WO2013168675A1 - ネガ型感光性樹脂組成物、硬化レリーフパターンの製造方法、及び半導体装置 - Google Patents
ネガ型感光性樹脂組成物、硬化レリーフパターンの製造方法、及び半導体装置 Download PDFInfo
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- WO2013168675A1 WO2013168675A1 PCT/JP2013/062766 JP2013062766W WO2013168675A1 WO 2013168675 A1 WO2013168675 A1 WO 2013168675A1 JP 2013062766 W JP2013062766 W JP 2013062766W WO 2013168675 A1 WO2013168675 A1 WO 2013168675A1
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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
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a photosensitive resin composition, a semiconductor device having a cured relief pattern obtained by curing the photosensitive resin composition, a display device, and the like.
- polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices.
- these polyimide resins those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by applying the precursor, exposing, developing, and curing. be able to.
- Such a photosensitive polyimide precursor has a feature that the process can be greatly shortened as compared with a conventional non-photosensitive polyimide resin.
- the mounting method of a semiconductor device on a printed wiring board has also been changed from the viewpoint of improving the degree of integration and calculation function and reducing the chip size.
- the polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which can be mounted at a higher density than conventional mounting methods using metal pins and lead-tin eutectic solder. Structures are being used. When such a bump structure is formed, the film is required to have high heat resistance and chemical resistance.
- the problem of wiring delay has become apparent as semiconductor devices become more miniaturized.
- the gold or aluminum wiring that has been used so far has been changed to a copper or copper alloy wiring having a lower resistance.
- a method of preventing wiring delay by increasing insulation between wirings is also employed.
- a low dielectric constant material often constitutes a semiconductor device as this highly insulating material.
- a low dielectric constant material tends to be brittle and fragile. When mounted on a low dielectric constant material, there is a problem that the low dielectric constant material portion is destroyed by shrinkage due to temperature change.
- Patent Document 1 discloses a photosensitive polyimide precursor in which a part of a photosensitive group having 4 or more carbon atoms having a terminal ethylene bond is substituted with a hydrocarbon group having 1 to 3 carbon atoms. Is disclosed.
- the photosensitive resin composition comprising the polyimide precursor described in Patent Document 1 improves the resolution or elongation, but the transparency of the photosensitive resin composition or the hardness (Young's modulus) as a polyimide film. There was room for improvement.
- the present invention provides a photosensitive resin composition that gives a cured product having high transparency as a resin composition and a high Young's modulus after heat curing, and a method for producing a cured relief pattern using the photosensitive resin composition And a semiconductor device or a display device including the cured relief pattern.
- the present inventor has intensively studied and repeated experiments, and as a result, by introducing a specific chemical structure into a part of the side chain of the polyimide precursor, a photosensitive material containing the polyimide precursor is obtained.
- the present inventors have found that a photosensitive resin composition can be obtained in which the transparency when forming the photosensitive resin composition is improved and the Young's modulus of the cured film is improved after thermosetting, and the present invention has been completed. That is, the present invention is as follows.
- R 1 and R 2 are each independently a hydrogen atom, or the following general formula (2) or (3): (Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10) -R 6 (3) (Wherein R 6 is a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or an aromatic group having 6 to 30 carbon atoms.) A monovalent organic group represented by the general formula (2) and a monovalent organic group represented by the general formula (3) for all of R 1 and R 2 .
- a negative photosensitive resin composition comprising:
- [5] The following steps: (1) A step of applying the negative photosensitive resin composition according to any one of [1] to [4] on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the photosensitive resin layer after the exposure to form a relief pattern; (4) A method for producing a cured relief pattern, comprising: heat-treating the relief pattern to form a cured relief pattern.
- a semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to [6].
- a display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to [6]. .
- a photosensitive resin composition that gives a cured product having high transparency as a resin composition and a high Young's modulus after thermosetting, and a method for producing a cured relief pattern using the photosensitive resin composition And a semiconductor device or a display device including the cured relief pattern can be provided.
- the photosensitive resin composition includes (A) a polyimide precursor, (B) an initiator, optionally (C) a thermal crosslinking agent, and optionally other components. Each component will be described in turn below.
- the (A) polyimide precursor is a resin component contained in the negative photosensitive resin composition, and is a polyamide having a structure represented by the following general formula (1). . ⁇ Wherein X 1 is a tetravalent organic group having 6 to 40 carbon atoms, Y 1 is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 150.
- R 1 and R 2 are each independently a hydrogen atom, or the following general formula (2) or (3): (Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10) -R 6 (3) (Wherein R 6 is a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or an aromatic group having 6 to 30 carbon atoms.) A monovalent organic group represented by the general formula (2) and a monovalent organic group represented by the general formula (3) with respect to all of R 1 and R 2. The total of the groups is 80 mol% or more, and the ratio of the monovalent organic group represented by the general formula (3) to all of R 1 and R 2 is 20 mol% to 80 mol%. ⁇
- X 1 is not limited as long as it is a tetravalent organic group having 6 to 40 carbon atoms. However, from the viewpoint of achieving both heat resistance and photosensitive properties, it is preferably a —COOR 1 group. And the —COOR 2 group and the —CONH— group are each an aromatic group or an alicyclic aliphatic group in the ortho position. Further, the tetravalent organic group represented by X 1 is more preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring.
- X 1 is a tetravalent organic group represented by the following general formula (5).
- X 1 may be one type or a combination of two or more types.
- Y 1 is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms. However, from the viewpoint of achieving both heat resistance and photosensitive properties, Y 1 may be a substituted fragrance.
