WO2023021688A1 - 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス - Google Patents
感光性樹脂組成物、電子デバイスの製造方法および電子デバイス 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a photosensitive resin composition, an electronic device manufacturing method, and an electronic device. More specifically, it relates to a photosensitive resin composition containing a polyamide resin and/or a polyimide resin, a method for producing an electronic device using the photosensitive resin composition, and an electronic device that can be produced by the method for producing an electronic device.
- photosensitive resin compositions containing polyamide resins and/or polyimide resins are sometimes used to form cured films such as insulating layers. Therefore, photosensitive resin compositions containing polyamide resins and/or polyimide resins have been investigated.
- US Pat. No. 5,300,002 discloses at least one fully imidized polyimide polymer having a weight average molecular weight ranging from about 20,000 Daltons to about 70,000 Daltons; at least one solubility-switching compound; at least one A photosensitive composition is described which comprises a photoinitiator; and at least one solvent and is capable of forming a film exhibiting a dissolution rate of greater than about 0.15 ⁇ m/sec when cyclopentanone is used as a developer. ing.
- Patent Documents 2 and 3 also describe photosensitive resin compositions containing polyamide resins and/or polyimide resins.
- the present invention was made in view of such circumstances.
- One of the objects of the present invention is to provide a photosensitive resin composition that can be cured by heating at about 170° C. to form a cured film, thereby enabling production of highly reliable electronic devices.
- the following photosensitive resin composition is provided.
- a photosensitive resin composition containing a polyamide resin and / or a polyimide resin The cured film obtained by heating the photosensitive resin composition at 170 ° C. for 2 hours is subjected to dynamic viscoelasticity measurement under the following conditions, and the storage elastic modulus E'220 at 220 ° C. is 0.5 to A photosensitive resin composition of 3.0 GPa.
- a method of manufacturing an electronic device comprising:
- An electronic device comprising a cured film of the above photosensitive resin composition is provided.
- a highly reliable electronic device can be manufactured by curing the photosensitive resin composition of the present invention by heating at about 170°C to form a cured film.
- the term “substantially” means that it includes a range that takes into account manufacturing tolerances, assembly variations, and the like, unless otherwise explicitly stated.
- the notation “X to Y” in the description of numerical ranges means X or more and Y or less, unless otherwise specified.
- “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
- alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
- (meth)acryl used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate”.
- organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified.
- a "monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
- electronic device in this specification refers to elements to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information communication terminals, light emitting diodes, physical batteries, chemical batteries, etc. , devices, final products, etc.
- the photosensitive resin composition of this embodiment contains a polyamide resin and/or a polyimide resin.
- a cured film obtained by heating the photosensitive resin composition of the present embodiment at 170 ° C. for 2 hours is subjected to dynamic viscoelasticity measurement under the following conditions. 0.5 to 3.0 GPa. [conditions] Frequency: 1Hz Temperature: 30-300°C Heating rate: 5°C/min Measurement mode: Tensile mode
- the cured film may reach a high temperature due to various "heating" being performed.
- the present inventors considered that the high temperature due to heating adversely affects the cured film in the electronic device, and as a result reduces the reliability of the electronic device. More specifically, since the cured film deteriorates/softens at high temperatures, for example, the adhesive strength between the cured film and the substrate decreases, causing peeling of the cured film, and as a result, the reliability of the electronic device does not decrease. I thought.
- the present inventors found that, for example, in heating such as a reflow process, it is difficult to soften at 220 ° C., which can be used as a heating temperature (it can also be expressed that the elastic modulus at 220 ° C. is relatively large). It was thought that if a photosensitive resin composition capable of forming a film could be designed, the decrease in adhesion of the cured film due to heating could be suppressed, and as a result, the reliability of electronic devices would be enhanced. In addition, it was thought that if such a cured film could be formed by heating at about 170° C., it would be possible to follow the recent trends in the manufacture of electronic devices.
- the present inventors found that, in a photosensitive resin composition containing a polyamide resin and/or a polyimide resin, (i) as an indicator of the difficulty of softening the cured film at 220 ° and ( ii) newly designed a photosensitive resin composition having E' 220 of 0.5 GPa or more.
- a photosensitive resin composition having E' 220 of 0.5 GPa or more.
- the condition for forming the cured film "2 hours at 170° C.” was adopted based on the recent trend in the manufacture of electronic devices.
- this new photosensitive resin composition to the manufacture of electronic devices (for example, the formation of insulating layers in electronic devices), the present inventors have succeeded in improving the reliability of electronic devices.
- E' 220 the larger E' 220 is, the better.
- the upper limit of E'220 is set to 3.0 GPa in this embodiment.
- E′ 220 may be 0.5 to 3.0 GPa, preferably 0.6 to 2.5 GPa, more preferably 0.7 to 2.0 GPa.
- the photosensitive resin composition having an E′ 220 of 0.5 GPa or more and 3.0 GPa or less according to the present embodiment can be produced by appropriately selecting materials, their formulation, preparation methods, and the like. Preferred materials for the photosensitive resin composition of the present embodiment will be described below.
- an appropriate polyfunctional (meth) acrylate is selected. and so on.
- the photosensitive resin composition of this embodiment contains a polyamide resin and/or a polyimide resin.
- E'220 is 0.5 to 3.0 GPa, the structure, molecular weight, usage amount, etc. of the polyamide resin and/or polyimide resin are not limited.
- the photosensitive resin composition of the present embodiment preferably contains a polyimide resin, and more preferably contains a polyimide resin having an imide ring structure.
- the imidization rate is represented by ⁇ IM/(IM+AM) ⁇ 100 (%). is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.
- the polyimide resin preferably has little or no ring-opening amide structure and many ring-closing imide structures.
- the imidization rate can be known, for example, from the area of the peak corresponding to the amide group or the area of the peak corresponding to the imide group in the NMR spectrum.
- the imidization rate can be known from the area of the peak corresponding to the amide group, the area of the peak corresponding to the imide group, and the like in the infrared absorption spectrum.
- the polyamide resin and/or polyimide resin preferably contain fluorine atoms.
- the present inventors have found that polyamide resins and/or polyimide resins containing fluorine atoms tend to have better solubility in organic solvents than those containing no fluorine atoms. Therefore, by using a polyamide resin and/or a polyimide resin containing fluorine atoms, the photosensitive resin composition can easily be made into a varnish.
- the amount (mass ratio) of fluorine atoms in the polyamide resin and/or polyimide resin containing fluorine atoms is, for example, 1 to 30% by mass, preferably 3 to 28% by mass, more preferably 5 to 25% by mass.
- a sufficient amount of fluorine atoms contained in the resin facilitates obtaining sufficient organic solvent solubility.
- it is preferable that the amount of fluorine atoms is not too large.
- the mechanical properties (tensile elongation, etc.) of the cured product can be further improved.
- polyamide resins and/or polyimide resins preferably have groups at their ends that can react with epoxy groups to form bonds.
- groups include acid anhydride groups, hydroxy groups, amino groups, carboxy groups, and the like.
- the polyamide resin and/or polyimide resin has an acid anhydride group at its end.
- the acid anhydride group and the epoxy group are sufficiently easy to form a bond.
- the acid anhydride group is preferably a group having a cyclic acid anhydride skeleton.
- the "cyclic structure" herein is preferably a 5- or 6-membered ring, more preferably a 5-membered ring.
- the polyamide resin and/or the polyimide resin do not have a maleimide structure at its terminal.
- the polyamide resin preferably contains a structural unit represented by the following general formula (PA-1).
- the polyimide resin preferably contains a structural unit represented by the following general formula (PI-1).
- X is a divalent organic group
- Y is a tetravalent organic group
- At least one of X and Y is preferably a fluorine atom-containing group.
- both X and Y in general formulas (PA-1) and (PI-1) are preferably fluorine atom-containing groups.
- the divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, and may contain a benzene ring structure. More preferred. This tends to further increase the heat resistance.
- the benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom or a fluorinated alkyl group (preferably a trifluoromethyl group), or may be substituted with other groups.
- the divalent organic group for X and/or the tetravalent organic group for Y preferably have 2 to 6 benzene rings each of which is a single bond or a divalent have a structure in which they are bonded via a linking group of Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.
- the divalent organic group of X has, for example, 6 to 30 carbon atoms.
- the tetravalent organic group of Y has, for example, 6 to 20 carbon atoms.
- Each of the two imide rings in general formula (PI-1) is preferably a 5-membered ring.
- the polyamide resin more preferably contains a structural unit represented by the following general formula (PA-2).
- the polyimide resin more preferably contains a structural unit represented by the following general formula (PI-2).
- X is synonymous with X in general formulas (PA-1) and (PI-1), Y' represents a single bond or an alkylene group.
- the alkylene group of Y' may be linear or branched. Some or all of the hydrogen atoms in the alkylene group of Y' are preferably substituted with fluorine atoms.
- the number of carbon atoms in the alkylene group of Y' is, for example, 1-6, preferably 1-4, more preferably 1-3.
- a polyamide resin can typically be obtained by reacting (condensing) a diamine and an acid dianhydride.
- a polyimide resin can be obtained by imidating a polyamide resin (performing a ring closure reaction).
- a desired functional group may be introduced at the terminal of the polymer, if necessary. Specific reaction conditions can be referred to Examples described later, the description of Patent Document 1 described above, and the like.
- the diamine is incorporated into the polymer as the divalent organic group X in general formula (PA-1) or (PI-1).
- the acid dianhydride is incorporated into the polymer as the tetravalent organic group Y in general formula (PA-1) or (PI-1).
- one or more diamines can be used, and one or more acid dianhydrides can be used.
- Raw material diamines include, for example, 3,4′-diaminodiphenyl ether (3,4′-ODA), 4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl (TFMB), 3,3 ',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenylsulfone, 3,3'dimethylbenzidine, 3,3'- Bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB) , 2,2′-trifluoromethyl-4,4′-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)
- acid dianhydrides used as raw materials include pyromellitic anhydride (PMDA), diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride (ODPA), benzophenone-3,3′, 4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenylsulfone-3,3',4,4'- Tetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis (3,4-Phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA) and the like can be mentioned.
- acid dianhydrides that can be used are not limited to these.
- the usage ratio of the diamine and the acid dianhydride is basically 1:1 in terms of molar ratio. However, one may be used in excess to obtain the desired terminal structure. Specifically, by using an excessive amount of diamine, the terminals (both terminals) of the polyamide resin and/or the polyimide resin tend to become amino groups. On the other hand, by using an excessive amount of acid dianhydride, the ends (both ends) of the polyamide resin and/or the polyimide resin tend to become acid anhydride groups. As described above, in the present embodiment, the polyamide resin and/or polyimide resin preferably has an acid anhydride group at its end. Therefore, in the present embodiment, it is preferable to use an excessive amount of acid dianhydride when synthesizing the polyamide resin and/or the polyimide resin.
- terminal amino groups and/or acid anhydride groups of the polyamide resin and/or polyimide resin obtained by condensation polymerization may be reacted with some kind of reagent so that the resin terminals have desired functional groups.
- the weight average molecular weight of the polyamide resin and/or polyimide resin is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000.
- the weight average molecular weight of the polyamide resin and/or the polyimide resin is large to some extent, for example, sufficient heat resistance of the cured film can be obtained. Further, when the weight average molecular weight of the polyamide resin and/or the polyimide resin is not too large, the polyamide resin and/or the polyimide resin are easily dissolved in the organic solvent.
- the weight average molecular weight can usually be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- the photosensitive resin composition of this embodiment preferably contains a polyfunctional (meth)acrylate compound.
- polyfunctional (meth)acrylate compounds include those having two or more (meth)acryloyl groups in one molecule without particular limitation.
- a photosensitive resin composition having an E'220 of 0.5 to 3.0 GPa can be obtained by using a polyamide resin and/or a polyimide resin together with a polyfunctional (meth)acrylate compound. It is easy to design and tends to make the performance of the cured film even better.
- the polyfunctional (meth)acrylate compound is cured (polymerized), a complex “entangled” structure is formed with the polyamide resin and/or the polyimide resin.
- the polyfunctional (meth)acrylate compound is a polyimide resin having a cyclic skeleton such as an imide ring by polymerization, or a cyclic skeleton of a polyamide resin that may have a cyclic skeleton due to at least a portion of the polyamide structure being closed by heat. is assumed to form a network structure that “wraps” the It is speculated that the formation of such a complexly entangled structure results in an E′ 220 of 0.5 to 3.0 GPa and improved performance of the cured film.
