WO2015141618A1 - 感光性樹脂組成物、硬化レリーフパターンの製造方法、並びに半導体装置 - Google Patents
感光性樹脂組成物、硬化レリーフパターンの製造方法、並びに半導体装置 Download PDFInfo
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- WO2015141618A1 WO2015141618A1 PCT/JP2015/057678 JP2015057678W WO2015141618A1 WO 2015141618 A1 WO2015141618 A1 WO 2015141618A1 JP 2015057678 W JP2015057678 W JP 2015057678W WO 2015141618 A1 WO2015141618 A1 WO 2015141618A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- 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
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
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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 is, for example, a photosensitive resin composition used for forming a relief pattern such as an insulating material of an electronic component, a passivation film, a buffer coat film and an interlayer insulating film in a semiconductor device, and a method for producing a cured relief pattern using the same.
- the present invention relates to a semiconductor device having a cured relief pattern and a resin film having excellent adhesion to a polybenzoxazole resin.
- resins such as polyimide 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 of semiconductor devices.
- resins such as polyimide the resin provided in the form of a photosensitive polyimide precursor can be easily formed into a heat-resistant relief pattern film by thermal imidization treatment by applying the precursor, exposing, developing, and curing. Can be formed.
- the photosensitive polyimide precursor has a feature that the process can be greatly shortened as compared with the conventional non-photosensitive polyimide.
- the interlayer insulation film forming process is performed separately by the former process manufacturer and the later process manufacturer, so that the resin such as polyimide is formed on the polybenzoxazole film formed in the previous process.
- the conventional photosensitive resin composition has a problem in that when an additional film is formed on the polybenzoxazole film, the adhesiveness is insufficient, and thus peeling occurs after development and curing.
- an adhesion assistant that improves the adhesion of the resin to the Si substrate and the Cu substrate has been conventionally known.
- the adhesion assistant is used, there is a problem that the resolution or heat resistance of the relief pattern deteriorates.
- the opening of the photosensitive resin pattern has a forward taper type whose side surface is gentler than the vertical to the bottom surface when patterning is completed, and preferably the taper angle is 80 ° or less.
- a conventional photosensitive resin composition it is difficult to make the side surface of the opening portion into a forward taper type when patterning is completed.
- the problem to be solved by the present invention is a cured film having excellent adhesion to a polybenzoxazole resin, a Si substrate and a Cu substrate, high resolution and heat resistance, and a side surface of the opening having a forward taper type.
- a photosensitive resin composition for producing a cured resin, a method for producing a cured relief pattern using the photosensitive resin composition, a semiconductor device provided with the cured relief pattern, and a resin film having excellent adhesion to a polybenzoxazole resin It is to provide a laminate that is laminated on a resin substrate having a glass transition temperature of 250 ° C. or lower.
- the inventors of the present invention provide a photosensitive resin composition obtained by specifying any one of a resin structure, a type of initiator, and a type of coupler, which is in close contact with a polybenzoxazole resin, a Si substrate, and a Cu substrate. It provides excellent curing, high resolution and heat resistance, and gives a cured relief pattern that has a tapered front side, and contains a specific resin and has a specific crosslink density and a specific 5% weight reduction.
- the present inventors have found that a resin film having a temperature can be laminated on a resin substrate having a glass transition temperature of 250 ° C. or lower while being excellent in adhesiveness with a polybenzoxazole resin. That is, the present invention is as follows.
- the following ingredients (A) Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin; (B) a photosensitive agent; and (C) at least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000;
- a photosensitive resin composition comprising: [2]
- the component (A) is a polyimide precursor consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole.
- the component (A) is represented by the following general formula (A1): ⁇ Wherein, X 1 is a tetravalent organic group, Y 1 is a divalent organic group, l is an integer of 2 to 150, and R 1 and R 2 are each independently A hydrogen atom or a monovalent organic group capable of radical polymerization. However, R 1 and R 2 are not simultaneously hydrogen atoms.
