合体(A)は、下記一般式(a-2)で表される構成単位(A2)を有することが好ましい。
前記炭化水素基の炭素数は1~20であることが好ましい。更に、分岐状、直鎖状のアルキル基としては、炭素数1~12が好ましく、1~6が最も好ましい。
環状のアルキル基としては、炭素数6~20が好ましく、6~12が最も好ましい。置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基としては、炭素数6~20が好ましく、6~12が最も好ましい。
炭素数が20以下であればアルカリ解像性は十分であり、炭素数が1以上であれば層間絶縁膜の誘電率を低減できて好ましい。
また、上記共重合体(A)には、本発明の目的に反しない範囲で構成単位(A1)~(A3)以外の構成単位(A4)を有していてもよい。この構成単位(A4)は、エチレン性二重結合を有する化合物から誘導される構成単位であれば、特に限定されない。このような構成単位(A4)としては、例えば、アクリルアミド類、メタクリルアミド類、アリル化合物、ビニルエーテル類、ビニルエステル類、及びスチレン類等から選ばれる化合物から誘導される構成単位が挙げられる。
上記共重合体(A)の質量平均分子量(Mw:ゲルパーミエーションクロマトグラフィ(GPC)のポリスチレン換算による測定値)は、2000~50000であることが好ましく、5000~30000であることがより好ましい。分子量を2000以上とすることにより、容易に膜状に形成することが可能となる。また、分子量50000以下とすることによって、適度なアルカリ溶解性を得ることが可能となる。
感光剤(B)としては、感光成分として使用できる化合物であれば特に限定されるものではないが、好ましい例としてキノンジアジド基含有化合物が挙げられる。
本実施形態の層間絶縁膜形成用感光性樹脂組成物は、熱酸発生剤(T)を含有する。
本実施形態の層間絶縁膜形成用感光性樹脂組成物は、熱酸発生剤(T)を含有するため、熱硬化処理時に、熱により発生する酸の作用により、感光性樹脂膜中の重合反応(特にアルカリ可溶性樹脂中のエポキシ基での重合)がさらに促進され、膜密度が向上すると考えられる。
熱酸発生剤(T)としては、公知のものから適宜選択して用いればよく、トリフルオロメタンスルホン酸塩、三フッ化ホウ素エーテル錯化合物、六フッ化リン酸塩、パーフルオロブタンスルホン酸、三フッ化ホウ素等のカチオン系又はプロトン酸触媒等を用いることができる。中でも、6フッ化リン酸塩、トリフルオロメタンスルホン酸、パーフルオロブタンスルホン酸が好まく、トリフルオロメタンスルホン酸がより好ましい。
その具体例としては、トリフルオロメタンスルホン酸ジエチルアンモニウム、トリフルオロメタンスルホン酸トリエチルアンモニウム、トリフルオロメタンスルホン酸ジイソプロピルアンモニウム、トリフルオロメタンスルホン酸エチルジイソプロピルアンモニウム等が挙げられる。また、酸発生剤としても用いられる芳香族オニウム塩のうち、熱によりカチオン種を発生するものがあり、これらも熱カチオン重合開始剤として用いることができる。例えば、サンエイドSI-45、SI-47、SI-60、SI-60L、SI-80、SI-80L、SI-100、SI-100L、SI-110L、SI-145、I-150、SI-160、SI-180L、SIーB3、SIーB3A(三新化学工業(株)製)等が挙げられる。その他にも、CI-2921、CI-2920、CI-2946、CI-3128、CI-2624、CI-2639、CI-2064(日本曹達(株)製)、CP-66、CP-77((株)ADEKA製)、FC-520(3M社製)K―PURE TAG-2396、TAG-2713S、TAG-2713、TAG-2172、TAG-2179、TAG-2168E、TAG-2722、TAG-2507、TAG-2678、TAG-2681、TAG-2679、TAG-2690、TAG-2700、TAG-2710、TAG-2100、CDX-3027、CXC-1615、CXC-1616、CXC-1750、CXC-1738、CXC-1614、CXC-1742、CXC-1743、CXC-1613、CXC-1739、CXC-1751、CXC-1766、CXC-1763、CXC-1736、CXC-1756、CXC-1821、CXC-1802-60(KING INDUSTRY社製)等が挙げられる。
上記のなかでも、トリフルオロメタンスルホン酸塩又は六フッ化リン酸塩が好ましく、トリフルオロメタンスルホン酸塩がより好ましい。
なお、熱酸発生剤(T)の酸発生温度がプリベーク温度よりも低いと、プリベーク時に熱酸発生剤(T)から酸が発生し、感光性樹脂膜中で重合が進行してしまうため、露光部におけるアルカリ溶解性が低下してしまい、良好なパターンが形成できない。
一方、熱酸発生剤(T)の酸発生温度を上記の範囲とした場合には、感光性樹脂膜形成後の熱硬化処理時において、感光性樹脂膜中の重合を促進できるため、パターン形成を阻害することなく、膜密度の向上に寄与できると考えられる。