- the polyfunctional (meth)acrylate compound is preferably trifunctional or higher.
- the upper limit for the number of functional groups is, for example, 11 functional groups in consideration of the availability of raw materials.
- the chemical resistance of the cured film tends to increase.
- a polyfunctional (meth)acrylate compound having a small number of functional groups ((meth)acryloyl groups) is used, mechanical properties such as tensile elongation of the cured film tend to be improved.
- the polyfunctional (meth)acrylate compound preferably contains a (meth)acrylate compound with a functionality of 7 or more.
- the polyfunctional (meth)acrylate compound preferably contains a 5- to 6-functional (meth)acrylate compound.
- the polyfunctional (meth)acrylate compound preferably contains a tri- to tetra-functional (meth)acrylate compound.
- the polyfunctional (meth)acrylate compound can include compounds represented by the following general formula.
- R' is a hydrogen atom or a methyl group
- n is 0 to 3
- R is a hydrogen atom or a (meth)acryloyl group.
- Plural R's may be the same or different.
- polyfunctional (meth)acrylate compounds include the following. Of course, polyfunctional (meth)acrylate compounds are not limited to these.
- Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10 , NK Ester A-GLY-9E, NK Ester A-9550, NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the photosensitive resin composition contains a polyfunctional (meth)acrylate compound
- it may contain only one polyfunctional (meth)acrylate compound, or may contain two or more polyfunctional (meth)acrylate compounds. In the latter case, it is preferable to use together polyfunctional (meth)acrylate compounds having different numbers of functional groups.
- polyfunctional (meth)acrylate compounds having different numbers of functional groups By using polyfunctional (meth)acrylate compounds having different numbers of functional groups together, it is believed that a more complicated "entangled structure" is formed and the properties of the cured film are further improved.
- the amount of the polyfunctional (meth) acrylate compound relative to 100 parts by mass of the polyamide resin and/or polyimide resin is preferably 50 to 200 parts by mass, more preferably 60 to 150 parts by mass. be.
- the amount of polyfunctional (meth)acrylate compound used is not particularly limited, but by appropriately adjusting the amount used as described above, one or more of the various properties can be enhanced.
- the polyamide resin and / or polyimide resin and polyfunctional (meth) acrylate "entangled structure" is formed by curing, but the polyamide
- the polyamide resin and/or polyimide resin and the polyfunctional (meth)acrylate compound are moderately entangled, and participate in the entanglement. It is thought that there will be fewer unnecessary ingredients. And it is considered that the performance is further improved.
- the photosensitive resin composition of this embodiment preferably contains a photosensitive agent.
- the photosensitive agent is not particularly limited as long as it can generate active species by light and cure the photosensitive resin composition.
- the photosensitizer preferably contains a photoradical generator.
- Photoradical generators are particularly effective in polymerizing polyfunctional (meth)acrylate compounds.
- the photoradical generator that can be used is not particularly limited, and known ones can be used as appropriate.
- Biimidazole compounds 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-,1-(O-acetyloxime) and other oxime ester compounds; bis( ⁇ 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3 -(1H-pyrrol-1-yl)-phenyl) titanocene compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; etc. can be mentioned.
- oxime ester compounds can be preferably used.
- the photosensitive resin composition contains a photosensitive agent, it may contain only one kind of photosensitive agent, or may contain two or more kinds thereof.
- the amount used is, for example, 1 to 30 parts by mass, preferably 3 to 20 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.
- the photosensitive resin composition of this embodiment preferably contains a thermal radical initiator.
- a thermal radical initiator By using a thermal radical initiator, it is easy to appropriately adjust the value of CTE2/CTE1, which will be described later, to further improve the reliability of the electronic device, and to further increase the heat resistance of the cured film. This is probably because the use of the thermal radical initiator further accelerates the polymerization reaction of the polyfunctional (meth)acrylate compound.
- the thermal radical initiator preferably contains an organic peroxide.
- Organic peroxides include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl- 2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroper
- thermal radical initiator only one thermal radical initiator may be used, or two or more thermal radical initiators may be used.
- its amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate compound.
- epoxy resin The photosensitive resin composition of this embodiment preferably contains an epoxy resin. Although the details are unknown, it is believed that epoxy resins react (form bonds) with, for example, polyamide resins and/or polyimide resins. Then, probably due to the flexibility of the ether structure formed by the reaction, the cured film tends to have higher mechanical properties (tensile elongation, etc.).
- epoxy resin all compounds having one or more (preferably two or more) epoxy groups in one molecule can be appropriately used.
- epoxy resins include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol poly Glycidyl ethers such as glycidyl ether, sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), glycidyl esters such as diglycidyl adipate, diglycidyl o-phthalate, 3,4-epoxycyclohexylmethyl (3, 4-epoxycyclohexane)carboxylate, 3,4-e
- Aliphatic polyglycidyl ether 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (for example, DMS-E09 (manufactured by Gelest) )) and the like.
- the epoxy resin one having 2 to 4 epoxy groups in one molecule is preferable, and one having 2 to 3 epoxy groups in one molecule is more preferable.
- the epoxy resin preferably has an aromatic ring structure and/or an alicyclic structure. The use of such an epoxy resin is particularly preferable from the viewpoint of heat resistance.
- an epoxy resin When using an epoxy resin, only one epoxy resin may be used, or two or more epoxy resins may be used in combination. When an epoxy resin is used, its amount is, for example, 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, based on 100 parts by mass of the polyamide resin and/or polyimide resin. be.
- the photosensitive resin composition of this embodiment preferably contains a curing catalyst.
- This curing catalyst functions to accelerate the reaction of the epoxy resin.
- the reaction involving the epoxy resin proceeds sufficiently, and for example, the tensile elongation of the cured film can be further improved.
- Curing catalysts include compounds known as curing catalysts for epoxy resins (often called curing accelerators). For example, diazabicycloalkenes such as 1,8-diazabicyclo[5,4,0]undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; triphenyl Organic phosphines such as phosphine and methyldiphenylphosphine; tetra-substituted phosphonium salts such as phosphonium/tetranaphthyloxyborate and tetraphenylphosphonium/4,4'-sulfonyldiphenolate; and triphenylphosphine obtained by adducting benzoquinone. Among them, organic phosphines are preferred.
- the amount thereof is, for example, 1 to 80 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the epoxy resin.
- the photosensitive resin composition of this embodiment preferably contains a silane coupling agent.
- a silane coupling agent for example, the adhesion between the substrate and the cured film can be further enhanced.
- Silane coupling agents include, for example, amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, (meth)acryloyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, and vinyl group-containing silane coupling agents.
- a silane coupling agent such as a ureido group-containing silane coupling agent, a sulfide group-containing silane coupling agent, and a silane coupling agent having a cyclic anhydride structure can be used.
- amino group-containing silane coupling agents include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane.
- Silane ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -amino Propylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldiethoxysilane, N-phenyl- ⁇ -amino-propyltrimethoxysilane and the like.
- epoxy group-containing silane coupling agents include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -glycidyl. propyltrimethoxysilane and the like.
- Examples of (meth)acryloyl group-containing silane coupling agents include ⁇ -((meth)acryloyloxypropyl)trimethoxysilane, ⁇ -((meth)acryloyloxypropyl)methyldimethoxysilane, ⁇ -((meth) acryloyloxypropyl)methyldiethoxysilane and the like.
- Mercapto group-containing silane coupling agents include, for example, 3-mercaptopropyltrimethoxysilane.
- Vinyl group-containing silane coupling agents include, for example, vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane and the like.
- Ureido group-containing silane coupling agents include, for example, 3-ureidopropyltriethoxysilane.
- sulfide group-containing silane coupling agents include bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide.
- Silane coupling agents having a cyclic anhydride structure include, for example, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, and 3-dimethylmethoxysilylpropylsuccinic anhydride. be done.
- a silane coupling agent having a cyclic anhydride structure is particularly preferably used.
- the details are unknown, it is speculated that the cyclic anhydride structure readily reacts with the main chain, side chains and/or terminals of the polyamide resin and/or polyimide resin, resulting in a particularly good effect of improving adhesion.
- a silane coupling agent When a silane coupling agent is used, it may be used alone, or two or more adhesion aids may be used in combination.
- the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass when the amount of polyamide resin and/or polyimide resin used is 100 parts by mass. , more preferably 0.4 to 12 parts by mass, more preferably 0.5 to 10 parts by mass.
- the photosensitive resin composition of this embodiment preferably contains a surfactant. This can further improve the applicability of the photosensitive resin composition and the flatness of the film.
- surfactants include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic surfactants.
- the surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improvement of coatability), improvement of developability, and improvement of adhesive strength.
- the surfactant is preferably nonionic.
- the use of nonionic surfactants is preferable, for example, from the viewpoint of suppressing unintentional reactions with other components in the composition and enhancing the storage stability of the composition.
- Examples of commercial products that can be preferably used as surfactants include F-251, F-253, F-281, F-430, F-477 and F-551 of the "Megafac" series manufactured by DIC Corporation. , F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F -565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc.
- fluorine-containing oligomer structure surfactants fluorine-containing nonionic surfactants such as Phthagent 250 and Phthagent 251 manufactured by Neos Co., Ltd., SILFOAM (registered trademark) series manufactured by Wacker Chemie (for example, SD 100 TS, SD 670, SD 850, SD 860, SD 882) and other silicone surfactants.
- SILFOAM registered trademark
- FC4430 and FC4432 manufactured by 3M are also preferable surfactants.
- the photosensitive resin composition of this embodiment contains a surfactant
- it can contain one or more surfactants.
- the amount thereof is, for example, 0.001 to 1 part by mass when the content of the polyamide resin and / or polyimide resin is 100 parts by mass, preferably It is 0.005 to 0.5 parts by mass.
- the photosensitive resin composition of this embodiment may contain water.
- the presence of water facilitates the hydrolysis reaction of the silane coupling agent, and tends to further increase the adhesion between the substrate and the cured film.
- the amount is preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total solid content (non-volatile components) of the photosensitive resin composition. It is preferably 0.2 to 3 parts by mass, more preferably 0.5 to 2 parts by mass.
- the water content of the photosensitive resin composition can be quantified by the Karl Fischer method.
- the photosensitive resin composition of this embodiment preferably contains a solvent. Thereby, a photosensitive resin film can be easily formed on a substrate (particularly, a substrate having a step) by a coating method.
- a solvent usually contains an organic solvent.
- the solvent is not particularly limited as long as it can dissolve or disperse each component described above and does not substantially chemically react with each component.
- solvents examples include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxy and propionate.
- a solvent may be used individually or may be used in multiple combinations.
- the photosensitive resin composition of the present embodiment contains a solvent
- the photosensitive resin composition of the present embodiment is usually in the form of varnish.
- the photosensitive resin composition of the present embodiment is preferably a varnish-like composition in which at least polyamide resin and/or polyimide resin are dissolved in a solvent. Since the photosensitive resin composition of the present embodiment is in the form of varnish, it is possible to form a uniform film by coating. In addition, since the polyamide resin and/or the polyimide resin are "dissolved" in the solvent, a homogeneous cured film can be obtained.
- the concentration of the total solid content (nonvolatile components) in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 45% by mass.
- concentration of the total solid content (nonvolatile components) in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 45% by mass.
- each component can fully be melt
- good coatability can be ensured, which in turn leads to improvement in flatness during spin coating.
- the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the non-volatile component.
- the proportion of the polyamide resin and/or polyimide resin and polyfunctional (meth)acrylate compound in the entire composition is preferably 20 to 50% by mass.
- the photosensitive resin composition of the present embodiment may contain components other than the components listed above, if necessary.
- examples of such components include antioxidants, fillers such as silica, sensitizers, film-forming agents, and the like.
- the thermal expansion behavior of the cured product of the photosensitive resin composition of the present embodiment is appropriate, so that the reliability of the electronic device can be further enhanced.
- Tg [° C.] The glass transition temperature of the cured film obtained by heating the photosensitive resin composition at 170 ° C. for 2 hours
- CTE1 The thermal expansion coefficient of the cured film in the temperature range from Tg-50 [° C.] to Tg-20 [° C.]
- CTE2 is the thermal expansion coefficient of the cured film in the temperature range from Tg + 20 [°C] to Tg + 50 [°C]
- the value of CTE2/CTE1 is preferably 1 to 10, more preferably 1 to 7, and further It is preferably 1-5.