- component (C) is represented by the following general formula (C1): ⁇ Wherein R 3 is a single bond, a hydrogen atom or a monovalent to trivalent organic group, and R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and m is an integer of 1 or more.
- the component (A) is represented by the following general formula (A2): ⁇ Wherein X 2 is a tetravalent organic group, Y 2 is a divalent organic group, n is an integer of 2 to 150, and R 6 and R 7 are each independently A hydrogen atom, the following general formula (A3): (Wherein R 8 , R 9 and R 10 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10) Or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 6 and R 7 are not both hydrogen atoms at the same time.
- the component (C) is represented by the following general formula (C2): ⁇ In the formula, R 11 is a single bond, a hydrogen atom or a monovalent to trivalent organic group; R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and q is an integer of 2 to 4.
- the component (B) is the following components (B1) and (B2): (B1) an oxime ester compound in which the 0.001 wt% solution has an i-ray absorbance of 0.15 to 0.5, and the 0.001 wt% solution has a g-ray absorbance and an h-ray absorbance of 0.2 or less; and (B2) An oxime ester compound in which the i-line absorbance of the 0.001 wt% solution is 0.1 or less and the g-ray absorbance or h-ray absorbance of the 0.001 wt% solution is 0.05 or more;
- the photosensitive resin composition according to any one of [1] to [7], comprising at least one selected from the group consisting of: [9]
- the component (B1) is represented by the following general formulas (B11) and (B12): ⁇ Wherein R 14 is a C 1 -C 10 fluorine-containing alkyl group, and R 15 , R 16 , and R 17 are each independently a C 1 -C 20 alkyl group, C 3 -C 20 A cycloalkyl group, a C 6 -C 20 aryl group, or a C 1 -C 20 alkoxy group, and r is an integer of 0-5. ⁇ ⁇ Wherein R 18 is a C 1 -C 30 divalent organic group, and R 19 -R 26 are each independently a C 1 -C 20 alkyl group or a C 3 -C 20 cycloalkyl group.
- component (A) For 100 parts by mass of component (A), 0.1 to 20 parts by mass of the component (B); Component (C) 10 to 35 parts by mass; and component (D) 0.1 to 20 parts by mass;
- the photosensitive resin composition as described in [11] or [12].
- the photosensitive resin composition according to [13] comprising: [19] For 100 parts by mass of component (A), 0.1 to 20 parts by mass of the component (B); Component (C) 10 to 35 parts by mass; and component (E) 0.1 to 20 parts by mass;
- the component (B1) is represented by the following general formulas (B11) and (B12): ⁇ Wherein R 14 is a C 1 -C 10 fluorine-containing alkyl group, and R 15 , R 16 , and R 17 are each independently a C 1 -C 20 alkyl group, C 3 -C 20 A cycloalkyl group, a C 6 -C 20 aryl group, or a C 1 -C 20 alkoxy group, and r is an integer of 0-5. ⁇ ⁇ Wherein R 18 is a C 1 -C 30 divalent organic group, and R 19 -R 26 are each independently a C 1 -C 20 alkyl group or a C 3 -C 20 cycloalkyl group.
- the total content of the component (B1) and the component (B2) with respect to 100 parts by mass of the (AX) component is 0.1 to 10 parts by mass, according to any one of [20] to [23] Photosensitive resin composition.
- Resin composition [26] The following ingredients: (AY) polyimide precursor; and (D) the following general formula (D1): ⁇ Wherein R 27 and R 28 are C 1 to C 4 alkyl groups, R 29 is a C 1 to C 6 divalent organic group, and R 30 is composed of nitrogen, oxygen, and sulfur.
- An organic group of C 1 to C 20 bonded to a carbonyl group by an atom selected from the group, t is an integer selected from 1, 2, and 3, and u is an integer selected from 0, 1, and 2. And t and u satisfy the relationship t + u 3.