- a cyclic organic group having 1 to 4 aromatic rings or aliphatic rings, or an aliphatic group or siloxane group having no cyclic structure is preferable. More preferably, Y 1 is a structure represented by the following general formula (6) or (7). (In the formula, each A independently represents a methyl group (—CH 3 ), an ethyl group (—C 2 H 5 ), a propyl group (—C 3 H 7 ), or a butyl group (—C 4 H 9 ). . ⁇
- the structure of Y 1 may be one type or a combination of two or more types.
- R 1 and R 2 in the general formula (1) are each independently a hydrogen atom or a monovalent organic group represented by the general formula (2) or (3).
- N in the general formula (1) is not limited as long as it is an integer of 2 to 150, but is preferably an integer of 3 to 100 from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition. Is more preferable.
- the monovalent organic group represented by the general formula (2) and the general formula for all of R 1 and R 2 The total ratio of the monovalent organic group represented by (3) is 80 mol% or more, and the monovalent organic group represented by the above general formula (3) with respect to all of R 1 and R 2 . The ratio is 20 mol% to 80 mol%. Furthermore, in the general formula (1), the total of the monovalent organic group represented by the general formula (2) and the monovalent organic group represented by the general formula (3) for all of R 1 and R 2 The ratio of the monovalent organic group represented by the general formula (3) to all of R 1 and R 2 is 25 mol% to 75 mol%. More preferred.
- R 3 in the general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. From the viewpoint of the photosensitive properties of the photosensitive resin composition, R 3 is a hydrogen atom or a methyl group. It is preferable that
- R 4 and R 5 in the general formula (2) are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but from the viewpoint of the photosensitive properties of the photosensitive resin composition To a hydrogen atom.
- M in the general formula (2) is an integer of 2 or more and 10 or less, and is preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.
- R 6 in the general formula (3) may be a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or an aromatic group having 6 to 30 carbon atoms. Although not limited, it is preferably an aliphatic group having 5 to 30 carbon atoms, and more preferably an aliphatic group having 5 to 30 carbon atoms having an ethylene glycol structure.
- the aliphatic group having 5 to 30 carbon atoms may be a saturated hydrocarbon group, and part or all of the hydrogen atoms of the saturated hydrocarbon group may be a monovalent saturated organic group containing a hetero atom, or a monovalent The aromatic group may be substituted.
- R 6 in the general formula (3) is selected from the group consisting of a neopentyl group, an octyl group, a benzyl group, and a group derived from polyethylene glycol monomethyl ether.
- the hetero atom in the present invention includes an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.
- the polyimide precursor is converted into polyimide by performing a cyclization treatment (for example, 200 ° C. or higher).
- the polyimide precursor represented by the general formula (1) in the present embodiment includes, for example, the above-described tetracarboxylic dianhydride containing a tetravalent organic group X 1 having 6 to 40 carbon atoms, and (a) the above Alcohols formed by bonding a monovalent organic group represented by the general formula (2) and a hydroxyl group, and (b) a monovalent organic group represented by the general formula (3) and a hydroxyl group are bonded.
- a partially esterified tetracarboxylic acid hereinafter also referred to as an acid / ester
- divalent organic group Y 1 having 6 to 40 carbon atoms. It can be obtained by polycondensation with diamines.
- examples of the tetracarboxylic dianhydride containing a tetravalent organic group X 1 having 6 to 40 carbon atoms include pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic acid.
- Acid dianhydride benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′ , 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2, Examples thereof include 2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane. Moreover, these can be used individually by 1 type or in mixture of 2 or more types.
- (a) alcohols having a structure represented by the general formula (2) include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, methylol vinyl ketone, -Hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Examples thereof include propyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, and the like.
- Examples of aliphatic having 5 to 30 carbon atoms or aromatic alcohol having 6 to 30 carbon atoms represented by the general formula (3) include 1-pentanol, 2-pentanol, and 3-pentanol. , Neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl Examples include ether, tetraethylene glycol monoethyl ether, benzyl alcohol and the like.
- the total content of the component (a) and the component (b) in the negative photosensitive resin composition is 80 mol% or more based on the total content of R 1 and R 2 in the general formula (1).
- the content of component (b) is preferably 20 mol% to 80 mol% with respect to the total content of R 1 and R 2 .
- the content of the component (b) is 80 mol% or less, it is preferable because desired photosensitive characteristics can be obtained.
- the content of the component (b) is 20 mol% or more, transparency is improved. It is preferable because it is easy to express.
- the above tetracarboxylic dianhydride and the above alcohols are stirred, dissolved and mixed in a reaction solvent at a reaction temperature of 20 to 50 ° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine.
- a basic catalyst such as pyridine.
- the reaction solvent is preferably one that dissolves the acid / ester compound and a polyimide precursor that is a polycondensation product of the acid / ester compound and a diamine, such as N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gammabutyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobut Emission
- a known dehydration condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate and the like are added and mixed to form an acid / ester product as a polyanhydride.
- a polyimide precursor that can be used in the embodiment by adding dropwise a solution obtained by dissolving or dispersing a diamine containing a divalent organic group Y 1 having 6 to 40 carbon atoms in a solvent and polycondensing it. Can be obtained.
- diamines containing a divalent organic group Y 1 having 6 to 40 carbon atoms include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzoph
- diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can be copolymerized.
- the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is removed.
- the polyimide precursor that can be used in the embodiment is charged into the reaction solution to precipitate the polymer component, and further, by re-dissolving, re-precipitation and the like, to purify the polymer and vacuum-dry it. Isolate the body.
- the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.
- the molecular weight of the polyimide precursor is preferably 8,000 to 150,000, preferably 9,000 to 50,000, as measured by polystyrene-reduced weight average molecular weight by gel permeation chromatography. Is more preferable, and 20,000 to 40,000 is particularly preferable. When the weight average molecular weight is 8,000 or more, it is preferable because the mechanical properties are good. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility in the developer and the resolution performance of the relief pattern are good. It is preferable because it is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography.