前記上限値以下とすることにより、熱酸発生剤自身の光吸収の影響が低減されるため、光の透過性を良好なものとすることができ、良好にパターンを形成できると考えられる。
また、前記下限値以上とすることにより、重合に必要な酸発生量を確保し、重合が促進されるため、膜密度の高い膜を形成することができると考えられる。この結果、感光性樹脂膜の耐薬品性が向上すると考えられる。具体的には、例えば、半導体製造工程に供されるときに曝される溶剤(例えば、PGMEA、PGME、N-メチルピロリドン(NMP)等)、酸(フッ化水素酸等)、アルカリ(TMAH等)に対して優れた耐性を発揮できる。
本実施形態の層間絶縁膜形成用感光性樹脂組成物は、シランカップリング剤(C)を含有する。本実施形態の層間絶縁膜形成用感光性樹脂組成物は、シランカップリング剤(C)を含有することにより、感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、感光性樹脂組成物により形成された膜の性質を調整することができたりする。
シランカップリング剤(C)として、具体的には、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリアコキシシラン、γ-グリシドキシプロピルアルキルジアルコキシシラン、γ-メタクリロキシプロピルトリアルコキシシラン、γ-メタクリロキシプロピルアルキルジアルコキシシラン、γ-クロロプロピルトリアルコキシシラン、γ-メルカプトプロピルトリアルコキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ-グリシドキシプロピルトリアルコキシシランやγ-メタクリロキシプロピルトリアルコキシシランがより好ましく、γ-グリシドキシプロピルトリアルコキシシランがさらに好ましく、3-グリシドキシプロピルトリメトキシシランが特に好ましい。これらは1種単独または2種以上を組み合わせて使用することができる。
本実施形態の層間絶縁膜形成用感光性樹脂組成物は、さらに架橋剤(D)を含有することが好ましい。また、架橋剤(D)は、オキセタン含有化合物、エポキシ基含有化合物及びブロックイソシアネート化合物からなる群から選択される少なくとも1種であることがより好ましい。
オキセタン基又はエポキシ基を有する化合物としては、例えば、スチレンオキシド、フェニルグリシジルエーテル、o-フェニルフェノールグリシジルエーテル、p-フェニルフェノールグリシジルエーテル、グリシジルシンナメート、メチルグリシジルエーテル、ブチルグリシジルエーテル、2-エチルヘキシルグリシジルエーテル、デシルグリシジルエーテル、ステアリルグリシジルエーテル、アリルグリシジルエーテル、グリシドール、N-グリシジルフタルイミド、1,3-ジブロモフェニルグリシジルエーテル、セロキサイド2000(ダイセル化学工業株式会社製)、オキセタンアルコール等が挙げられる。
オキセタン含有化合物の具体例としては、アロンオキセタンOXT-121、OXT-221、OX-SQ、PNOX(以上、東亞合成(株)製)を用いることができる。
エポキシ基含有化合物の具体例としては、エポキシ樹脂EXA4850-150、エポキシ樹脂EXA4850-1000(ともにDIC株式会社製)を用いることができる。
ブロックイソシアネート化合物は、常温では不活性であり、加熱されることにより、オキシム類、ジケトン類、フェノール類、カプロラクタム類等のブロック剤が解離してイソシアネート基を再生する化合物である。ブロックイソシアネート化合物は1種を単独で使用できまたは2種以上を併用できる。
中でもアダクト体としては、脂肪族ジイソシアネートとトリメチロールプロパンとの付加体が、ビウレット体としてはヘキサメチレンジイソシアネートと水又は三級アルコールとの反応物が、イソシアヌレート体としてはヘキサメチレンジイソシアネートの三量体が好ましい。
ブロック化触媒としては公知のものを使用でき、たとえば、ナトリウムメチラート、ナトリウムエチラート、ナトリウムフェノラート、カリウムメチラートなどの金属アルコラート、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウムなどのテトラアルキルアンモニウムのハイドロオキサイド、これらの酢酸塩、オクチル酸塩、ミリスチン酸塩、安息香酸塩などの有機弱酸塩、酢酸、カプロン酸、オクチル酸、ミリスチン酸などのアルキルカルボン酸のアルカリ金属塩などが挙げられる。ブロック化触媒は1種を単独で使用できまたは2種以上を併用できる。
ブロックイソシアネート化合物の含有量は、本実施形態の感光性樹脂組成物の全固形分に対して好ましくは1~60質量%、より好ましくは5~50質量%、最も好ましくは10~40質量%である。
また、ブロックイソシアネート化合物の中でも、アダクト型のブロックイソシアネート化合物を採用することが好ましい。
アダクト型のブロックイソシアネート化合物を採用する場合、アダクト型のブロックイソシアネート化合物の含有量は、本実施形態の感光性樹脂組成物の全固形分に対して好ましくは10~40質量%、より好ましくは15~25質量%である。