- the photosensitive resin composition By designing the photosensitive resin composition so that the CTE2 is not excessively larger than the CTE1, it is believed that deterioration/softening of the cured film due to heating in the electronic device manufacturing process is further suppressed. And it is considered that the reliability of the electronic device is further improved.
- the value of CTE2/CTE1 is preferably close to 1, but from the viewpoint of realistic composition design, the lower limit is, for example, about 1.1.
- the value of CTE1 itself is preferably 2 ⁇ 10 ⁇ 5 to 8 ⁇ 10 ⁇ 5 /° C., more preferably 2 ⁇ 10 ⁇ 5 to 8 ⁇ 10 ⁇ 5 /° C., further preferably 3 ⁇ 10 ⁇ 5 to 7 ⁇ 10 -5 /°C, particularly preferably 4 ⁇ 10 -5 to 6 ⁇ 10 -5 /°C.
- the value of CTE2 itself is preferably 2 ⁇ 10 ⁇ 5 to 100 ⁇ 10 ⁇ 5 /° C., more preferably 2 ⁇ 10 ⁇ 5 to 80 ⁇ 10 ⁇ 5 /° C., still more preferably 5 ⁇ 10 ⁇ 5 to 60 ⁇ 10 -5 /°C, particularly preferably 5 ⁇ 10 -5 to 50 ⁇ 10 -5 /°C.
- the glass transition temperature Tg is preferably 170 to 270°C, more preferably 170 to 250°C, still more preferably 200 to 250°C, and particularly preferably 210 to 230°C.
- the storage elastic modulus E′250 at 250° C. of the cured film of the photosensitive resin composition of the present embodiment in the dynamic viscoelasticity measurement under the above [conditions] is preferably 0.3 GPa or more, more preferably 0 .3 GPa or more and 3.0 GPa or less, more preferably 0.5 GPa or more and 2.0 GPa or less.
- the storage elastic modulus E′280 at 280° C. of the cured film of the photosensitive resin composition of the present embodiment in the dynamic viscoelasticity measurement under the above [conditions] is preferably 0.1 GPa or more, more preferably 0 .1 GPa or more and 2.0 GPa or less, more preferably 0.2 GPa or more and 1.0 GPa or less.
- the method for manufacturing an electronic device includes: A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition described above; an exposure step of exposing the photosensitive resin film; a developing step of developing the exposed photosensitive resin film; including. Moreover, it is preferable that the method for manufacturing an electronic device of the present embodiment includes a thermosetting step of heating and curing the exposed photosensitive resin film after the above-described developing step. Thereby, a cured film having sufficient heat resistance can be obtained. As described above, an electronic device provided with a cured film of the photosensitive resin composition of the present embodiment can be manufactured.
- the film forming step is usually performed by applying a photosensitive resin composition onto the substrate.
- the film forming step can be performed using a spin coater, bar coater, spray device, inkjet device, or the like.
- Appropriate heating is preferably performed for the purpose of drying the solvent in the coated photosensitive resin composition before the next exposure step.
- the heating at this time is performed, for example, at a temperature of 80 to 150° C. for 1 to 60 minutes.
- the thickness of the photosensitive resin film after drying varies depending on the structure of the final electronic device to be obtained.
- the amount of exposure in the exposure step is not particularly limited. 100 to 2000 mJ/cm 2 is preferred, and 200 to 1000 mJ/cm 2 is more preferred.
- the light source used for exposure is not particularly limited as long as it emits light of a wavelength (eg, g-line or i-line) with which the photosensitive agent in the photosensitive resin composition reacts.
- a high pressure mercury lamp is typically used.
- Post-exposure baking may be performed as necessary.
- the post-exposure baking temperature is not particularly limited. It is preferably 50 to 150°C, more preferably 50 to 130°C, still more preferably 55 to 120°C, and particularly preferably 60 to 110°C.
- the post-exposure bake time is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, still more preferably 1 to 15 minutes.
- a photomask can be used in the exposure step. Thereby, a desired "pattern" can be formed using the photosensitive resin composition.
- the developer examples include organic developer and water-soluble developer.
- the developer preferably contains an organic solvent. More specifically, the developer is preferably a developer containing an organic solvent as a main component (a developer in which 95% by mass or more of the component is an organic solvent). By developing with a developer containing an organic solvent, swelling of the pattern due to the developer can be suppressed more than in the case of developing with an alkaline developer (aqueous). That is, it is easy to obtain a finer pattern.
- ketone solvents such as cyclopentanone
- ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate
- ether solvents such as propylene glycol monomethyl ether, etc.
- an organic solvent developer containing only an organic solvent and containing only unavoidable impurities may be used as the developer.
- Impurities that are unavoidably contained include metal elements and moisture, but from the viewpoint of preventing contamination of electronic devices, it is better that the impurities that are unavoidably contained are as small as possible.
- the method of bringing the developer into contact with the photosensitive resin layer 2510 is not particularly limited. A generally known dipping method, paddle method, spray method, or the like can be appropriately applied.
- the time for the development process is usually in the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the film thickness of the resin film, the shape of the pattern to be formed, and the like.
- the conditions for the heat curing process are not particularly limited, but for example, the heating temperature can be about 160 to 250° C. for about 30 to 240 minutes.
- a specific example of the method of manufacturing an electronic device will be described below with reference to the drawings.
- a specific example of the method for manufacturing an electronic device to be described is a method characterized by sealing the semiconductor chip 40 from the side opposite to the side on which the electrode pads 30 are arranged in the semiconductor chip 40, which is a so-called A fan-out wafer level package (FO-WLP) type electronic device manufacturing method.
- a fan-out wafer level package (FO-WLP) type electronic device manufacturing method is characterized by sealing the semiconductor chip 40 from the side opposite to the side on which the electrode pads 30 are arranged in the semiconductor chip 40.
- a plurality of semiconductor chips 40 obtained by singulating a semiconductor wafer passivated in advance by forming a passivation film 50 are separated at predetermined intervals.
- a structure is prepared in which the terminal surface of the semiconductor chip 40 (the surface on the side where the electrode pads 30 are arranged) is attached to the adhesive surface of the adhesive member 200 .
- a photosensitive resin composition used for forming the first insulating resin film 60 described later can be used.
- the plurality of semiconductor chips 40 are embedded inside the encapsulant 10 so that the electrode pads 30 provided on the surfaces of the plurality of semiconductor chips 40 all face the same direction.
- a pillar-shaped conductor made of metal such as copper may be formed on the electrode pad 30 provided on the semiconductor chip 40 .
- a solder bump may be formed on the end face of the conductor portion opposite to the side on which the electrode pads are arranged.
- the plurality of semiconductor chips 40 attached to the adhesive member 200 are covered and sealed with a cured resin composition for semiconductor sealing.
- cured material of the resin composition for semiconductor sealing shows a sealing material.
- Known materials can be used as the resin composition for semiconductor encapsulation, and examples thereof include an epoxy resin composition containing an epoxy resin, an inorganic filler, and a curing agent.
- Examples of methods for encapsulating the semiconductor chip 40 using the semiconductor encapsulating resin composition include transfer molding, compression molding, injection molding, and lamination.
- the transfer molding method, the compression molding method, or the lamination method is preferable from the viewpoint of forming the sealing material 10 without leaving an unfilled portion. Therefore, the resin composition for semiconductor encapsulation used in this production method is preferably in the form of granules, particles, tablets, or sheets.
- the compression molding method is particularly preferable from the viewpoint of suppressing the positional deviation of the semiconductor chip 40 during molding of the encapsulant 10 .
- the adhesive member 200 is peeled off. By doing so, it is possible to obtain a structure in which a plurality of semiconductor chips 40 having electrode pads 30 on their surfaces are embedded inside the sealing material 10 .
- the adhesive member 200 is preferably peeled off from the structure after reducing the adhesion between the adhesive member 200 and the structure. Specifically, the adhesive layer of the adhesive member 200 forming the adhesive portion is deteriorated by, for example, performing ultraviolet irradiation or heat treatment on the adhesive portion between the adhesive member 200 and the structure, thereby improving the adhesion. can be reduced.
- the adhesive member 200 is not particularly limited as long as it adheres to the semiconductor chip 40, but for example, a member formed by laminating a back grind tape and an adhesive layer can be used.
- the structure shown in FIG. 1C relates to a mode in which the surface of the semiconductor chip 40 opposite to the side on which the electrode pads 30 are arranged is covered with the sealing material 10.
- the sealing material 10 is polished and removed by a known method so that the surface of the semiconductor chip 40 opposite to the side on which the electrode pads 30 are arranged is exposed. There may be a step of
- a first insulating resin film 60 is formed on the surface of the obtained structure on which the electrode pads 30 are embedded. Specifically, a varnish-like resin composition is applied to the surface of the structure on which the electrode pads 30 are embedded, and dried to form the first insulating resin film 60 . do.
- the film thickness of the first insulating resin film 60 can be, for example, 1 to 300 ⁇ m.
- known techniques such as a spin coating method, a slit coating method and an inkjet method can be employed. Among them, it is preferable to employ a spin coating method.
- the above-described photosensitive resin composition (the composition described in the ⁇ Photosensitive resin composition> section) as the resin material forming the first insulating resin film 60 .
- the surface of the sealing material 10 on which the first insulating resin film 60 is to be formed is preferably plasma-treated.
- the wettability of the first insulating resin film 60 can be improved.
- the adhesion between the sealing material 10 and the first insulating resin film 60 can be further improved.
- plasma processing for example, argon gas, oxidizing gas, or fluorine-based gas can be used as processing gas.
- Oxidizing gases include O2 gas, O3 gas, CO gas, CO2 gas, NO gas, NO2 gas, and the like.
- the processing gas it is preferable to use, for example, an oxidizing gas.
- the oxidizing gas it is preferable to use O 2 gas, for example. Thereby, a specific functional group can be formed on the surface of the sealing material 10 . Therefore, the adhesion and coatability of the first insulating resin film 60 to the sealing material 10 can be further improved, and the reliability of the electronic device can be further improved.
- the conditions for the plasma treatment are not particularly limited, but in addition to the ashing treatment, the treatment may be contact with plasma derived from an inert gas.
- the plasma treatment according to the present manufacturing method is preferably a plasma treatment performed without applying a bias voltage to the object to be treated, or a plasma treatment performed using a non-reactive gas.
- chemical treatment may be performed instead of plasma treatment, or both plasma treatment and chemical treatment may be performed. Examples of chemicals that can be used for chemical treatment include alkaline permanganate aqueous solutions such as potassium permanganate and sodium permanganate.
- a first opening 250 that partially exposes the electrode pad 30 is formed in the first insulating resin film 60. Then, as shown in FIG. 2(b), a first opening 250 that partially exposes the electrode pad 30 is formed in the first insulating resin film 60. Then, as shown in FIG. As a method for forming the first opening 250, an exposure development method or a laser processing method can be used. Further, it is preferable to perform a descum treatment for removing scum (resin residue) generated when forming the first opening 250 for the formed first opening 250 .
- the descum treatment may be performed by plasma irradiation.
- argon gas, O2 gas, O3 gas, CO gas, CO2 gas, NO gas, NO2 gas, or fluorine-based gas can be used as the processing gas.
- a conductive film 110 is formed to cover the exposed electrode pads 30 and the first insulating resin film 60 .
- the conductive film 110 is, for example, an electrolytic copper plating film, a solder plating film, a tin plating film, a plating film having a two-layer structure in which a gold plating film is laminated on a nickel plating film, or an under bump metal (UBM) formed by electroless plating. It can be any of the membranes and the like. Also, the film thickness of the conductive film 110 can be, for example, 2 to 10 ⁇ m. From the viewpoint of improving the durability of the finally obtained electronic device 100, the surface of the obtained conductive film 110 may be subjected to plasma treatment in the same manner as described above.
- the conductive film 110 can be formed as follows. Although an example of forming the conductive film 110 including two layers of nickel and gold is described below, the present invention is not limited to this. First, a nickel plating film is formed. When performing electroless nickel plating, the structure shown in FIG. 2(b) is immersed in a plating solution. By doing so, the conductive film 110 can be formed on the surfaces of the electrode pads 30 and the first insulating resin film 60 . A plating solution containing nickel lead and, for example, hypophosphite as a reducing agent can be used. Subsequently, electroless gold plating is performed on the nickel plating film. Although the method of electroless gold plating is not particularly limited, for example, immersion gold plating performed by replacing gold ions with ions of a base metal can be used.
- the semiconductor chip 40 is embedded with the sealing material 10.
- the circuit surface of the semiconductor chip 40 is exposed to the outside, forming a boundary between the semiconductor chip 40 and the sealing material 10 .