- the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene.
- standard monodisperse polystyrene it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
- (B) Photopolymerization initiator The (B) photopolymerization initiator in this embodiment is demonstrated.
- (B) As a photoinitiator the compound conventionally used as a photoinitiator for UV hardening can be selected arbitrarily.
- (B) photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives; 2,2′-diethoxyacetophenone Acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzyl, benzyldimethyl ketal, benzyl- Benzyl derivatives such as ⁇ -methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl)
- the blending amount of the (B) photopolymerization initiator is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. preferable.
- the photosensitive resin composition is excellent in photosensitivity by mix
- the photosensitive resin composition is excellent in thick film curability.
- the negative photosensitive resin composition further contains (C) a thermal crosslinking agent.
- the thermal crosslinking agent can crosslink (A) the polyimide precursor, or the thermal crosslinking agent itself can form a crosslinked network. Can be an agent.
- the thermal crosslinking agent is preferable because it can further enhance the heat resistance and chemical resistance of the cured film formed from the negative photosensitive resin composition.
- amino resins and derivatives thereof are preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used.
- Particularly preferred are alkoxymethylated urea compounds and alkoxymethylated melamine compounds, for example, MX-290 (manufactured by Nippon Carbide), UFR-65 (manufactured by Nippon Cytec), and MW-390 (manufactured by Nippon Carbide). ).
- the blending amount in the case of containing a thermal crosslinking agent is not limited as long as it is 0.1 to 30 parts by mass with respect to 100 parts by mass of (A) polyimide precursor. Among them, the amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass. When the blending amount is 0.1 part by mass or more, good heat resistance and chemical resistance are expressed, and when it is 30 parts by mass or less, storage stability is excellent, which is preferable.
- the negative photosensitive resin composition may further contain components other than the above components (A) to (C).
- Other components include, for example, a solvent, a resin component other than the (A) polyimide precursor, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion assistant, a thermal polymerization inhibitor, an azole compound, and a hinder.
- a dophenol compound, an organic titanium compound, etc. are mentioned.
- a polar organic solvent from the viewpoint of solubility in the (A) polyimide precursor.
- the solvent is, for example, in the range of 30 parts by weight to 1500 parts by weight, preferably 100 parts, based on 100 parts by weight of the polyimide precursor (A), depending on the desired coating thickness and viscosity of the negative photosensitive resin composition. It can be used in the range of parts by mass to 1000 parts by mass.
- Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples include methyl alcohol, ethyl alcohol, n- Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; lactic acid esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Propylene glycol monoalkyl ethers such as -1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether Le ethers, ethylene glycol methyl ether, ethylene glycol methyl ether, ethylene glycol
- lactic acid esters propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, And propylene glycol-1- (n-propyl) ether is more preferred.
- the content of the alcohol having no olefinic double bond in the total solvent is 5% by mass to 50% based on the mass of the entire solvent.
- the mass is preferably 10% by mass, more preferably 10% by mass to 30% by mass.
- the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the negative photosensitive resin composition is improved.
- the content is 50% by mass or less, (A ) Since the solubility of a polyimide precursor becomes favorable, it is preferable.
- the negative photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor.
- a resin component other than the (A) polyimide precursor examples include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.
- the blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- a sensitizer can be arbitrarily blended in the negative photosensitive resin composition in order to improve photosensitivity.
- the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal).
- the blending amount of the sensitizer is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- a monomer having a photopolymerizable unsaturated bond can be arbitrarily added to the negative photosensitive resin composition.
- a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate.
- the amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- an adhesion assistant may be arbitrarily added to the negative photosensitive resin composition.
- the adhesion assistant include ⁇ -aminopropyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) ) Succinimide, N- [3- (triethoxysilyl) propyl] phthal
- adhesion assistants it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength.
- the blending amount of the adhesion assistant is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition at the time of storage, particularly in the state of a solution containing a solvent, a thermal polymerization inhibitor can be arbitrarily added.
- the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2 , 6-Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl- N-sulfopropylamino) phenol, N-nitroso-
- the blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- an azole compound can be arbitrarily added to the negative photosensitive resin composition in order to suppress discoloration of the substrate.
- the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl.
- the compounding amount of the azole compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. More preferably.
- the compounding amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the negative photosensitive resin composition is formed on copper or a copper alloy, copper or Discoloration of the surface of the copper alloy is suppressed, and on the other hand, the amount of 20 parts by mass or less is preferable because of excellent photosensitivity.
- a hindered phenol compound can be arbitrarily added to the negative photosensitive resin composition in order to suppress discoloration on copper.
- the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl.
- 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione is particularly preferred.
- the amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. More preferably, it is a part.
- the compounding quantity with respect to 100 mass parts of (A) polyimide precursor of a hindered phenol compound is 0.1 mass part or more, for example, when forming a negative photosensitive resin composition on copper or a copper alloy, copper Alternatively, discoloration / corrosion of the copper alloy is prevented, and on the other hand, the content of 20 parts by mass or less is preferable because of excellent photosensitivity.
- the negative photosensitive resin composition may contain an organic titanium compound.
- an organic titanium compound By containing an organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250 ° C.
- Examples of usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom through a covalent bond or an ionic bond.
- Titanium chelate compound a titanium chelate having two or more alkoxy groups is more preferable because it provides storage stability and a good pattern of the negative photosensitive resin composition, and a specific example is titanium bis (Triethanolamine) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate), titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis (Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.
- titanium bis (Triethanolamine) diisopropoxide titanium di (n-butoxide) bis (2,4-pentanedionate), titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis (Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.
- Tetraalkoxytitanium compounds for example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonoxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis ⁇ 2,2- (allyloxymethyl) Butoxide ⁇ ] and the like.
- Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5 ⁇ 2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
- Monoalkoxytitanium compound For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.
- Titanium oxide compound for example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
- Titanium tetraacetylacetonate compound For example, titanium tetraacetylacetonate.
- Titanate coupling agent For example, isopropyltridodecylbenzenesulfonyl titanate.
- the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanocene compound, It is preferable from the viewpoint of exhibiting good chemical resistance.
- titanium diisopropoxide bis (ethyl acetoacetate), titanium tetra (n-butoxide), and bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) phenyl) titanium is preferred.
- the blending amount is preferably 0.05 parts by weight to 10 parts by weight and preferably 0.1 parts by weight to 2 parts by weight with respect to 100 parts by weight of the resin (A). More preferred.
- the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are expressed.
- it is 10 parts by mass or less, storage stability is excellent, which is preferable.
- the following steps (1) to (4) are performed: (1) The process of apply
- a manufacturing method can be provided.
- substrate the negative photosensitive resin composition of embodiment is formed. It apply
- a coating method a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spray coating with a spray coater A method or the like can be used.
- the coating film made of the negative photosensitive resin composition can be dried, and examples of the drying method include air drying, heat drying with an oven or hot plate, and vacuum drying. Moreover, it is desirable to perform drying of a coating film on the conditions that the imidation of the (A) polyimide precursor in a negative photosensitive resin composition does not occur. Specifically, when air drying or heat drying is performed, the drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. Thus, a photosensitive resin layer can be formed on the substrate.
- Step of exposing the photosensitive resin layer the photosensitive resin layer formed in the step (1) is patterned using an exposure apparatus such as a contact aligner, mirror projection, or stepper. Alternatively, exposure is performed with an ultraviolet light source or the like via a reticle or directly.
- an exposure apparatus such as a contact aligner, mirror projection, or stepper.
- exposure is performed with an ultraviolet light source or the like via a reticle or directly.
- post-exposure baking PEB
- pre-development baking with any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity.
- the temperature is preferably 40 ° C. to 120 ° C.
- the time is preferably 10 seconds to 240 seconds.
- the various characteristics of the negative photosensitive resin composition are not impaired, It is not restricted to this range.
- Step of developing the exposed photosensitive resin layer to form a relief pattern the unexposed portion of the exposed photosensitive resin layer is developed and removed.
- a developing method for developing the photosensitive resin layer after exposure any of conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, etc. The method can be selected and used.
- post-development baking at any combination of temperature and time may be performed as necessary.
- the developer used for development for example, a good solvent for the negative photosensitive resin composition or a combination of the good solvent and the poor solvent is preferable.
- the good solvent for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone and the like are preferable.
- the poor solvent for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water are preferable.
- the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition.
- two or more of each solvent for example, several types may be used in combination.
- Step of heat-treating the relief pattern to form a cured relief pattern the relief pattern obtained by the development is heated to dilute the photosensitive component, and (A) the polyimide precursor By imidizing, it is converted into a cured relief pattern made of polyimide.
- a method for heat curing various methods such as a method using a hot plate, a method using an oven, a method using a temperature rising oven capable of setting a temperature program can be selected. The heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, and an inert gas such as nitrogen or argon may be used.
- the semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. Therefore, the semiconductor device which has the base material which is a semiconductor element, and the hardening relief pattern of the polyimide formed on this base material by the hardening relief pattern manufacturing method mentioned above can be provided.
- the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of the process.
- the semiconductor device of the present invention is a semiconductor device having a surface relief film, an interlayer insulation film, a rewiring insulation film, a flip chip device protection film, or a bump structure as a cured relief pattern formed by the above-described cured relief pattern production method. And can be manufactured by combining with a known method for manufacturing a semiconductor device.
- a display body device including a display body element and a cured film provided on the display body element, wherein the cured film is the above-described cured relief pattern is provided.
- the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween.
- the cured film include surface protective films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA liquid crystal display devices, and partition walls for organic EL element cathodes. .
- the negative photosensitive resin composition of the present invention is used for applications such as the above-mentioned semiconductor devices as well as interlayer insulation of multilayer circuits, cover coats of flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is also useful.
- Weight average molecular weight The weight average molecular weight (Mw) of each polyimide precursor was measured by the gel permeation chromatography method (standard polystyrene conversion).
- the column used for the measurement is a trade name Shodex 805M / 806M series manufactured by Showa Denko KK, and the standard monodisperse polystyrene is Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent is N-methyl-2- It was pyrrolidone, and the detector used was a trade name Shodex RI-930 manufactured by Showa Denko.
- the photosensitive resin composition was spin-coated on a 3 cm square quartz substrate and dried to form a 10 ⁇ m thick coating film.
- the film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor).
- the absorbance at a wavelength of 365 nm was measured on this quartz substrate using a UV measuring device (manufactured by Shimadzu Corporation, UV-1600PC). If the absorbance at 10 ⁇ m thickness was 1.5 or less, it was judged as good.
- the obtained polyimide coating film was cut into a 3 mm width strip using a dicing saw (DAD3350 type, manufactured by DISCO), and then peeled off from the silicon wafer using 46% hydrofluoric acid to obtain a polyimide tape.
- the Young's modulus of the obtained polyimide tape was measured according to ASTM D882-09 using a tensile tester (UTM-II-20 type, manufactured by Orientec Corp.). If the Young's modulus was 5.0 GPa or more, it was considered good.
- the wafer on which the pattern is formed is heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and then at 300 ° C. for 2 hours using a temperature-programmed cure furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan).
- VF-2000 type temperature-programmed cure furnace
- a polyimide pattern having a thickness of 5 ⁇ m was obtained on the silicon wafer.