上記範囲とすることにより、層間絶縁膜の機械特性の向上に加え、熱耐性も付与することができる。
本実施形態に係る感光性樹脂組成物は、塗布性を改善したり、粘度を調整したりするために、有機溶剤(S)を含有することが好ましい。
本実施形態の層間絶縁膜形成用感光性樹脂組成物は、界面活性剤(E)を含有していてもよい。
界面活性剤(E)としては、シリコーン系界面活性剤またはフッ素系界面活性剤が挙げられる。具体的には、シリコーン系界面活性剤は、BYK-Chemie社のBYK-077、BYK-085、BYK-300、BYK-301、BYK-302、BYK-306、BYK-307、BYK-310、BYK-320、BYK-322、BYK-323、BYK-325、BYK-330、BYK-331、BYK-333、BYK-335、BYK-341v344、BYK-345v346、BYK-348、BYK-354、BYK-355、BYK-356、BYK-358、BYK-361、BYK-370、BYK-371、BYK-375、BYK-380、BYK-390などを使用することができる。
フッ素系界面活性剤としては、DIC(DaiNippon Ink&Chemicals)社のF-114、F-177、F-410、F-411、F-450、F-493、F-494、F-443、F-444、F-445、F-446、F-470、F-471、F-472SF、F-474、F-475、F-477、F-478、F-479、F-480SF、F-482、F-483、F-484、F-486、F-487、F-172D、MCF-350SF、TF-1025SF、TF-1117SF、TF-1026SF、TF-1128、TF-1127、TF-1129、TF-1126、TF-1130、TF-1116SF、TF-1131、TF1132、TF1027SF、TF-1441、TF-1442などを使用することができるが、これらにのみ限定されるものではない。
また、界面活性剤(E)としては、上記以外のものであってもよく、アニオン系、カチオン系、ノニオン系等の化合物が挙げられる。具体的には、X-70-090(商品名、信越化学工業社製)等を挙げることができる。
また、本実施形態に係る感光性樹脂組成物は、増感剤、消泡剤等の各種添加剤を含有していてもよい。
本実施形態の層間絶縁膜は、前記層間絶縁膜形成用感光性樹脂組成物を用いたものである。
本実施形態の層間絶縁膜は、液晶表示素子、集積回路素子、固体撮像素子等の電子部品における層状に配置される配線の間を絶縁するために設ける層間絶縁膜として好適に用いることができる。
本実施形態の層間絶縁膜の形成方法は、支持体上に、前記層間絶縁膜形成用感光性樹脂組成物を用いて感光性樹脂組成物層を形成する工程と、前記感光性樹脂組成物層を露光する工程と、露光された前記感光性樹脂組成物層を現像して層間絶縁膜パターンを形成する工程と、前記層間絶縁膜パターンを加熱硬化する工程と、を有する。
以下、本実施形態に係る感光性樹脂組成物を用いて層間絶縁膜を形成する方法について説明する。
最後に、前記パターンを加熱硬化する。この加熱硬化は、例えば300℃以下の条件で行うことが好ましく、250℃以下の条件で行うことがより好ましい。
表1に示す各成分を混合し、PGMEA/PGME=60/40(質量比)の混合溶剤に溶解して、感光性樹脂組成物を調製した。なお、実施例1~12及び比較例1の感光性樹脂組成物の固形分濃度は40質量%である。
(A)-1:下記高分子化合物(A)-1、ゲルパーミエーションクロマトグラフィ(GPC)のポリスチレン換算による質量平均分子量(Mw)は17000、13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はx/y/z=50/30/20
(B)-2:下記化合物(B)-1の1モルに対し、ナフトキノンジアジド-5-スルホン酸エステルを2モル反応させたもの
(C)-1:下記化合物(C)-1
(T)-1:熱カチオン重合開始剤
(KING INDUSTRY社製、TAG-2678)
(T)-2:熱カチオン重合開始剤
(KING INDUSTRY社製、TAG-2689)
(T)-3:熱カチオン重合開始剤
(KING INDUSTRY社製、TAG-2690)
(T)-4:熱カチオン重合開始剤
(KING INDUSTRY社製、TAG-2700)
(T)-5:熱カチオン重合開始剤
(KING INDUSTRY社製、CXC-1821)
(T)-6:熱カチオン重合開始剤
(KING INDUSTRY社製、CXC-1738)
(T)-7:熱カチオン重合開始剤
(KING INDUSTRY社製、CXC-1802-60)
(E)-1:シリコーン系界面活性剤(ビックケミー・ジャパン社製、BYK-310)
実施例および比較例で調製した各感光性樹脂組成物を、8インチシリコン基板上にスピンコーター(TR25000:東京応化工業(株)製)を用いて塗布し、110℃で300秒間プリベークを行い、膜厚10μmの塗膜(感光性樹脂組成物層)を形成した。
次いで、超高圧水銀灯(ghi-line)を使用し、塗膜にマスクを介して紫外線を照射した。露光量は、1000mJ/cm2とした。