- a conductive film 110 (rewiring layer) connected to the electrode pads 30 of the semiconductor chip 40 is also provided in the region of the sealing material 10 in which the semiconductor chip 40 is embedded, and the bumps are formed through the conductive film 110 (rewiring layer). It is electrically connected to the electrode pad 30 of the semiconductor chip 40 .
- the pitch of the bumps can be set larger than the pitch of the electrode pads 30 of the semiconductor chip 40 .
- a second insulating resin film 70 is formed on the surface of the conductive film 110.
- a second opening 300 is formed to partially expose the conductive film 110 .
- a method of forming the second insulating resin film 70 and the second opening 300 the same method as the method of forming the first insulating resin film 60 and the first opening 250 can be used.
- a material for forming the second insulating resin film 70 a photosensitive resin composition used for forming the first insulating resin film 60 (that is, described in the section ⁇ Photosensitive resin composition>) composition) can be used.
- the ends of the solder bumps 80 or bonding wires are melted and fused onto the conductive film 110 exposed in the second openings 300 .
- the electronic device 100 which concerns on this embodiment can be obtained.
- the electronic device 100 is cut along dicing lines formed in the electronic device 100 so as to include at least one semiconductor chip 40, thereby forming a plurality of semiconductor packages (electronic devices) into individual pieces. can be
- this manufacturing method starting from the structure shown in FIG. Devices can also be made.
- an electronic device including four layers of conductive films (wiring layers) and five layers of insulating resin films can be manufactured.
- the same method as the method for forming the conductive film 110 can be used as the method for forming the conductive film (wiring layer).
- a method for forming the insulating resin film a technique similar to the method for forming the first insulating resin film 60 can be used.
- the solder bumps 80 or the ends of the bonding wires are melted and melted into the conductive film (wiring layer) as the outermost layer in the same manner as the method described above.
- the resulting electronic device can be electrically connected by attaching.
- This manufacturing method starts with the structure shown in FIG. 1(c) is in a state in which the surface of the semiconductor chip 40 opposite to the side on which the electrode pads 30 are arranged is also exposed, an insulating resin film is formed on both surfaces of the structure. You may
- this manufacturing method can also be applied to a process of manufacturing a chip-sized semiconductor package, from the viewpoint of improving the productivity of semiconductor packages, a process of manufacturing a so-called wafer-level package, or a process of manufacturing a larger size than the wafer size. It may be applied to the process of manufacturing a panel level package on the premise of using an area panel.
- the obtained polyimide solution was poured into 1,000 g of methanol while stirring in a 5 L container to precipitate the polyimide resin. After that, the solid polyimide resin was separated by filtration using a suction filtration device, and further washed with 1,000 g of methanol. Then, using a vacuum dryer, drying was performed at 100° C. for 24 hours, and further drying was performed at 200° C. for 3 hours. As a result, a polyimide powder polymer (A-1) having an acid anhydride group at the end was obtained. The weight average molecular weight (Mw) of polymer (A-1) measured by GPC was 25,000.
- the polymer (A-1) was subjected to 1 H-NMR measurement, and the imidization ratio (defined above) was calculated from the quantitative value of the amide peak relative to the aromatic ring peak of the polyimide.
- the imidization rate was 99% or more.
- C-1 Irugacure OXE01 (manufactured by BASF, oxime ester type photoradical generator)
- C-2 ADEKA Arkles NCI-730 (manufactured by ADEKA Co., Ltd., oxime ester type photoradical generator)
- F-1 Tetraphenylphosphonium/4,4'-sulfonyldiphenolate
- a method for synthesizing the curing catalyst (F-1) is as follows. A separable flask equipped with a stirrer was charged with 37.5 g (0.15 mol) of 4,4′-bisphenol S and 100 mL of methanol, and dissolved under stirring at room temperature to prepare Solution 1. A solution prepared by dissolving 4.0 g (0.1 mol) of sodium hydroxide in 50 mL of methanol in advance was added to solution 1 while stirring to obtain solution 2 .
- a solution 3 was prepared by adding a solution prepared by dissolving 41.9 g (0.1 mol) of tetraphenylphosphonium bromide in 150 mL of methanol in advance. Stirring of Solution 3 was continued for a while, and 300 mL of methanol was added to Solution 3 to obtain Solution 4 . After that, the solution 4 in the flask was added dropwise to a large amount of water while stirring to obtain a white precipitate. The precipitate was filtered and dried. As a result, the desired product was obtained as white crystals.
- ⁇ Dynamic viscoelasticity measurement of cured film (measurement of E'220 , etc.)> (Preparation of test piece)
- the photosensitive resin composition was spin-coated on an 8-inch silicon wafer so that the film thickness after drying was 10 ⁇ m, followed by heating at 120° C. for 3 minutes to obtain a coating film.
- the obtained coating film was exposed to light of 1000 mJ/cm 2 with a high-pressure mercury lamp. After that, post-exposure baking was performed at 120° C. for 3 minutes, followed by immersion in cyclopentanone for 30 seconds. Furthermore, after that, it was cured by heating at 170° C. for 2 hours in a nitrogen atmosphere. A cured film of the photosensitive resin composition was thus obtained.
- the resulting cured product was cut together with the silicon wafer into individual pieces with a dicing saw so as to have a width of 5 mm.
- the cured film was peeled off from the wafer by immersing this individual piece in a 2 mass % hydrofluoric acid aqueous solution.
- the peeled cured film was dried at 60° C. for 10 hours to obtain a test piece (30 mm ⁇ 5 mm ⁇ 10 ⁇ m thick).
- the resulting test piece is heated from 30°C to 300°C under the conditions of a nitrogen atmosphere, a frequency of 1 Hz, a tensile mode, and a heating rate of 5°C/min using a dynamic viscoelasticity measuring device (TA, Q800). and the storage modulus against temperature was measured.
- the storage modulus [MPa] at 220°C, 250°C and 280°C was read from the obtained storage modulus (E') curve.
- thermomechanical analyzer manufactured by Seiko Instruments Inc., TMA/SS6000
- a test piece obtained in the same manner as the dynamic viscoelasticity measurement of the cured film was heated to 300 ° C. at a heating rate of 10 ° C./min. heated to The temperature-displacement relationship at this time was graphed.
- the glass transition temperature (Tg) of the cured product was obtained from the position of the inflection point in the obtained graph.
- the coefficient of linear expansion in the region from Tg-50 [° C.] to Tg-20 [° C.] is CTE1
- the coefficient of linear expansion in the region from Tg+20 [° C.] to Tg+50 [° C.] is CTE2.
- ⁇ Reliability evaluation (temperature cycle test)> (Creation of board for reliability evaluation)
- the photosensitive resin composition was spin-coated on a 12-inch silicon wafer so that the film thickness after drying was 5 ⁇ m, followed by heating at 120° C. for 3 minutes to obtain a coating film.
- the obtained coating film was exposed to light of 1000 mJ/cm 2 with a high-pressure mercury lamp. After that, post-exposure baking was performed at 120° C. for 3 minutes, followed by immersion in cyclopentanone for 30 seconds. Furthermore, after that, it was cured by heating at 170° C. for 2 hours in a nitrogen atmosphere. As described above, a first cured film of the photosensitive resin composition was obtained.
- the substrate for reliability evaluation obtained as described above is set in a temperature cycle test device (TCT device), and the temperature is raised from -60 ° C. to 200 ° C. and then lowered to -60 ° C. for one cycle. As such, 1000 cycles of processing were performed. Subsequently, a cross section of the Cu wiring portion was taken out by FIB (focused ion beam) processing and observed by SEM. In each example and comparative example, a total of 10 interfaces between the wiring and the resin film were observed. ⁇ (very good) when no peeling was observed at all 10 locations, ⁇ (good) when peeling was observed at 1 or 2 locations out of 10, and peeling at 3 or more locations. Observations were evaluated as x (bad).
- a Cu wiring substrate was prepared by forming comb-shaped Cu wiring having a width of 5 ⁇ m, a pitch of 5 ⁇ m, and a height of 5 ⁇ m on a silicon wafer with an oxide film.
- the photosensitive resin composition is applied onto the Cu wiring substrate by spin coating so that the film thickness after drying (the thickness of the portion without wiring) is 10 ⁇ m, and dried at 120° C. for 3 minutes to make it photosensitive.
- a resin film was formed.
- the resulting photosensitive resin film was exposed to light of 300 mJ/cm 2 using a high-pressure mercury lamp. After that, it was immersed in cyclopentanone for 30 seconds. After that, heat treatment was performed at 170° C. for 2 hours in a nitrogen atmosphere to obtain a cured film. This was used as a sample for insulation reliability evaluation.
- a simulated electronic device for evaluation was produced by soldering the ends (Cu electrodes) of the Cu wiring of the substrate produced in the above (preparation of insulation reliability sample) and the electrode wiring. This was placed in an environment of 130° C./85% RH while applying a bias of 3.5 V with a B-HAST apparatus. The insulation resistance value between the Cu wirings of the Cu wiring substrate was automatically measured at intervals of 6 minutes, and the dielectric breakdown was determined when the insulation resistance value was 1.0 ⁇ 10 4 ⁇ or less. Then, the time from the start of the test to dielectric breakdown was measured. In the table shown later, the case of 210 hours or more was indicated by ⁇ (very good), the case of 50 hours to 210 hours by ⁇ (good), and the case of less than 50 hours by x (bad).
- the photosensitive resin composition was spin-coated onto an 8-inch silicon wafer so that the film thickness after drying was 10 ⁇ m. Subsequently, heating was performed at 120° C. for 3 minutes to obtain a photosensitive resin film. The resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 with a high-pressure mercury lamp. After that, it was immersed in cyclopentanone for 30 seconds and then dried by spin drying to obtain a film after development of the photosensitive resin composition. The film thickness of the film after this development was measured and designated as film thickness A. After that, the film was cured after development by heat treatment at 170° C. for 2 hours in a nitrogen atmosphere.
- a cured film of the photosensitive resin composition was obtained.
- the film thickness of this cured film was measured and designated as film thickness B.
- the curing shrinkage rate was calculated by substituting the film thickness A and the film thickness B into the following formula.
- a Cu wiring substrate was prepared by forming Cu wiring having a width of 5 ⁇ m, a pitch of 5 ⁇ m, and a height of 5 ⁇ m on a silicon wafer with an oxide film.
- a photosensitive resin composition was applied onto the Cu wiring substrate by spin coating so that the film thickness after drying was 10 ⁇ m, and dried at 120° C. for 3 minutes to form a photosensitive resin film.
- the resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 with a high-pressure mercury lamp. After that, it was immersed in cyclopentanone for 30 seconds. After that, heat treatment was performed at 170° C.
- a test piece was prepared in the same manner as in (Preparation of test piece) in ⁇ Measurement of dynamic viscoelasticity of cured film (measurement of E' 220 , etc.)>.
- the resulting test piece was subjected to a tensile test using a tensile tester (Tensilon RTC-1210A, manufactured by Orientec Co., Ltd.) in an atmosphere of 23° C. in accordance with JIS K 7161, and the tensile elongation of the test piece was measured. It was measured.
- the drawing speed in the tensile test was 5 mm/min.
- the photosensitive resin composition was applied onto an 8-inch silicon wafer using a spin coater so that the film thickness after drying was 5 ⁇ m. Then, it was dried on a hot plate at 120° C. for 3 minutes to obtain a photosensitive resin film (photosensitive resin film A).
- This photosensitive resin film is passed through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a cut pattern with a width of 0.5 to 50 ⁇ m are drawn), and an i-line stepper (NSR-4425i manufactured by Nikon Corporation). ) was used to irradiate the i-line while changing the exposure amount.
- the film was developed using cyclopentanone as a developer for 30 seconds, dried by spinning at 2500 rpm for 10 seconds, and a film after development (negative pattern) was obtained.
- a case where a via hole of 7 ⁇ m ⁇ was opened was evaluated as ⁇ (very good)
- a case where a via hole of 10 ⁇ m ⁇ was opened was evaluated as ⁇ (good)
- a case where a via hole of 10 ⁇ m was not opened was evaluated as ⁇ (bad).
- Table 1 summarizes the composition of raw materials for each composition and the measurement/evaluation results.