- the component (AY) is represented by the following general formula (A2): ⁇ Wherein X 2 is a tetravalent organic group, Y 2 is a divalent organic group, n is an integer of 2 to 150, and R 6 and R 7 are each independently A hydrogen atom, the following general formula (A3): (Wherein R 8 , R 9 and R 10 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10) Or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 6 and R 7 are not both hydrogen atoms at the same time.
- the component (A) is a polyimide precursor consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole.
- the resin film according to [35] or [36] which is at least one selected resin.
- [38] [35] A laminate in which the resin film according to any one of [37] is laminated on a resin substrate having a glass transition temperature of 200 ° C. or lower.
- [39] [35] A laminate in which the resin film according to any one of [37] is laminated on a resin substrate having a glass transition temperature of 250 ° C. or lower.
- a photosensitive film for producing a cured film having excellent adhesion to a polybenzoxazole resin, a Si substrate, and a Cu substrate, high resolution and heat resistance, and a side surface of an opening having a forward taper type.
- Resin composition, method for producing a cured relief pattern using the photosensitive resin composition, a semiconductor device provided with the cured relief pattern, a resin film having excellent adhesion to a polybenzoxazole resin, and the resin film having a glass transition Provided is a laminate laminated on a resin substrate having a temperature of 250 ° C. or lower.
- ⁇ Resin composition> Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin; (B) a photosensitive agent; and (C) at least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000; The resin composition containing is described.
- component (A) component used in this composition is polyhydroxyamide, polyaminoamide which can be a polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyoxazole precursor which is a polyimide precursor, It is at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin.
- a group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole At least one resin selected from the above is preferred.
- the weight average molecular weight of these resins is preferably 1,000 or more and more preferably 5,000 or more in terms of polystyrene by gel permeation chromatography from the viewpoint of heat resistance after heat treatment and mechanical properties.
- the upper limit of the weight average molecular weight is preferably 100,000 or less.
- Component resin is preferably a photosensitive resin in order to form a relief pattern with the resin composition.
- the photosensitive resin is a resin that forms a photosensitive resin composition and causes development by dissolution or non-dissolution in a subsequent development step when used together with the later-described (B) photosensitive agent.
- Photosensitive resins include polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamidoimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzthiazole, which are polyimide precursors, after heat treatment. From the viewpoint that these resins are excellent in heat resistance and mechanical properties, polyimide precursors, polyamides, and / or polyimides are preferably used. These photosensitive resins should be selected according to the desired application from the viewpoint of whether to prepare a negative type or a positive type photosensitive resin composition together with the photosensitive agent (B) described later. Can do.
- polyimide precursor In the resin composition of the present invention, from the viewpoint of heat resistance and photosensitivity, one of (A) resin, (AX) photosensitive polyimide precursor, and (AY) polyimide precursor is preferably represented by the following general formula (A1). ): ⁇ Wherein, X 1 is a tetravalent organic group, Y 1 is a divalent organic group, l is an integer of 2 to 150, and R 1 and R 2 are each independently A hydrogen atom or a monovalent organic group capable of radical polymerization. However, R 1 and R 2 are not simultaneously hydrogen atoms.
- the polyamide has a structure represented by the following general formula (A2): ⁇ Wherein X 2 is a tetravalent organic group, Y 2 is a divalent organic group, n is an integer of 2 to 150, and R 6 and R 7 are each independently A hydrogen atom, the following general formula (A3): (Wherein R 8 , R 9 and R 10 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10) Or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 6 and R 7 are not both hydrogen atoms at the same time.
- the tetravalent organic group represented by X 2 is preferably an organic group having 6 to 40 carbon atoms, more preferably a —COOR 6 group, from the viewpoint of heat resistance and photosensitive properties.
- the —COOR 7 group and the —CONH— group are each an aromatic group or an alicyclic aliphatic group in the ortho position.
- the tetravalent organic group represented by X 2 is more preferably the following formula: Although the structure represented by these is mentioned, it is not limited to these. Structure of X 2 may be two or more kinds in combination.
- the divalent organic group represented by Y 2 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of heat resistance and photosensitive properties.