- variety of the pattern shape and the pattern part was observed under the optical microscope, and the resolution was calculated
- a pattern having a plurality of openings with different areas is formed by the above method by exposing through a reticle with a test pattern, and the area of the obtained pattern opening is equal to the corresponding pattern mask opening area.
- the resolution is good if it is 10 ⁇ m or less, that is, if the aspect ratio (film thickness after coating / drying) is 1 or more.
- the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer.
- the produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polymer A).
- polymer A weight average molecular weight
- a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated.
- Polymer A 100 g ((A) polyimide precursor), which is a polyimide precursor, was converted into 4 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime ((B) photopolymerization initiator), 0.15 g of triazole, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, N-phenyldiethanolamine 10 g, methoxymethylated urea resin (MX-290) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid 1.5 g , And 0.05
- the composition was evaluated according to the above-mentioned method. As a result, the absorbance was 1.36, the Young's modulus was as good as 5.6 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 2 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer B, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.29, the Young's modulus was as good as 5.5 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 3 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer C, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.40, the Young's modulus was 5.4 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 4 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer F, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.48, the Young's modulus was as good as 5.6 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 5 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer G, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.50, the Young's modulus was good at 6.0 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 6 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer H, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.48, the Young's modulus was as good as 5.6 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 7 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer I, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.50, the Young's modulus was good at 5.0 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 8> A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer J, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.27, the Young's modulus was as good as 5.6 GPa, the resolution was 8 ⁇ m, and the pattern accuracy was also good.
- Example 1 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer D, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.68, the Young's modulus was 4.8 GPa, and the pattern accuracy was poor.
- Example 2 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer E, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.57, the Young's modulus was 4.9 GPa, and the pattern accuracy was poor.
- Example 3 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer K, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.58, the Young's modulus was 4.9 GPa, and the pattern accuracy was not satisfactory.
- Example 4 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer L, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.25 and the Young's modulus was 5.6 GPa, but the pattern accuracy was poor.
- Example 5 A negative photosensitive resin composition similar to that of Example 1 was prepared except that (A) the polyimide precursor in Example 1 of the present invention was changed to polymer M, and evaluation similar to that of Example 1 was performed. As a result, the absorbance was 1.63, the Young's modulus was 4.9 GPa, and the pattern accuracy was poor.
- the negative photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards.
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Abstract
Description
-R6 (3)
(式中、R6は、ヘテロ原子を有していてもよい炭素数5~30の脂肪族基、又は炭素数6~30の芳香族基から選択される1価の基である。)