- the results of the temperature cycle test of the photosensitive resin compositions of Examples 1 to 14 (containing polyamide resin and/or polyimide resin and having E'220 of 0.5 to 3.0 GPa). , the insulation reliability evaluation results, and the shear strength at 250° C. were all good. From these evaluation results, it was shown that a highly reliable electronic device can be manufactured by curing the photosensitive resin composition of the present embodiment by heating at about 170° C. to form a cured film. In addition, the cure shrinkage of the cured products of the photosensitive resin compositions of Examples 1 to 14 was small, and the evaluation of the step embedding flatness was good. Furthermore, the cured products of the photosensitive resin compositions of Examples 1 to 14 were moderately stretchable. In addition, the photosensitive resin compositions of Examples 1 to 14 had sufficient patterning performance during the manufacture of electronic devices.
- Example 11 From the comparison between Example 11 and other examples, the use of the thermal radical generator tends to increase the glass transition temperature of the cured product and decrease the CTE2/CTE1 ratio. Reliability tends to be improved by using a thermal radical generator. This is probably because the use of the thermal radical generator further accelerates the polymerization of the polyfunctional (meth)acrylate compound.
- thermal radical generator By comparison with Examples 12 and 13 and other Examples, there is a tendency that the tensile elongation is improved by using an epoxy resin and its curing catalyst. Presumably, the polyamide resin and/or polyimide resin and the epoxy resin bond (crosslink) to form a cured film that is more stretchable and less likely to break.
- crosslink crosslink
- sealing material 30 electrode pad 40 semiconductor chip 50 passivation film 60 insulating resin film (first insulating resin film) 70 insulating resin film (second insulating resin film) 80 Solder bump 100 Electronic device 110 Conductive film 200 Adhesive member 250 Opening (first opening) 300 opening (second opening)
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Abstract
Description
また、近年、半導体チップへの熱ダメージ低減のため、硬化膜を形成する際の加熱温度を比較的低くすること(例えば、170℃程度とすること)が求められてきている。
ポリアミド樹脂および/またはポリイミド樹脂を含む感光性樹脂組成物であって、
当該感光性樹脂組成物を170℃で2時間加熱して得られた硬化膜を、以下条件で動的粘弾性測定をしたときの、220℃での貯蔵弾性率E'220が0.5~3.0GPaである、感光性樹脂組成物。
[条件]
周波数:1Hz
温度:30~300℃
昇温速度:5℃/分
測定モード:引張りモード
基板上に、上記の感光性樹脂組成物を用いて感光性樹脂膜を形成する膜形成工程と、
前記感光性樹脂膜を露光する露光工程と、
露光された前記感光性樹脂膜を現像する現像工程と、
を含む、電子デバイスの製造方法
が提供される。
上記の感光性樹脂組成物の硬化膜を備える電子デバイス
が提供される。
すべての図面において、同様な構成要素には同様の符号を付し、適宜説明を省略する。
煩雑さを避けるため、(i)同一図面内に同一の構成要素が複数ある場合には、その1つのみに符号を付し、全てには符号を付さない場合や、(ii)特に図2以降において、図1と同様の構成要素に改めては符号を付さない場合がある。
すべての図面はあくまで説明用のものである。図面中の各部材の形状や寸法比などは、必ずしも現実の物品と対応しない。
本明細書中、数値範囲の説明における「X~Y」との表記は、特に断らない限り、X以上Y以下のことを表す。例えば、「1~5質量%」とは「1質量%以上5質量%以下」を意味する。
本明細書における「(メタ)アクリル」との表記は、アクリルとメタクリルの両方を包含する概念を表す。「(メタ)アクリレート」等の類似の表記についても同様である。
本明細書における「有機基」の語は、特に断りが無い限り、有機化合物から1つ以上の水素原子を除いた原子団のことを意味する。例えば、「1価の有機基」とは、任意の有機化合物から1つの水素原子を除いた原子団のことを表す。
本明細書における「電子デバイス」の語は、半導体チップ、半導体素子、プリント配線基板、電気回路ディスプレイ装置、情報通信端末、発光ダイオード、物理電池、化学電池など、電子工学の技術が適用された素子、デバイス、最終製品等を包含する意味で用いられる。
本実施形態の感光性樹脂組成物は、ポリアミド樹脂および/またはポリイミド樹脂を含む。
本実施形態の感光性樹脂組成物を170℃で2時間加熱して得られた硬化膜を、以下条件で動的粘弾性測定をしたときの、220℃での貯蔵弾性率E'220は、0.5~3.0GPaである。
[条件]
周波数:1Hz
温度:30~300℃
昇温速度:5℃/分
測定モード:引張りモード
本発明者らは、加熱による高温が、電子デバイス中の硬化膜に悪影響を及ぼし、結果として電子デバイスの信頼性を低下させるのではないかと考えた。より具体的には、硬化膜が高温において変質/軟化するため、例えば硬化膜-基板間の密着力が低下して硬化膜の剥離が生じ、結果として電子デバイスの信頼性が低下するのではないかと考えた。
この新たな感光性樹脂組成物を、電子デバイス製造(例えば電子デバイスにおける絶縁層の形成など)に適用することで、本発明者らは電子デバイスの信頼性を高めることに成功した。
E'220は0.5~3.0GPaであればよく、好ましくは0.6~2.5GPa、より好ましくは0.7~2.0GPaである。
本実施形態の感光性樹脂組成物は、ポリアミド樹脂および/またはポリイミド樹脂を含む。E'220が0.5~3.0GPaとなる限り、ポリアミド樹脂および/またはポリイミド樹脂の構造、分子量、使用量などは限定されない。
ポリイミド樹脂中に含まれるイミド基のモル数をIMとし、ポリイミド樹脂に含まれるアミド基のモル数をAMとしたとき、{IM/(IM+AM)}×100(%)で表されるイミド化率は、好ましくは90%以上、より好ましくは95%以上、さらに好ましくは98%以上である。要するに、ポリイミド樹脂は、開環しているアミド構造が無いまたは少なく、閉環しているイミド構造が多い樹脂であることが好ましい。このようなポリイミド樹脂を用いることで、加熱による収縮(硬化収縮)を一層抑えることができる(閉環反応による脱水が起こらないため)。これにより、電子デバイスの信頼性の一層の向上や、硬化膜の平坦性の一層の向上などを図ることができる。
イミド化率は、一例として、NMRスペクトルにおける、アミド基に対応するピークの面積やイミド基に対応するピークの面積などから知ることができる。別の例として、イミド化率は、赤外吸収スペクトルにおける、アミド基に対応するピークの面積やイミド基に対応するピークの面積などから知ることができる。
フッ素原子を含むポリアミド樹脂および/またはポリイミド樹脂中のフッ素原子の量(質量比率)は、例えば1~30質量%、好ましくは3~28質量%、より好ましくは5~25質量%である。ある程度多くの量のフッ素原子が樹脂中に含まれることで、十分な有機溶剤溶解性を得やすい。一方、他の性能とのバランスの観点からは、フッ素原子の量が多すぎないことが好ましい。
酸無水物基は、好ましくは、環状構造の酸無水物骨格を有する基である。ここでの「環状構造」は、好ましくは5員環または6員環、より好ましくは5員環である。
Xは2価の有機基であり、
Yは4価の有機基である。
一般式(PA-1)および(PI-1)におけるXの2価の有機基および/またはYの4価の有機基は、好ましくは、2~6個のベンゼン環が、単結合または2価の連結基を介して結合した構造を有する。ここでの2価の連結基としては、アルキレン基、フッ化アルキレン基、エーテル基などを挙げることができる。アルキレン基およびフッ化アルキレン基は、直鎖状であっても分岐状であってもよい。
一般式(PA-1)および(PI-1)において、Xの2価の有機基の炭素数は、例えば6~30である。
一般式(PA-1)および(PI-1)において、Yの4価の有機基の炭素数は、例えば6~20である。
一般式(PI-1)中の2つのイミド環は、それぞれ、5員環であることが好ましい。
Xは、一般式(PA-1)および(PI-1)におけるXと同義であり、
Y'は、単結合またはアルキレン基を表す。
Y'のアルキレン基は、直鎖状でも分岐状でもよい。Y'のアルキレン基の水素原子の一部または全部は、フッ素原子で置換されていることが好ましい。Y'のアルキレン基の炭素数は、例えば1~6、好ましくは1~4、さらに好ましくは1~3である。
ポリアミド樹脂および/またはポリイミド樹脂の合成においては、1または2以上のジアミンを用いることができ、また、1または2以上の酸二無水物を用いることができる。
重量平均分子量は、通常、ポリスチレンを標準物質として用いたゲルパーミエーションクロマトグラフィー(GPC)法により求めることができる。
本実施形態の感光性樹脂組成物は、好ましくは、多官能(メタ)アクリレート化合物を含む。多官能(メタ)アクリレート化合物としては、1分子中に2以上の(メタ)アクリロイル基を有するものを特に制限なく挙げることができる。
大まかな傾向として、官能基((メタ)アクリロイル基)の数が多い多官能(メタ)アクリレート化合物を用いた場合、硬化膜の耐薬品性が高まる傾向がある。一方、官能基((メタ)アクリロイル基)の数が少ない多官能(メタ)アクリレート化合物を用いた場合、硬化膜の引張り伸びなどの機械物性が良好となる傾向がある。
ちなみに、市販の多官能(メタ)アクリレート化合物の中には、官能基数が異なる(メタ)アクリレートの混合物もある。
多官能(メタ)アクリレート化合物の使用量は特に限定されないが、上述のように使用量を適切に調整することで、諸性能のうち1または2以上をより高めうる。前述のように、本実施形態の感光性樹脂組成物においては、硬化により、ポリアミド樹脂および/またはポリイミド樹脂と多官能(メタ)アクリレートとの「絡み合い構造」が形成されると考えられるが、ポリアミド樹脂および/またはポリイミド樹脂に対する多官能(メタ)アクリレート化合物の使用量を適切に調整することで、ポリアミド樹脂および/またはポリイミド樹脂と多官能(メタ)アクリレート化合物が適度に絡み合い、また、絡み合いに関与しない余分な成分が少なくなると考えられる。そして、性能が一層良化すると考えられる。
本実施形態の感光性樹脂組成物は、好ましくは感光剤を含む。感光剤は、光により活性種を発生して感光性樹脂組成物を硬化させることが可能なものである限り、特に限定されない。