- A 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 ).
- Y 2 may be two or more kinds in combination.
- R 8 in the general formula (A3) is preferably a hydrogen atom or a methyl group
- R 9 and R 10 are preferably a hydrogen atom from the viewpoint of photosensitive properties.
- p is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, from the viewpoint of photosensitive characteristics.
- Examples include an ester bond type and an ion bond type.
- the former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, into the side chain of the polyimide precursor by an ester bond, and the latter has a carboxyl group and an amino group of the polyimide precursor ( In this method, a photopolymerizable group is imparted by bonding an amino group of a (meth) acrylic compound via an ionic bond.
- the polyimide precursor of the ester-linked firstly, a tetracarboxylic acid dianhydride containing tetravalent organic group X 2 described above, the photopolymerizable alcohols and optionally saturated aliphatic alcohols having an unsaturated double bond And a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and this and a diamine containing the divalent organic group Y 2 described above. Obtained by polycondensation.
- tetracarboxylic dianhydrides containing a tetravalent organic group X 2 that are preferably used for preparing an ester-bonded polyimide precursor include pyromellitic anhydride, diphenyl ether-3, 3 ′, 4 , 4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl Sulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) Acid) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropan
- Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing an ester-linked polyimide precursor include 2-acryloyloxyethyl alcohol and 1-acryloyloxy-3-propyl.
- methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. are mixed as saturated aliphatic alcohols having 1 to 4 carbon atoms with alcohols having photopolymerizable unsaturated double bonds. Can also be used.
- the preferred tetracarboxylic dianhydride described above and the preferred alcohol described above are mixed in a suitable reaction solvent at a 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 a solvent that completely dissolves the acid / ester body and the polyimide precursor that is an amide polycondensation product of this with a diamine component.
- a solvent that completely dissolves the acid / ester body and the polyimide precursor that is an amide polycondensation product of this with a diamine component for example, N-methyl-2-pyrrolidone, N, N— Examples include dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and ⁇ -butyrolactone.
- reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc., for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate.
- an appropriate dehydration condensation 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 convert the acid / ester into a polyanhydride.
- the preferred divalent diamines containing organic group Y 1 was allowed to separate dissolved or dispersed in a solvent solution or dispersion was added dropwise to polyanhydrides, by engaged amide polycondensation, the photosensitive resin of interest Obtainable.
- Preferred diamines containing a divalent organic group Y 1 include, for example, p-phenylene diamine, m-phenylene diamine, 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'-diaminobenzophenone, 3,4'
- a polyimide precursor is used as the resin of component (A).
- (AX) photosensitive polyimide precursor or (AY) polyimide precursor 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3- It is also possible to copolymerize diaminosiloxanes such as (aminopropyl) tetraphenyldisiloxane.
- 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 polymer component is added to the polymer component, and the polymer component is precipitated. Further, the polymer is purified by repeating redissolution, reprecipitation and the like, and vacuum drying is performed to obtain the target polyimide precursor. Isolate.
- 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 weight average molecular weight of the ester bond type polyimide precursor is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000 in terms of polystyrene by gel permeation chromatography.
- the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. Tetrahydrofuran and / or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography.
- the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is preferable to select an organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
- Photosensitizer As the photosensitizer, a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected.
- compounds that can be suitably used as a photosensitizer include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; 2,2 ′ -Acetophenone derivatives such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzil Benzyl derivatives such as benzyl dimethyl ketal and benzyl- ⁇ -me
- the oximes used as photosensitizers are the following components (B1) and (B2): (B1) an oxime ester compound having a g-line absorbance and h-line absorbance of 0.2 or less and an i-line absorbance of 0.15 to 0.5 with respect to a 0.001 wt% solution; and (B2) 0.001 wt An oxime ester compound having a g-line absorbance or h-line absorbance of 0.05 or more and an i-line absorbance of 0.1 or less with respect to a% solution; It is preferably at least one selected from the group consisting of The absorbance of the oxime ester compound can be measured by dissolving the compound in N-methylpyrrolidone at a concentration of 0.001 wt% and using a 1 cm quartz cell and a normal spectrophotometer.