で表される1価の有機基であり、そしてR1及びR2の全てに対する上記一般式(2)で表される1価の有機基と上記一般式(3)で表される1価の有機基の合計の割合は、80モル%以上であり、かつR1及びR2の全てに対する上記一般式(3)で表される1価の有機基の割合は、20モル%~80モル%である。}
で表される構造を有するポリイミド前駆体:100質量部;及び
(B)光重合開始剤:0.1質量部~20質量部;
を含むネガ型感光性樹脂組成物。
(1)[1]~[4]のいずれか1項に記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程と、
(2)該感光性樹脂層を露光する工程と、
(3)該露光後の感光性樹脂層を現像して、レリーフパターンを形成する工程と、
(4)該レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と
を含む硬化レリーフパターンの製造方法。
実施の形態では、(A)ポリイミド前駆体は、ネガ型感光性樹脂組成物に含まれる樹脂成分であり、下記一般式(1)で表される構造を有するポリアミドである。
-R6 (3)
(式中、R6は、ヘテロ原子を有していてもよい炭素数5~30の脂肪族基、又は炭素数6~30の芳香族基から選択される1価の基である。)
で表される1価の有機基であり、R1及びR2の全てに対する上記一般式(2)で表される1価の有機基と上記一般式(3)で表される1価の有機基の合計は、80モル%以上であり、かつR1及びR2の全てに対する上記一般式(3)で表される1価の有機基の割合は、20モル%~80モル%である。}
なお、本発明におけるヘテロ原子は、酸素原子、硫黄原子、窒素原子、リン原子が挙げられる。
本実施形態における上記一般式(1)で表されるポリイミド前駆体は、例えば、前述の炭素数6~40の4価の有機基X1を含むテトラカルボン酸二無水物と、(a)上記一般式(2)で表される1価の有機基と水酸基とが結合して成るアルコール類、及び(b)上記一般式(3)で表される1価の有機基と水酸基とが結合して成るアルコール類を反応させて、部分的にエステル化したテトラカルボン酸(以下、アシッド/エステル体ともいう)を調製し、続いて前述の炭素数6~40の2価の有機基Y1を含むジアミン類と重縮合させることにより得られる。
本実施形態において、炭素数6~40の4価の有機基X1を含むテトラカルボン酸二無水物としては、例えば、無水ピロメリット酸、ジフェニルエーテル-3,3’,4,4’-テトラカルボン酸二無水物、ベンゾフェノン-3,3’,4,4’-テトラカルボン酸二無水物、ビフェニル-3,3’,4,4’-テトラカルボン酸二無水物、ジフェニルスルホン-3,3’,4,4’-テトラカルボン酸二無水物、ジフェニルメタン-3,3’,4,4’-テトラカルボン酸二無水物、2,2-ビス(3,4-無水フタル酸)プロパン、2,2-ビス(3,4-無水フタル酸)-1,1,1,3,3,3-ヘキサフルオロプロパン等を挙げることができる。また、これらは、1種を単独で、又は2種以上を混合して、使用されることができる。
上記アシッド/エステル体(典型的には上記反応溶媒中の溶液)に、氷冷下、既知の脱水縮合剤、例えば、ジシクロヘキシルカルボジイミド、1-エトキシカルボニル-2-エトキシ-1,2-ジヒドロキノリン、1,1-カルボニルジオキシ-ジ-1,2,3-ベンゾトリアゾール、N,N’-ジスクシンイミジルカーボネート等を投入混合してアシッド/エステル体をポリ酸無水物とした後、これに、炭素数6~40の2価の有機基Y1を含むジアミン類を別途溶媒に溶解又は分散させたものを滴下投入し、重縮合させることにより、実施の形態で用いることができるポリイミド前駆体を得ることができる。
本実施形態における(B)光重合開始剤について説明する。(B)光重合開始剤としては、UV硬化用の光重合開始剤として従来用いられている化合物を任意に選択できる。例えば、(B)光重合開始剤としては、ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-ベンゾイル-4’-メチルジフェニルケトン、ジベンジルケトン、フルオレノン等のベンゾフェノン誘導体;2,2’-ジエトキシアセトフェノン、2-ヒドロキシ-2-メチルプロピオフェノン、1-ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン誘導体;チオキサントン、2-メチルチオキサントン、2-イソプロピルチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体;ベンジル、ベンジルジメチルケタール、ベンジル-β-メトキシエチルアセタール等のベンジル誘導体;ベンゾイン、ベンゾインメチルエーテル等のベンゾイン誘導体;1-フェニル-1,2-ブタンジオン-2-(O-メトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-メトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-ベンゾイル)オキシム、1,3-ジフェニルプロパントリオン-2-(O-エトキシカルボニル)オキシム、1-フェニル-3-エトキシプロパントリオン-2-(O-ベンゾイル)オキシム等のオキシム類;N-フェニルグリシン等のN-アリールグリシン類;ベンゾイルパークロライド等の過酸化物類;芳香族ビイミダゾール類等が好ましく挙げられるが、これらに限定されるものではない。また、これらは、1種を単独で又は2種以上を混合して使用されることができる。上記の(B)光重合開始剤の中では、特に光感度の点で、オキシム類がより好ましい。
実施の形態では、ネガ型感光性樹脂組成物は、更に(C)熱架橋剤を含むことが好ましい。熱架橋剤は、ネガ型感光性樹脂組成物を用いて形成されたレリーフパターンを加熱硬化するときに、(A)ポリイミド前駆体を架橋できるか、又は熱架橋剤自身が架橋ネットワークを形成できる架橋剤であることができる。(C)熱架橋剤は、ネガ型感光性樹脂組成物から形成された硬化膜の耐熱性及び耐薬品性を更に強化することができるため好ましい。(C)熱架橋剤としては、アミノ樹脂及びその誘導体が好適に用いられ、中でも、尿素樹脂、グリコール尿素樹脂、ヒドロキシエチレン尿素樹脂、メラミン樹脂、ベンゾグアナミン樹脂、及びこれらの誘導体が好適に用いられる。特に好ましくは、アルコキシメチル化尿素化合物及びアルコキシメチル化メラミン化合物であり、例として、MX-290(日本カーバイド社製)、UFR-65(日本サイテック社製)、及びMW-390(日本カーバイド社製)が挙げられる。
実施の形態では、ネガ型感光性樹脂組成物は、上記(A)~(C)成分以外の成分をさらに含有してもよい。その他の成分としては、例えば、溶剤、前記(A)ポリイミド前駆体以外の樹脂成分、増感剤、光重合性の不飽和結合を有するモノマー、接着助剤、熱重合禁止剤、アゾール化合物、ヒンダードフェノール化合物、有機チタン化合物などが挙げられる。
I)チタンキレート化合物:中でも、アルコキシ基を2個以上有するチタンキレートが、ネガ型感光性樹脂組成物の保存安定性及び良好なパターンが得られることからより好ましく、具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
実施の形態では、以下の工程(1)~(4):
(1)実施の形態のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程、
(2)該感光性樹脂層を露光する工程、
(3)該露光後の感光性樹脂層を現像して、レリーフパターンを形成する工程、及び
(4)該レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程
を含む、硬化レリーフパターンの製造方法を提供することができる。
(1)実施の形態のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程
本工程では、実施の形態のネガ型感光性樹脂組成物を基材上に塗布し、必要に応じて、その後に乾燥させて、感光性樹脂層を形成する。塗布方法としては、従来から感光性樹脂組成物の塗布に用いられていた方法、例えば、スピンコーター、バーコーター、ブレードコーター、カーテンコーター、スクリーン印刷機等で塗布する方法、スプレーコーターで噴霧塗布する方法等を用いることができる。
本工程では、上記(1)工程で形成した感光性樹脂層を、コンタクトアライナー、ミラープロジェクション、ステッパー等の露光装置を用いて、パターンを有するフォトマスク又はレチクルを介して又は直接に、紫外線光源等により露光する。
本工程では、露光後の感光性樹脂層のうち未露光部を現像除去する。露光(照射)後の感光性樹脂層を現像する現像方法としては、従来知られているフォトレジストの現像方法、例えば、回転スプレー法、パドル法、超音波処理を伴う浸漬法等の中から任意の方法を選択して使用することができる。また、現像の後、レリーフパターンの形状を調整する等の目的で、必要に応じて、任意の温度及び時間の組合せによる現像後ベークを施してもよい。現像に使用される現像液としては、例えば、ネガ型感光性樹脂組成物に対する良溶媒、又は該良溶媒と貧溶媒との組合せが好ましい。良溶媒としては、例えば、N-メチル-2-ピロリドン、N-シクロヘキシル-2-ピロリドン、N,N-ジメチルアセトアミド、シクロペンタノン、シクロヘキサノン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン等が好ましい。貧溶媒としては、例えば、トルエン、キシレン、メタノール、エタノール、イソプロピルアルコール、乳酸エチル、プロピレングリコールメチルエーテルアセテート及び水等が好ましい。良溶媒と貧溶媒とを混合して用いる場合には、ネガ型感光性樹脂組成物中のポリマーの溶解性によって良溶媒に対する貧溶媒の割合を調整することが好ましい。また、各溶媒を2種以上、例えば数種類組合せて用いることもできる。