例えば、2,2-ジエトキシアセトフェノン、2,2-ジメトキシー2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-〔4-(2-ヒドロキシエトキシ)フェニル〕-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-〔4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル〕フェニル}-2-メチルプロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-〔(4-メチルフェニル)メチル〕-1-〔4-(4-モルホリニル)フェニル〕-1-ブタノン等のアルキルフェノン系化合物;ベンゾフェノン、4,4′-ビス(ジメチルアミノ)ベンゾフェノン、2-カルボキシベンゾフェノン等のベンゾフェノン系化合物;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテ等のベンゾイン系化合物;チオキサントン、2-エチルチオキサントン、2-イソプロピルチオキサントン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン等のチオキサントン系化合物;2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-メトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシカルボキニルナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン等のハロメチル化トリアジン系化合物;2-トリクロロメチル-5-(2′-ベンゾフリル)-1,3,4-オキサジアゾール、2-トリクロロメチル-5-〔β-(2′-ベンゾフリル)ビニル〕-1,3,4-オキサジアゾール、4-オキサジアゾール、2-トリクロロメチル-5-フリル-1,3,4-オキサジアゾール等のハロメチル化オキサジアゾール系化合物;2,2′-ビス(2-クロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール、2,2′-ビス(2,4-ジクロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール、2,2′-ビス(2,4,6-トリクロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール等のビイミダゾール系化合物;1,2-オクタンジオン,1-〔4-(フェニルチオ)フェニル〕-2-(O-ベンゾイルオキシム)、エタノン,1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-,1-(O-アセチルオキシム)等のオキシムエステル系化合物;ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム等のチタノセン系化合物;p-ジメチルアミノ安息香酸、p-ジエチルアミノ安息香酸等の安息香酸エステル系化合物;9-フェニルアクリジン等のアクリジン系化合物;等を挙げることができる。これらの中でも、特にオキシムエステル系化合物を好ましく用いることができる。
感光剤を用いる場合、その使用量は、多官能(メタ)アクリレート化合物100質量部に対して、例えば1~30質量部であり、好ましくは3~20質量部である。
本実施形態の感光性樹脂組成物は、好ましくは、熱ラジカル開始剤を含む。熱ラジカル開始剤を用いることにより、後述するCTE2/CTE1の値を適切に調整したり、電子デバイスの信頼性の一層の向上を図ったり、硬化膜の耐熱性をより高めたりしやすい。これは、熱ラジカル開始剤を用いることにより、多官能(メタ)アクリレート化合物の重合反応がさらに促進されるためと考えられる。
熱ラジカル開始剤を用いる場合、その量は、多官能(メタ)アクリレート化合物100質量部に対して、好ましくは0.1~30質量部、より好ましくは1~20質量部である。
本実施形態の感光性樹脂組成物は、好ましくは、エポキシ樹脂を含む。詳細は不明であるが、エポキシ樹脂は、例えばポリアミド樹脂および/またはポリイミド樹脂と反応(結合形成)すると考えられる。そして、おそらくは反応により形成されるエーテル構造の柔軟性により、硬化膜の機械物性(引張り伸びなど)がより高まる傾向がある。
エポキシ樹脂の具体例としては、n-ブチルグリシジルエーテル、2-エトキシヘキシルグリシジルエーテル、フェニルグリシジルエーテル、アリルグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ビスフェノールA(又はF)のグリシジルエーテル等のグリシジルエーテル、アジピン酸ジグリシジルエステル、o-フタル酸ジグリシジルエステル等のグリシジルエステル、3,4-エポキシシクロヘキシルメチル(3,4-エポキシシクロヘキサン)カルボキシレート、3,4-エポキシ-6-メチルシクロヘキシルメチル(3,4-エポキシ-6-メチルシクロヘキサン)カルボキシレート、ビス(3,4-エポキシ-6-メチルシクロヘキシルメチル)アジペート、ジシクロペンタンジエンオキサイド、ビス(2,3-エポキシシクロペンチル)エーテルや、ダイセル社製のセロキサイド2021P、セロキサイド2081、セロキサイド2083、セロキサイド2085、セロキサイド8000、エポリードGT401などの脂環式エポキシ樹脂、2,2'-(((((1-(4-(2-(4-(オキシラン-2-イルメトキシ)フェニル)プロパン-2-イル)フェニル)エタン-1,1-ジイル)ビス(4,1-フェニレン))ビス(オキシ))ビス(メチレン))ビス(オキシラン))(例えば、プリンテック社製のTechmore VG3101L)、エポライト100MF(共栄社化学工業社製)、エピオールTMP(日油株式会社製)などの脂肪族ポリグリシジルエーテル、1,1,3,3,5,5-ヘキサメチル-1,5-ビス(3-(オキシラン-2-イルメトキシ)プロピル)トリ・シロキサン(例えば、DMS-E09(ゲレスト社製))などを挙げることができる。
別観点として、エポキシ樹脂としては、芳香環構造および/または脂環構造を有するものが好ましい。このようなエポキシ樹脂を用いることは、特に耐熱性の観点で好ましい。
エポキシ樹脂を用いる場合、その量は、ポリアミド樹脂および/またはポリイミド樹脂100質量部に対して、例えば0.5~30質量部、好ましくは1~20質量部、さらに好ましくは3~15質量部である。
本実施形態の感光性樹脂組成物は、好ましくは、硬化触媒を含む。この硬化触媒は、エポキシ樹脂の反応を促進する働きを有する。硬化触媒を用いることにより、エポキシ樹脂が関与する反応が十分に進行し、例えば硬化膜の引張り伸び率を一層向上させることができる。
本実施形態の感光性樹脂組成物は、好ましくは、シランカップリング剤を含む。シランカップリング剤を用いることにより、例えば基板と硬化膜との密着性をより高めることができる。
エポキシ基含有シランカップリング剤としては、例えばγ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-グリシジルプロピルトリメトキシシラン等が挙げられる。
(メタ)アクリロイル基含有シランカップリング剤としては、例えばγ-((メタ)アクリロイルオキシプロピル)トリメトキシシラン、γ-((メタ)アククリロイルオキシプロピル)メチルジメトキシシラン、γ-((メタ)アクリロイルオキシプロピル)メチルジエトキシシラン等が挙げられる。
メルカプト基含有シランカップリング剤としては、例えば3-メルカプトプロピルトリメトキシシラン等が挙げられる。
ビニル基含有シランカップリング剤としては、例えばビニルトリス(β-メトキシエトキシ)シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン等が挙げられる。
ウレイド基含有シランカップリング剤としては、例えば3-ウレイドプロピルトリエトキシシラン等が挙げられる。
スルフィド基含有シランカップリング剤としては、例えばビス(3-(トリエトキシシリル)プロピル)ジスルフィド、ビス(3-(トリエトキシシリル)プロピル)テトラスルフィド等が挙げられる。
環状無水物構造を有するシランカップリング剤としては、例えば3-トリメトキシシリルプロピルコハク酸無水物、3-トリエトキシシシリルプロピルコハク酸無水物、3-ジメチルメトキシシリルプロピルコハク酸無水物等が挙げられる。
シランカップリング剤が用いられる場合、その使用量は、ポリアミド樹脂および/またはポリイミド樹脂の使用量を100質量部としたとき、例えば0.1~20質量部、好ましくは0.3~15質量部、より好ましく0.4~12質量部、さらに好ましくは0.5~10質量部である。
本実施形態の感光性樹脂組成物は、好ましくは、界面活性剤を含む。これにより、感光性樹脂組成物の塗布性や、膜の平坦性を一層高めうる。
界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、アルキル系界面活性剤、アクリル系界面活性剤などが挙げられる。
別観点として、界面活性剤は、非イオン性であることが好ましい。非イオン性の界面活性剤の使用は、例えば、組成物中の他成分との非意図的な反応を抑え、組成物の保存安定性を高める点で好ましい。
また、スリーエム社製のFC4430やFC4432なども、好ましい界面活性剤として挙げることができる。
本実施形態の感光性樹脂組成物が界面活性剤を含む場合、その量は、ポリアミド樹脂および/またはポリイミド樹脂の含有量を100質量部としたとき、例えば0.001~1質量部、好ましくは0.005~0.5質量部である。
本実施形態の感光性樹脂組成物は、水を含んでもよい。水の存在により、例えば、シランカップリング剤の加水分解反応が進行しやすくなり、基板と硬化膜との密着性がより高まる傾向がある。
感光性樹脂組成物の水分量は、カールフィッシャー法により定量することができる。
本実施形態の感光性樹脂組成物は、好ましくは溶剤を含む。これにより、基板(特に、段差を有する基板)に対して塗布法により感光性樹脂膜を容易に形成することができる。
溶剤は、通常、有機溶剤を含む。
上述の各成分を溶解または分散可能で、かつ、各構成成分と実質的に化学反応しないものである限り、溶剤は特に限定されない。
本実施形態の感光性樹脂組成物がワニス状であることにより、塗布による均一な膜形成を行うことができる。また、ポリアミド樹脂および/またはポリイミド樹脂が、溶剤に「溶解」していることで、均質な硬化膜を得ることができる。
別観点として、組成物全体中の、ポリアミド樹脂および/またはポリイミド樹脂および多官能(メタ)アクリレート化合物の割合は、好ましくは20~50質量%である。ある程度多量のポリアミド樹脂および/またはポリイミド樹脂と、多官能(メタ)アクリレート化合物とを用いることで、適度な厚さの膜を形成しやすい。
本実施形態の感光性樹脂組成物は、上記の成分に加えて、必要に応じて、上掲の成分以外の成分を含んでもよい。そのような成分としては、例えば、酸化防止剤、シリカ等の充填材、増感剤、フィルム化剤等が挙げられる。
本実施形態の感光性樹脂組成物に関しては、E'220が0.5~3.0GPaとなるように組成物を設計することに加え、その他の物性を満足することで、一層の性能向上を図ることができる。
具体的には、
・感光性樹脂組成物を170℃で2時間加熱して得られた硬化膜のガラス転移温度をTg[℃]、
・Tg-50[℃]からTg-20[℃]までの温度領域における上記硬化膜の熱膨張係数をCTE1、
・Tg+20[℃]からTg+50[℃]までの温度領域における上記硬化膜の熱膨張係数をCTE2、としたとき、CTE2/CTE1の値は、好ましくは1~10、より好ましくは1~7、さらに好ましくは1~5である。
CTE2がCTE1に比べて過度に大きくならないように感光性樹脂組成物を設計することで、電子デバイス製造工程における加熱による硬化膜の変質/軟化が一層抑制されると考えられる。そして、電子デバイスの信頼性が一層向上すると考えられる。
CTE2/CTE1の値は理想的には1に近いことが好ましいが、現実的な組成物設計の観点から、下限は例えば1.1程度である。
また、CTE2そのものの値は、好ましくは2×10-5~100×10-5/℃、より好ましくは2×10-5~80×10-5/℃、さらに好ましくは5×10-5~60×10-5/℃、特に好ましくは5×10-5~50×10-5/℃である。
また、ガラス転移温度Tgは、好ましくは170~270℃、より好ましくは170~250℃、さらに好ましくは200~250℃、特に好ましくは210~230℃である。
前述の[条件]での動的粘弾性測定における、本実施形態の感光性樹脂組成物の硬化膜の280℃での貯蔵弾性率E'280は、好ましくは0.1GPa以上、より好ましくは0.1GPa以上2.0GPa以下、さらに好ましくは0.2GPa以上1.0GPa以下である。
E'250やE'280が上記数値範囲内となるように感光性樹脂組成物を設計することで、例えば、高温が必要とされるリフロー工程においても硬化膜の剥離が抑えられ、電子デバイスの信頼性の一層の向上が図られると考えられる。
本実施形態の電子デバイスの製造方法は、
基板上に、上述の感光性樹脂組成物を用いて感光性樹脂膜を形成する膜形成工程と、
感光性樹脂膜を露光する露光工程と、
露光された感光性樹脂膜を現像する現像工程と、
を含む。
また、本実施形態の電子デバイスの製造方法は、上述の現像工程の後に、露光された感光性樹脂膜を加熱して硬化させる熱硬化工程を含むことが好ましい。これにより、耐熱性が十二分な硬化膜を得ることができる。
以上のようにして、本実施形態の感光性樹脂組成物の硬化膜を備える電子デバイスを製造することができる。
次の露光工程の前に、塗布された感光性樹脂組成物中の溶剤を乾燥させるなどの目的で、適切な加熱を行うことが好ましい。この際の加熱は、例えば80~150℃の温度で、1~60分間加熱することで行う。
乾燥後の感光性樹脂膜の厚みは、最終的に得ようとする電子デバイスの構造に応じて適宜変わるが、例えば1~100μm程度、具体的には1~50μm程度である。
露光に用いられる光源は特に限定されず、感光性樹脂組成物中の感光剤が反応する波長の光(例えばg線やi線)を発する光源であればよい。典型的には高圧水銀灯が用いられる。