- Preferred compounds as the component (B1) include, for example, Irgacure OXE03 (trade name, manufactured by BASF), Adekaoptomer NCI831 (trade name, manufactured by ADEKA), TR-PBG326 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., trade name) ), HTPI 426 (manufactured by Heraeus, trade name), HTPI 428 (manufactured by Heraeus, trade name), or a mixture thereof.
- the absorbance is not sufficient, and a large amount of initiator needs to be added for curing. In that case, since it becomes difficult to be influenced by oxygen inhibition on the surface of the coating film, the degree of surface hardening increases, and the opening after exposure and development does not become a forward tapered shape. Even when the i-ray absorbance exceeds 0.5, or when at least one of the g-ray absorbance and the h-ray absorbance exceeds 0.2, the absorbance is too high and surface hardening tends to proceed. The part does not have a forward tapered shape.
- More preferred component (B1) is an oxime ester compound having an i-line absorbance of 0.15 to 0.35 in a 0.001 wt% solution, and more preferred components (B1) are represented by the following general formulas (B11) and (B12) :
- R 14 is a C 1 -C 10 fluorine-containing alkyl group
- R 15 , R 16 , and R 17 are each independently a C 1 -C 20 alkyl group, C 3 -C 20 A cycloalkyl group, a C 6 -C 20 aryl group, or a C 1 -C 20 alkoxy group
- r is an integer of 0-5.
- R 18 is a C 1 -C 30 divalent organic group
- R 19 -R 26 are each independently a C 1 -C 20 alkyl group or a C 3 -C 20 cycloalkyl group.
- ⁇ Is at least one selected from the group consisting of oxime ester compounds represented by:
- the oxime ester compound (B2) also functions as a photopolymerization initiator.
- the absorbance of the oxime ester compound (B2) can be measured in the same manner as in the case of the oxime ester compound (B1).
- TR-PBG340 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., trade name
- a component (B2) when a compound having a g-ray absorbance and h-ray absorbance of less than 0.05 is used as a 0.001 wt% solution, the absorbance is not sufficient, so that a large amount of initiator needs to be added for curing. . In that case, since it becomes difficult to be influenced by oxygen inhibition on the surface of the coating film, the degree of surface hardening increases, and the opening after exposure and development does not become a forward tapered shape. Even in the case where the i-line absorbance exceeds 0.1, the absorbance is too high and surface hardening is likely to proceed, and the opening after exposure and development does not have a forward tapered shape.
- the total amount of the component (B1) and the component (B2) used for 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor is in the range of 0.1 to 20 parts by mass. It is preferably in the range of 0.5 to 5 parts by mass.
- the total amount of the (B1) component and the (B2) component is 0.1 parts by mass or more with respect to 100 parts by mass of the (A) resin, the (AX) photosensitive polyimide precursor, or the (AY) polyimide precursor. When it is excellent in photosensitivity and is 20 parts by mass or less, the forward taper property is excellent.
- component (C) At least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000.
- the component (C) comprises a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000. It is at least one selected from the group.
- “(Meth) acrylate” means acrylate or methacrylate.
- Component (C) may be a polymerizable monomer.
- the glass transition temperature of the homopolymer obtained by polymerizing only the component (C) is preferably 200 ° C. or higher.
- isocyanuric acid tri (meth) acrylate isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate.
- the low molecular weight imide compound having a molecular weight of less than 1000 is represented by the following general formula (C1): ⁇ Wherein R 3 is a single bond, a hydrogen atom or a monovalent to trivalent organic group, and R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and m is an integer of 1 or more. ⁇ It is preferable that it is maleimide represented by these. In the formula (C1), m may be an integer of 2 or more or an integer of 3 or more.