本工程では、上記現像により得られたレリーフパターンを加熱して感光成分を希散させるとともに、(A)ポリイミド前駆体をイミド化させることによって、ポリイミドから成る硬化レリーフパターンに変換する。加熱硬化の方法としては、例えば、ホットプレートによるもの、オーブンを用いるもの、温度プログラムを設定できる昇温式オーブンを用いるもの等種々の方法を選ぶことができる。加熱は、例えば、200℃~400℃で30分~5時間の条件で行うことができる。加熱硬化時の雰囲気気体としては空気を用いてもよく、窒素、アルゴン等の不活性ガスを用いることもできる。
実施の形態では、上述した硬化レリーフパターンの製造方法により得られる硬化レリーフパターンを有して成る、半導体装置も提供される。したがって、半導体素子である基材と、上述した硬化レリーフパターン製造方法により該基材上に形成されたポリイミドの硬化レリーフパターンとを有する半導体装置が提供されることができる。また、本発明は、基材として半導体素子を用い、上述した硬化レリーフパターンの製造方法を工程の一部として含む半導体装置の製造方法にも適用できる。本発明の半導体装置は、上記硬化レリーフパターン製造方法で形成される硬化レリーフパターンを、表面保護膜、層間絶縁膜、再配線用絶縁膜、フリップチップ装置用保護膜、又はバンプ構造を有する半導体装置の保護膜等として形成し、既知の半導体装置の製造方法と組合せることで製造することができる。
実施の形態では、表示体素子と該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は上述の硬化レリーフパターンである表示体装置が提供される。ここで、当該硬化レリーフパターンは、当該表示体素子に直接接して積層されていてもよく、別の層を間に挟んで積層されていてもよい。例えば、該硬化膜として、TFT液晶表示素子及びカラーフィルター素子の表面保護膜、絶縁膜、及び平坦化膜、MVA型液晶表示装置用の突起、並びに有機EL素子陰極用の隔壁を挙げることができる。
各ポリイミド前駆体の重量平均分子量(Mw)をゲルパーミエーションクロマトグラフィー法(標準ポリスチレン換算)で測定した。測定に用いたカラムは、昭和電工社製 商標名 Shodex 805M/806M直列であり、標準単分散ポリスチレンは、昭和電工(株)製Shodex STANDARD SM-105を選び、展開溶媒はN-メチル-2-ピロリドンであり、検出器は昭和電工製 商標名 Shodex RI-930を使用した。
感光性樹脂組成物を3cm角の石英基板上にスピン塗布し、乾燥して10μm厚の塗膜を形成した。膜厚測定は、Tencor P-15型段差計(ケーエルエーテンコール社製)を用いて行った。この石英基板をUV測定器(島津社製、UV-1600PC)を用いて波長365nmにおける吸光度を測定した。10μm厚における吸光度が1.5以下であれば良好とした。
6インチシリコンウエハー上に、硬化後の膜厚が約10μmとなるように感光性樹脂組成物をスピン塗布乾燥した後、昇温プログラム式キュア炉(VF-2000型、光洋リンドバーグ社製)を用いて、窒素雰囲気下、200℃で1時間、300℃で2時間加熱して硬化レリーフパターン(熱硬化したポリイミドの塗膜)を得た。得られたポリイミド塗膜をダイシングソー(DAD3350型、DISCO社製)を用いて3mm幅の短冊状にカットした後、46%フッ化水素酸を用いてシリコンウエハーから剥がしてポリイミドテープとした。得られたポリイミドテープのヤング率を引張試験機(UTM-II-20型、オリエンテック社製)を用いて、ASTM D882-09に従って測定した。ヤング率が5.0GPa以上であれば良好とした。
感光性樹脂組成物を6インチシリコンウエハー上にスピン塗布し、乾燥して10μm厚の塗膜を形成した。この塗膜にテストパターン付レチクルを用いてi線ステッパーNSR1755i7B(ニコン社製)により、300mJ/cm2のエネルギーを照射した。次いで、ウエハー上に形成した塗膜を、シクロペンタノンを用いて現像機(D-SPIN636型、大日本スクリーン製造社製)でスプレー現像し、プロピレングリコールメチルエーテルアセテートでリンスして、ポリアミド酸エステルのパターンを得た。
解像度に関しては、テストパターン付きレチクルを介して露光することにより複数の異なる面積の開口部を有するパターンを上記の方法で形成し、得られたパターン開口部の面積が、対応するパターンマスク開口面積の1/2以上であれば解像されたものとみなし、解像された開口部のうち最小面積を有するものに対応するマスクの開口辺の長さを解像度とした。解像度は、10μm以下、すなわちアスペクト比(塗布乾燥後の膜厚/解像度)が1以上であれば良好である。
以下の基準に基づき、上記(4)で形成したポリイミドのパターンの精度を評価した。
「良好」:パターン断面が裾引きしておらず、アンダーカット、膨潤又はブリッジングが起こっていないパターンであり、且つアスペクト比が1以上であるパターンであり、加熱硬化時にパターン形状が変動しないパターン。
「不良」:上記「良好」の複数の条件の少なくとも1つを満足していないパターン。
4,4’-オキシジフタル酸二無水物(ODPA)155.1g(0.5mol)を2リットル容量のセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)とγ―ブチロラクトン400mlを入れて室温下で攪拌し、攪拌しながらピリジン81.5gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間放置した。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)32.6g(0.25mol)とトリエチレングリコールモノメチルエーテル123.3g(0.75mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーBを得た。ポリマーBの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は32,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)97.7g(0.75mol)とトリエチレングリコールモノメチルエーテル41.1g(0.25mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーCを得た。ポリマーCの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は32,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)130.2g(1.0mol)を用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーDを得た。ポリマーDの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は29,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とエタノール23.0g(0.5mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーEを得た。ポリマーEの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は27,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とネオペンチルアルコール44.0g(0.5mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーFを得た。ポリマーFの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は28,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)と1-オクタノール65.0g(0.5mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーGを得た。ポリマーGの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は33,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とベンジルアルコール54.0g(0.5mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーHを得た。ポリマーHの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は35,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)104.1g(0.8mol)とトリエチレングリコールモノメチルエーテル32.8g(0.2mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーIを得た。ポリマーIの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は32,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)26.0g(0.2mol)とトリエチレングリコールモノメチルエーテル131.4g(0.8mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーJを得た。ポリマーJの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は33,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)13.0g(0.9mol)とトリエチレングリコールモノメチルエーテル147.8g(0.1mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーKを得た。ポリマーKの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は30,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)117.1g(0.1mol)とトリエチレングリコールモノメチルエーテル16.4g(0.9mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーLを得た。ポリマーLの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は33,000であった。