必要に応じて、露光後ベークを施してもよい。露光後ベークの温度は、特に限定されない。好ましくは50~150℃、より好ましくは50~130℃、さらに好ましくは55~120℃、特に好ましくは60~110℃である。また、露光後ベークの時間は、好ましくは1~30分間、より好ましくは1~20分間、さらに好ましくは1~15分間である。
露光工程においては、フォトマスクを用いることができる。これにより、感光性樹脂組成物を用いて所望の「パターン」を形成することができる。
現像液としては、有機溶剤のみからなり、不可避的に含まれる不純物以外は含まない有機溶剤現像液を使用してもよい。不可避的に含まれる不純物としては、金属元素や水分があるが、電子デバイスの汚染防止などの観点からは不可避的に含まれる不純物は少ないに越したことは無い。
図1(a)の構造体において、複数の半導体チップ40は、それぞれの表面に設けられた電極パッド30がすべて同一方向を向くように、複数の半導体チップ40が封止材10の内部に埋め込まれていることが好ましい。
半導体チップ40に備わる電極パッド30上には、銅などの金属からなるピラー形状の導体部が形成されていてもよい。さらに、導体部の電極パッドが配されている側とは反対側の端面にはハンダバンプが形成されていてもよい。
粘着部材200は、半導体チップ40に接着するものであれば特に限定されないが、例えば、バックグラインドテープと、接着剤層とが積層されてなる部材が挙げられる。
図1(c)に示されている構造体は、半導体チップ40における電極パッド30が配されている側とは反対側の面が封止材10に覆われた態様に係るものであるが、本製造方法においては、粘着部材200を剥離する前に、半導体チップ40における電極パッド30が配されている側とは反対側の面が露出するように封止材10を公知の方法で研磨除去する工程があってもよい。
プラズマ処理においては、例えば処理ガスとして、アルゴンガス、酸化性ガスまたはフッ素系ガスを用いることができる。酸化性ガスとしては、O2ガス、O3ガス、COガス、CO2ガス、NOガス、NO2ガスなどが挙げられる。処理ガスとしては、例えば、酸化性ガスを用いることが好ましい。また、酸化性ガスとしては、例えば、O2ガスを用いることが好ましい。これにより、封止材10の表面に特定の官能基を形成できる。したがって、封止材10に対する、第1の絶縁性樹脂膜60の密着性、塗布性をより向上し、電子デバイスの信頼性をより向上できる。
また、本製造方法においては、プラズマ処理に代えて薬液処理を実施してもよいし、プラズマ処理と薬液処理の両方を実施してもよい。薬液処理に使用することができる薬剤としては、例えば、過マンガン酸カリウム、過マンガン酸ナトリウム等のアルカリ性過マンガン酸塩水溶液が挙げられる。
得られた導電膜110については、最終的に得られる電子デバイス100の耐久性を向上させる観点から、その表面に対し、上述した手法と同様の方法でプラズマ処理を施してもよい。
まず、ニッケルめっき膜を形成する。無電解ニッケルめっきを行う場合、めっき液に図2(b)に示した構造体を浸漬する。こうすることにより、電極パッド30と、第1の絶縁性樹脂膜60の表面上に導電膜110を形成できる。めっき液は、ニッケル鉛、および還元剤として、例えば次亜リン酸塩を含んだものを用いることができる。続いて、ニッケルめっき膜の上に無電解金めっきを行う。無電解金めっきの方法は特に限定されないが、例えば金イオンと下地金属のイオンとの置換により行う置換金めっきで行うことができる。
第2の絶縁性樹脂膜70および第2の開口部300の形成方法は、上記第1の絶縁性樹脂膜60および第1の開口部250の形成方法と、同様の手法を用いることができる。また、第2の絶縁性樹脂膜70を形成する材料としては、第1の絶縁性樹脂膜60を形成するために用いる感光性樹脂組成物(すなわち、<感光性樹脂組成物>の項で説明した組成物)を用いることができる。
その後、図示しないが、少なくとも1つの半導体チップ40を含むように電子デバイス100を、該電子デバイス100に形成されたダイシングラインに沿って切断することにより、複数の半導体パッケージ(電子デバイス)に個片化することができる。
上述した多層配線構造を有した電子デバイスを作製する場合においても、上述した方法と同様の方法で、最外層にハンダバンプ80または、ボンディングワイヤの端部を溶融して導電膜(配線層)に融着させることにより、得られた電子デバイスを電気的に接続することができる。
以下で、「DMAc」はジメチルアセトアミドの略号である。その他略号については文中で適宜説明する。
(ポリマー(A-1)の合成)
攪拌装置と撹拌翼を備えたガラス製の3Lのセパラブルフラスコに、TFMB<2,2'-ビス(トリフルオロメチル)-4,4'-ジアミノビフェニル>64.1g(0.20モル)、6FDA<4,4'-(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物>97.7g(0.22モル)およびDMAc500gを仕込んで撹拌し、TFMBと6FDAをDMAcに溶解させた。さらに窒素気流下で、12時間室温で撹拌を続けて重合反応を行い、ポリアミド酸溶液を得た。
ポリマー(A-1)のGPC測定による重量平均分子量(Mw)は25,000であった。
また、ポリマー(A-1)を1H-NMR測定し、ポリイミドの芳香環のピークに対するアミドピークの定量値から、イミド化率(定義は前述)を計算した。イミド化率は99%以上であった。
TFMB64.1g(0.20モル)の代わりに、TFMB56.4g(0.176モル)及びBAPP-F<2,2,-ビス[4-(4-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン>12.4g(0.024モル)を用いた以外はポリマー(A-1)と同様にポリマー合成を行った。そして、末端に酸無水物基を有するポリイミド粉体であるポリマー(A-2)を得た。
ポリマー(A-2)のGPC測定による重量平均分子量(Mw)は26,000であった。また、ポリマー(A-2)のNMR測定によるイミド化率は99%以上であった。
6FDA97.7g(0.22モル)の代わりに、6FDA78.2g(0.176モル)およびODPA<4,4'-オキシジフタル酸二無水物>13.7g(0.044モル)を用いた以外はポリマー(A-1)と同様にポリマー合成を行った。そして、末端に酸無水物基を有するポリイミド粉体であるポリマー(A-3)を得た。
ポリマー(A-3)のGPC測定による重量平均分子量(Mw)は24,000であった。また、ポリマー(A-3)のNMR測定によるイミド化率は99%以上であった。
6FDA97.7g(0.22モル)の代わりに、6FDA83.1g(0.187モル)およびBPDA<3,3',4,4'-ビフェニルテトラカルボン酸二無水物>9.71g(0.033モル)を用いた以外はポリマー(A-1)と同様にポリマー合成を行った。そして、末端に酸無水物基を有するポリイミド樹脂(A-4)を得た。
ポリマー(A-4)のGPC測定による重量平均分子量(Mw)は24,000であった。また、ポリマー(A-4)のNMR測定によるイミド化率は99%以上であった。
TFMB64.1g(0.20モル)の代わりに、1,4,-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ベンゼン85.7g(0.20モル)を用いた以外は、ポリマー(A-1)と同様にポリマーを合成した。そして、末端に酸無水物基を有するポリイミド粉体であるポリマー(A-5)を得た。
ポリマー(A-5)のGPC測定による重量平均分子量(Mw)は25,000であった。また、ポリマー(A-5)のNMR測定によるイミド化率は99%以上であった。
後掲の表1に従い配合された各原料を、室温下で原料が完全に溶解するまで撹拌し、溶液を得た。その後、その溶液を孔径0.2μmのナイロンフィルターで濾過した。このようにして、ワニス状の感光性樹脂組成物を得た。
(A-1)上記で合成したポリマー
(A-2)上記で合成したポリマー
(A-3)上記で合成したポリマー
(A-4)上記で合成したポリマー
(A-5)上記で合成したポリマー
(B-1)ビスコート#802 (大阪有機工業株式会社製、1分子あたりアクリロイル基を5~10個有する化合物の混合物)
(B-2)NKエステルA-9550 (新中村化学株式会社製、1分子あたりアクリロイル基を5~6個有する化合物の混合物)
(B-3)ビスコート#300 (大阪有機工業株式会社製、1分子あたりアクリロイル基を3~4個有する化合物の混合物)
(B-4)ビスコート#230 (大阪有機工業株式会社製、1分子あたりアクリロイル基を2個有する化合物)
(C-1)Irugacure OXE01(BASF社製、オキシムエステル型光ラジカル発生剤)
(C-2)アデカアークルズ NCI-730(株式会社ADEKA製、オキシムエステル型光ラジカル発生剤)
(D-1)パーカドックスBC(化薬ヌーリオン株式会社製、有機過酸化物、ジクミルパーオキシド)
(E-1)TECHMORE VG3101L(株式会社プリンテック製)
(E-2)セロキサイド2021P(株式会社ダイセル製)
(F-1)テトラフェニルホスホニウム・4,4'-スルフォニルジフェノラート
上記硬化触媒(F-1)の合成方法は以下の通りである。
撹拌装置付きのセパラブルフラスコに、4,4'-ビスフェノールS 37.5g(0.15mol)、メタノール100mLを仕込み、室温で撹拌溶解した溶液1を準備した。溶液1に対し、予め50mLのメタノールに水酸化ナトリウム4.0g(0.1mol)を溶解した溶液を、攪拌しながら添加して溶液2とした。次いで、予め150mLのメタノールにテトラフェニルホスホニウムブロマイド41.9g(0.1mol)を溶解した溶液を溶液2に加えて溶液3とした。しばらく溶液3の攪拌を継続し、溶液3に300mLのメタノールを追加して溶液4とした。その後、フラスコ内の溶液4を大量の水に撹拌しながら滴下し、白色沈殿を得た。沈殿を濾過、乾燥した。以上により白色結晶の目的物を得た。
(G-1)KBM-503(信越化学工業株式会社製、(メタ)アクリロイル基含有シランカップリング剤)
(G-2)X-12-967C(信越化学工業株式会社製、環状無水物構造を有するシランカップリング剤)
(H-1)FC4432(スリーエム社製、フッ素系)
(J-1)乳酸エチル(EL)
(J-2)γ-ブチロラクトン(GBL)
(試験片の作製)
感光性樹脂組成物を、8インチシリコンウェハ上に、乾燥後の膜厚が10μmとなるようにスピンコートし、続いて120℃で3分間加熱して、塗布膜を得た。
得られた塗布膜に、高圧水銀灯にて1000mJ/cm2の露光を行った。その後、120℃で3分間露光後ベークを行い、続いてシクロペンタノン中に30秒浸漬した。さらにその後、窒素雰囲気下、170℃で2時間加熱して硬化処理した。以上により感光性樹脂組成物の硬化膜を得た。
得られた硬化物を、シリコンウェハごと、幅5mmになるようにダイシングソーにてカットして個片とした。この個片を2質量%フッ酸水溶液中に浸漬することでウェハから硬化膜を剥離した。
剥離した硬化膜を60℃で10時間乾燥して、試験片(30mm×5mm×10μm厚)を得た。
熱機械分析装置(セイコーインスツルメンツ社製、TMA/SS6000)を用いて、上記の硬化膜の動的粘弾性測定と同様にして得られた試験片を、10℃/分の昇温速度で300℃まで加熱した。このときの温度-変位量の関係をグラフ化した。
得られたグラフの変曲点の位置から、硬化物のガラス転移温度(Tg)を求めた。また、得られたグラフにおける、Tg-50[℃]からTg-20[℃]の領域での線膨張係数をCTE1とし、Tg+20[℃]からTg+50[℃]の領域での線膨張係数をCTE2としてそれぞれ求めた。そして、CTE2/CTE1の値を算出した。
(信頼性評価用の基板の作成)
感光性樹脂組成物を、12インチのシリコンウェハ上に、乾燥後の膜厚が5μmとなるようにスピンコートし、続いて120℃で3分間加熱して、塗布膜を得た。
得られた塗布膜に、高圧水銀灯にて1000mJ/cm2の露光を行った。その後、120℃で3分間露光後ベークを行い、続いてシクロペンタノン中に30秒浸漬した。さらにその後、窒素雰囲気下、170℃で2時間加熱して硬化処理した。以上により1層目の感光性樹脂組成物の硬化膜を得た。
得られた硬化膜上に、Ti及びCuを、それぞれ500Åおよび3000Åの厚みでスパッタ処理にて蒸着した。その後、レジストを介して電解メッキ法にて高さ5μmとなるようにCu配線を作成した。レジスト層を剥離後、スパッタCu及びスパッタTiをエッチングし、ライン/スペース=2μm/2μmのCu配線を作成した。
続いて、膜厚を10μmに変更した以外は1層目と同様に感光性樹脂組成物を処理し、信頼性評価用の基板を得た。
上記のようにして得られた信頼性評価用の基板を、温度サイクル試験装置(TCT装置)にセットし、-60℃から200℃への昇温およびその後の-60℃への降温を1サイクルとして、1000サイクルの処理を行った。
続いて、FIB(集束イオンビーム)処理にて、Cu配線部の断面を出し、SEMにて観察した。各実施例および比較例において、それぞれ、合計10か所の配線と樹脂膜の界面を観察した。
10か所すべてで剥離が観察されなかった場合を◎(とても良い)、10か所のうち1か所あるいは2か所で剥離が観察された場合を○(良い)、3か所以上剥離が観察されたものを×(悪い)と評価した。
(絶縁信頼性用サンプルの作製)
酸化膜付きシリコンウェハ上に、幅5μm/ピッチ5μm、高さ5μmの櫛歯型のCu配線を形成したCu配線基板を作製した。
感光性樹脂組成物を、上記Cu配線基板上に、スピンコートによって、乾燥後の膜厚(配線がない部分の厚み)が10μmになるように塗布し、120℃で3分乾燥して感光性樹脂膜を形成した。