露光後の塗膜を、23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で60秒間現像し、100℃で30分間、その後120℃で30分間、その後200℃で60分間の加熱硬化処理を行い、感光性樹脂パターンを形成した。
[赤外線吸収(IR)スペクトル測定]
加熱硬化処理により感光性樹脂膜(塗膜)中の重合が促進されることによる膜密度の向上の有無を評価するため、加熱硬化処理後において、赤外線吸収(IR)スペクトル測定を行った。
加熱硬化処理後のIR測定により、エポキシ基に由来するピーク(920cm-1付近)が消失していれば、加熱硬化処理により重合が促進された、即ち、膜密度が向上したことを示す。また、加熱硬化処理後のIR測定により、エポキシ基に由来するピーク(920cm-1付近)が消失していなければ、加熱硬化処理により重合が促進されなかったことを示す。
上記で形成した感光性樹脂パターンについて、N-メチルピロリドンと、2%テトラメチルアンモニウムヒドロキシド水溶液との混合溶剤(混合比92/8)に、40℃で15分間のディップ処理を行い、感光性樹脂パターンの剥がれの有無を目視で観察した。
表2中、感光性樹脂パターンの剥がれが見受けられなかったものを「Good」、感光性樹脂パターンが部分的に剥がれていたものを「Poor」として記載する。
Claims (9)
- 前記熱酸発生剤(T)の酸発生温度が、110℃以上である、請求項1又は2に記載の層間絶縁膜形成用感光性樹脂組成物。
- 前記熱酸発生剤(T)は、トリフルオロメタンスルホン酸塩、三フッ化ホウ素エーテル錯化合物、六フッ化リン酸塩、パーフルオロブタンスルホン酸、三フッ化ホウ素のカチオン系又はプロトン酸触媒からなる群から選択される少なくとも1種である、請求項1~3のいずれか1項に記載の層間絶縁膜形成用感光性樹脂組成物。
- 前記熱酸発生剤(T)の含有量は、感光性樹脂組成物の全固形分に対して0.1~1.5質量%である、請求項1~4のいずれか1項に記載の層間絶縁膜形成用感光性樹脂組成物。
- さらに架橋剤(D)を含有する、請求項1~5のいずれか1項に記載の層間絶縁膜形成用感光性樹脂組成物。
- 請求項1~6のいずれか1項に記載の層間絶縁膜形成用感光性樹脂組成物を用いた層間絶縁膜。
- 支持体上に、請求項1~6のいずれか1項に記載の層間絶縁膜形成用感光性樹脂組成物を用いて感光性樹脂組成物層を形成する工程と、
前記感光性樹脂組成物層を露光する工程と、
露光された前記感光性樹脂組成物層を現像して層間絶縁膜パターンを形成する工程と、
前記層間絶縁膜パターンを加熱硬化する工程と、
を有する、層間絶縁膜の形成方法。 - 前記加熱硬化の処理を300℃以下で行う、請求項8に記載の層間絶縁膜の形成方法。
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CN109478017A (zh) * | 2016-08-19 | 2019-03-15 | 罗门哈斯电子材料韩国有限公司 | 感光性树脂组合物及其制备的固化膜 |
US20200407545A1 (en) * | 2019-06-28 | 2020-12-31 | Tokyo Ohka Kogyo Co., Ltd. | Curable resin composition and cured product |
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TWI742515B (zh) * | 2016-07-21 | 2021-10-11 | 日商東京威力科創股份有限公司 | 半導體裝置之製造方法、真空處理裝置及基板處理裝置 |
JP7452959B2 (ja) * | 2019-08-19 | 2024-03-19 | 東京応化工業株式会社 | カラーフィルターの製造方法、カラーフィルター、及び樹脂組成物 |
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Also Published As
Publication number | Publication date |
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TWI741966B (zh) | 2021-10-11 |
KR20170045221A (ko) | 2017-04-26 |
US10067422B2 (en) | 2018-09-04 |
KR102448657B1 (ko) | 2022-09-28 |
JP6774876B2 (ja) | 2020-10-28 |
JPWO2016031580A1 (ja) | 2017-06-08 |
US20170255099A1 (en) | 2017-09-07 |
TW201624112A (zh) | 2016-07-01 |
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