製造例1の2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)とトリエチレングリコールモノメチルエーテル82.2g(0.5mol)に代えて2-ヒドロキシエチルメタクリレート(HEMA)65.1g(0.5mol)と1-ブタノール37.1g(0.5mol)をそれぞれ用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマーMを得た。ポリマーMの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は32,000であった。
ポリマーAを用いて以下の方法でネガ型感光性樹脂組成物を調製し、調製した組成物の評価を行った。ポリイミド前駆体であるポリマーA100g((A)ポリイミド前駆体)を、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)-オキシム((B)光重合開始剤)4g、ベンゾトリアゾール0.15g、1,3,5-トリス(4-t-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)-1,3,5-トリアジン-2,4,6-(1H,3H,5H)-トリオン1.5g、N-フェニルジエタノールアミン10g、メトキシメチル化尿素樹脂(MX-290)4g、テトラエチレングリコールジメタクリレート8g、N-[3-(トリエトキシシリル)プロピル]フタルアミド酸1.5g、及び2-ニトロソ-1-ナフト-ル0.05gと共に、N-メチル-2-ピロリドン(以下ではNMPという)80gと乳酸エチル20gから成る混合溶媒に溶解した。得られた溶液の粘度を、少量の該混合溶媒を更に加えることによって約35ポイズに調整し、ネガ型感光性樹脂組成物とした。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーBに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.29、ヤング率が5.5GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーCに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.40、ヤング率が5.4GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーFに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.48、ヤング率が5.6GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーGに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.50、ヤング率が6.0GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーHに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.48、ヤング率が5.6GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーIに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度1.50、ヤング率が5.0GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーJに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度1.27、ヤング率が5.6GPaと良好であり、解像度は8μmかつパターン精度も良好であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーDに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.68、ヤング率が4.8GPa、パターン精度が不良といずれも基準を満たさなかった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーEに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.57、ヤング率が4.9GPa、パターン精度が不良といずれも基準を満たさなかった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーKに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.58、ヤング率が4.9GPa、パターン精度が不良といずれも基準を満たさなかった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーLに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.25、ヤング率が5.6GPaと良好であったが、パターン精度が不良であった。
実施例1の、本発明における(A)ポリイミド前駆体をポリマーMに変えた以外は実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果、吸光度が1.63、ヤング率が4.9GPa、パターン精度が不良といずれも基準を満たさなかった。
Claims (8)
- (A)下記一般式(1):
-R6 (3)
(式中、R6は、ヘテロ原子を有していてもよい炭素数5~30の脂肪族基、又は炭素数6~30の芳香族基から選択される1価の基である。)
で表される1価の有機基であり、そしてR1及びR2の全てに対する上記一般式(2)で表される1価の有機基と上記一般式(3)で表される1価の有機基の合計の割合は、80モル%以上であり、かつR1及びR2の全てに対する上記一般式(3)で表される1価の有機基の割合は、20モル%~80モル%である。}
で表される構造を有するポリイミド前駆体:100質量部;及び
(B)光重合開始剤:0.1質量部~20質量部;
を含むネガ型感光性樹脂組成物。 - 前記R6は、エチレングリコール構造を有する炭素数5~30の脂肪族基である、請求項1に記載のネガ型感光性樹脂組成物。
- 前記一般式(1)において、R1及びR2の全てに対する前記一般式(2)で表される1価の有機基と前記一般式(3)で表される1価の有機基の合計の割合は、90モル%以上であり、かつR1及びR2の全てに対する前記一般式(3)で表される1価の有機基の割合は、25モル%~75モル%である、請求項1又は2に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体:100質量部に対して、(C)熱架橋剤:0.1質量部~30質量部をさらに含む、請求項1~3のいずれか1項に記載のネガ型感光性樹脂組成物。
- 以下の工程:
(1)請求項1~4のいずれか1項に記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程と、
(2)該感光性樹脂層を露光する工程と、
(3)該露光後の感光性樹脂層を現像して、レリーフパターンを形成する工程と、
(4)該レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と
を含む硬化レリーフパターンの製造方法。 - 請求項5に記載の方法により製造された硬化レリーフパターン。
- 半導体素子と、該半導体素子の上部に設けられた硬化膜とを備える半導体装置であって、該硬化膜は、請求項6に記載の硬化レリーフパターンである、半導体装置。
- 表示体素子と、該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は、請求項6に記載の硬化レリーフパターンである、表示体装置。
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KR101719045B1 (ko) | 2017-03-22 |
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KR20140148451A (ko) | 2014-12-31 |
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