得られた感光性樹脂膜に、高圧水銀灯を用いて、300mJ/cm2の露光を行った。その後、シクロペンタノン中に30秒浸漬した。その後、窒素雰囲気下、170℃で2時間熱処理して硬化膜を得た。これを絶縁信頼性評価用サンプルとした。
上記(絶縁信頼性用サンプル作製)で作製した基板のCu配線の端部(Cu電極)と電極配線とを半田接続した、評価用の模擬的な電子デバイスを作製した。これを、B-HAST装置にて3.5Vのバイアスを掛けながら、130℃/85%RHの環境下に置いた。
6分間隔でCu配線基板のCu配線間における絶縁抵抗値を自動的に計測し、絶縁抵抗値が1.0×104Ω以下になった場合を絶縁破壊とした。そして、試験開始から絶縁破壊までの時間を測定した。後掲の表には、この時間が210時間以上の場合を◎(とても良い)、50時間から210時間の場合を○(良い)、50時間未満の場合を×(悪い)と記載した。
上記<パターニング性の評価>と同様の方法で、メッキ銅が成膜された8インチシリコンウェハ上に100μm×100μmの残しパターンを作成した。その後、窒素雰囲気下、170℃で2時間の硬化処理を行い、シェア強度測定用のサンプルを得た。
得られたサンプルについて、ダイシェア装置(ノードソン社製、Dage-4000)を用い、シェア速度200nm/秒、シェア高さ1μmの条件で、250℃でのシェア強度(熱時シェア強度、単位:MPa)を測定した。この値が大きいことは、硬化膜が高温に晒されても剥離しにくいことを意味する。つまり、電子デバイスの信頼性の点で、この値は大きい方が好ましい。
感光性樹脂組成物を、8インチシリコンウェハ上に、乾燥後の膜厚が10μmとなるようにスピンコートした。続いて120℃で3分間加熱を行って、感光性樹脂膜を得た。
得られた感光性樹脂膜に、高圧水銀灯にて300mJ/cm2の露光を行った。その後、シクロペンタノン中に30秒浸漬した後、スピンドライにて乾燥を行い、感光性樹脂組成物の現像後膜を得た。この現像後膜の膜厚を測定し、膜厚Aとした。
さらにその後、窒素雰囲気下、170℃で2時間熱処理して現像後膜を硬化させた。以上により、感光性樹脂組成物の硬化膜を得た。この硬化膜の膜厚を測定し、膜厚Bとした。
膜厚A及び膜厚Bを下記式に代入して、硬化収縮率を算出した。硬化収縮率は、配線上への塗布後の平坦性を保つために小さい方が好ましい。
硬化収縮率[%]={(膜厚A-膜厚B)/膜厚A}×100
酸化膜付きシリコンウェハ上に、幅5μm/ピッチ5μm、高さ5μmのCu配線を形成したCu配線基板を作製した。このCu配線基板上に、感光性樹脂組成物を、スピンコートによって、乾燥後の膜厚が10μmになるように塗布し、120℃で3分乾燥して感光性樹脂膜を形成した。
得られた感光性樹脂膜に、高圧水銀灯にて、300mJ/cm2の露光を行った。その後、シクロペンタノン中に30秒浸漬した。さらにその後、窒素雰囲気下、170℃で2時間熱処理して、基板上に硬化膜を形成した。
得られた硬化膜付き基板を割って、その断面を研磨した。そして、断面SEM観察により、感光性樹脂膜の表面の凹凸を評価した。表面の凹凸が1μm以下のものを○(良い)、表面の凹凸が1~3μmのものを△(使用できるレベル)3μmを超えたものを×(悪い)として評価した。
まず、上記<硬化膜の動的粘弾性測定(E'220等の測定)>の(試験片の作製)と同様にして試験片を作成した。
得られた試験片について、引張試験機(オリエンテック社製、テンシロンRTC-1210A)を用い、23℃雰囲気下、JIS K 7161に準拠した方法で引張試験を実施し、試験片の引張伸び率を測定した。引張試験における延伸速度は、5mm/分とした。
感光性樹脂組成物を、8インチシリコンウェハ上に、スピンコーターを用いて、乾燥後の膜厚が5μmになるように塗布した。その後、ホットプレートにて120℃で3分間乾燥し、感光性樹脂膜(感光性樹脂膜A)を得た。
この感光性樹脂膜に、凸版印刷社製マスク(テストチャートNo.1:幅0.5~50μmの残しパターン及び抜きパターンが描かれている)を通して、i線ステッパー(ニコン社製・NSR-4425i)を用いて、露光量を変化させながらi線を照射した。
その後、現像液としてシクロペンタノンを用いて30秒間現像し、2500回転で10秒間スピンし乾燥し、現像後膜(ネガ型パターン)を得た。
7μmΦのビアホールが開口したものを◎(とても良い)、10μmΦのビアホールが開口したものを○(良い)、10μmのビアホールが開口しなかったものを×(悪い)として評価した。
また、実施例1~14の感光性樹脂組成物の硬化物の硬化収縮率は小さく、段差埋込み平坦性の評価は良好であった。さらに、実施例1~14の感光性樹脂組成物の硬化物は、適度に伸びるものであった。加えて、実施例1~14の感光性樹脂組成物は、電子デバイス製造の際に十分なパターニング性能を有していた。
・実施例11とその他の実施例との対比より、熱ラジカル発生剤の使用により、硬化物のガラス転移温度は上昇する傾向、CTE2/CTE1は小さくなる傾向がある。そして、熱ラジカル発生剤の使用により、信頼性は向上する傾向がある。これは、おそらくは、熱ラジカル発生剤の使用により、多官能(メタ)アクリレート化合物の重合が一層促進されるためと考えられる。
・実施例12および13と、その他の実施例との対比より、エポキシ樹脂やその硬化触媒を用いることで、引張伸び率が良化する傾向がある。おそらくは、ポリアミド樹脂および/またはポリイミド樹脂と、エポキシ樹脂とが結合形成(架橋)することにより、より伸びやすく破断しにくい硬化膜が形成されるものと考えられる。
・実施例14とその他の実施例との対比より、水の存在によっておそらくは密着助剤がよく働き、密着性が向上すると考えられる。
30 電極パッド
40 半導体チップ
50 パッシベーション膜
60 絶縁性樹脂膜(第1の絶縁性樹脂膜)
70 絶縁性樹脂膜(第2の絶縁性樹脂膜)
80 ハンダバンプ
100 電子デバイス
110 導電膜
200 粘着部材
250 開口部(第1の開口部)
300 開口部(第2の開口部)
Claims (13)
- ポリアミド樹脂および/またはポリイミド樹脂を含む感光性樹脂組成物であって、
当該感光性樹脂組成物を170℃で2時間加熱して得られた硬化膜を、以下条件で動的粘弾性測定をしたときの、220℃での貯蔵弾性率E'220が0.5~3.0GPaである、感光性樹脂組成物。
[条件]
周波数:1Hz
温度:30~300℃
昇温速度:5℃/分
測定モード:引張りモード - 請求項1に記載の感光性樹脂組成物であって、
前記硬化膜のガラス転移温度をTg[℃]とし、
Tg-50[℃]からTg-20[℃]までの温度領域における前記硬化膜の熱膨張係数をCTE1とし、Tg+20[℃]からTg+50[℃]までの温度領域における前記硬化膜の熱膨張係数をCTE2としたとき、CTE2/CTE1の値が1~10である感光性樹脂組成物。 - 請求項1または2に記載の感光性樹脂組成物であって、
イミド環構造を有するポリイミド樹脂を含む、感光性樹脂組成物。 - 請求項1~3のいずれか1項に記載の感光性樹脂組成物であって、
さらに、多官能(メタ)アクリレート化合物を含む、感光性樹脂組成物。 - 請求項1~4のいずれか1項に記載の感光性樹脂組成物であって、
さらに、感光剤を含む、感光性樹脂組成物。 - 請求項5に記載の感光性樹脂組成物であって、
前記感光剤は、光ラジカル発生剤を含む、感光性樹脂組成物。 - 請求項1~6いずれか1項に記載の感光性樹脂組成物であって、
さらに、熱ラジカル開始剤を含む、感光性樹脂組成物。 - 請求項1~7いずれか1項に記載の感光性樹脂組成物であって、
さらに、エポキシ樹脂を含む、感光性樹脂組成物。 - 請求項1~8いずれか1項に記載の感光性樹脂組成物であって、
少なくとも前記ポリアミド樹脂および/またはポリイミド樹脂が溶剤に溶解したワニス状である、感光性樹脂組成物。 - 請求項1~9のいずれか1項に記載の感光性樹脂組成物であって、
電子デバイスにおける絶縁層の形成に用いられる、感光性樹脂組成物。 - 基板上に、請求項1~10のいずれか1項に記載の感光性樹脂組成物を用いて感光性樹脂膜を形成する膜形成工程と、
前記感光性樹脂膜を露光する露光工程と、
露光された前記感光性樹脂膜を現像する現像工程と、
を含む、電子デバイスの製造方法。 - 請求項11に記載の電子デバイスの製造方法であって、
前記現像工程の後に、露光された前記感光性樹脂膜を加熱して硬化させる熱硬化工程を含む、電子デバイスの製造方法。 - 請求項1~10のいずれか1項に記載の感光性樹脂組成物の硬化膜を備える電子デバイス。
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| US18/683,961 US20250138422A1 (en) | 2021-08-20 | 2021-08-20 | Photosensitive resin composition, manufacturing method of electronic device, and electronic device |
| KR1020247008760A KR102921834B1 (ko) | 2021-08-20 | 감광성 수지 조성물, 전자 디바이스의 제조 방법 및 전자 디바이스 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017057281A1 (ja) * | 2015-09-30 | 2017-04-06 | 東レ株式会社 | ネガ型感光性樹脂組成物、硬化膜、硬化膜を具備する素子及び表示装置、並びにその製造方法 |
| WO2017104672A1 (ja) * | 2015-12-17 | 2017-06-22 | 富士フイルム株式会社 | 複素環含有ポリマー前駆体の製造方法、および複素環含有ポリマー前駆体、並びにその応用 |
| WO2017110982A1 (ja) * | 2015-12-25 | 2017-06-29 | 富士フイルム株式会社 | 樹脂、組成物、硬化膜、硬化膜の製造方法および半導体デバイス |
| WO2018221457A1 (ja) * | 2017-05-31 | 2018-12-06 | 富士フイルム株式会社 | 感光性樹脂組成物、ポリマー前駆体、硬化膜、積層体、硬化膜の製造方法および半導体デバイス |
| WO2020196764A1 (ja) * | 2019-03-27 | 2020-10-01 | 株式会社カネカ | アルカリ可溶性ポリイミドおよびその製造方法、ネガ型感光性樹脂組成物、硬化膜、ならびにパターン硬化膜の製造方法 |
| JP2021162834A (ja) * | 2020-03-31 | 2021-10-11 | 住友ベークライト株式会社 | 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス |
-
2021
- 2021-08-20 US US18/683,961 patent/US20250138422A1/en active Pending
- 2021-08-20 WO PCT/JP2021/030570 patent/WO2023021688A1/ja not_active Ceased
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017057281A1 (ja) * | 2015-09-30 | 2017-04-06 | 東レ株式会社 | ネガ型感光性樹脂組成物、硬化膜、硬化膜を具備する素子及び表示装置、並びにその製造方法 |
| WO2017104672A1 (ja) * | 2015-12-17 | 2017-06-22 | 富士フイルム株式会社 | 複素環含有ポリマー前駆体の製造方法、および複素環含有ポリマー前駆体、並びにその応用 |
| WO2017110982A1 (ja) * | 2015-12-25 | 2017-06-29 | 富士フイルム株式会社 | 樹脂、組成物、硬化膜、硬化膜の製造方法および半導体デバイス |
| WO2018221457A1 (ja) * | 2017-05-31 | 2018-12-06 | 富士フイルム株式会社 | 感光性樹脂組成物、ポリマー前駆体、硬化膜、積層体、硬化膜の製造方法および半導体デバイス |
| WO2020196764A1 (ja) * | 2019-03-27 | 2020-10-01 | 株式会社カネカ | アルカリ可溶性ポリイミドおよびその製造方法、ネガ型感光性樹脂組成物、硬化膜、ならびにパターン硬化膜の製造方法 |
| JP2021162834A (ja) * | 2020-03-31 | 2021-10-11 | 住友ベークライト株式会社 | 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス |
Non-Patent Citations (1)
| Title |
|---|
| SHI GENGGONGWO, PARK JIN WOO, PARK LEE SOON: "Black Photoresist for Patterning Pixel Define Layer of Organic Light Emitting Diode with Polyimide as Thermal Stabilizer", MATERIALS SCIENCES AND APPLICATION, SCIENTIFIC RESEARCH PUBLISHING, INC., US, vol. 09, no. 06, 1 May 2018 (2018-05-01), US , pages 554 - 564, XP093036388, ISSN: 2153-117X, DOI: 10.4236/msa.2018.96040 * |
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