- the low molecular weight imide compound having a molecular weight of less than 1000 is represented by the following general formula (C2): ⁇ In the formula, R 11 is a single bond, a hydrogen atom or a monovalent to trivalent organic group; R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and q is an integer of 2 to 4. ⁇ It is more preferable that it is maleimide represented by these.
- a cured film having excellent adhesion after development on a polybenzoxazole resin can be obtained.
- the mechanism by which the relief pattern on the polybenzoxazole resin is excellent in adhesion after development is not clear, in the heating step (about 100 ° C.) for drying the solvent when forming the coating film of the relief pattern, as the component (C)
- the low molecular weight imide compound and the polybenzoxazole resin are stacked and interact at the resin interface, so that the developer soaks into the interface between the coating film and the polybenzoxazole resin during development, or solvates. It is inferred that dissolution is suppressed and as a result, peeling of the relief pattern is suppressed.
- the low molecular weight imide compound examples include 1-phenylpyrrolidine-2,5-dione, succinimide, N-pentylsuccinimide, glutadine, 2,6 (1H, 3H) -pyridinedione, N-ethylmaleimide, Fluorimide, N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (2-chlorophenyl) maleimide, N- (4-methylphenyl) maleimide, N- (4-ethoxyphenyl) maleimide, N -Isopropylmaleimide, N-methylmaleimide, N- (2-nitrophenyl) maleimide, N- (2-methylphenyl) maleimide, 1- (2,4-dimethylphenyl) -3-pyrroline-2, 5-dione, 1- (1,1′-biphenyl-4-yl) -1H-pi 2,5-dione, N-cyclo
- the low molecular weight imide compound preferably has a cyclic structure, and more preferably has an unsaturated bond in the cyclic structure.
- low molecular weight imide compounds having an unsaturated bond in the cyclic structure as represented by the general formula (C1) or (C2), it has a maleimide structure that is planar and easily sterically stacks with benzoxazole.
- the compound is more preferable from the viewpoint of adhesion after development on the polybenzoxazole resin.
- a divalent maleimide is more preferable than a monovalent maleimide from the viewpoint that it is difficult to dissolve in a developer due to a crosslinking reaction.
- divalent maleimides have less steric hindrance than trivalent maleimides and are easier to stack with polybenzoxazoles. Therefore, bismaleimide is more preferable from the viewpoint of adhesion with the polybenzoxazole resin.
- bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4,4′-bismaleimide diphenylmethane, or polyphenylenemethanemaleimide suppresses shrinkage during curing of the photosensitive resin composition, and is a polyimide. Or from a viewpoint of improving adhesiveness with a polybenzoxazole resin, it is still more preferable.
- the amount of component (C) is 1 to 40 parts by weight when the photosensitive resin composition contains 100 parts by weight of resin (A) and 0.1 to 20 parts by weight of component (B).
- the amount is preferably 10 to 35 parts by mass.
- the blending amount of the component (C) is less than 1 part by mass, the adhesion is insufficient, and when it exceeds 40 parts by mass, the cured relief pattern obtained from the composition becomes brittle, and a passivation film and a buffer coat film. It is not suitable for applications such as interlayer insulation films.
- (D) Silicon-containing compound (D) The component is represented by the following general formula (D1): ⁇ Wherein R 27 and R 28 are C 1 -C 4 alkyl groups, R 29 is a C 1 -C 6 divalent organic group, and R 30 is selected from nitrogen, oxygen, and sulfur.
- An organic group of C 1 to C 20 bonded to a carbonyl group by an atom, t is an integer selected from 1, 2, and 3, u is an integer selected from 0, 1, and 2, and t And u satisfy the relationship t + u 3.
- R 30 specifically, Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-hexylamino group, n-octylamino group, isopropylamino group, isobutylamino group, t-butylamino group, isoamylamino group, Mono- and dialamino groups such as cyclopentyl group, cyclohexylamino group, dimethylamino group, diethylamino group, dibutylamino group, dicyclohexylamino group; Aromatic ring-containing amino groups such as phenylamino group, benzylamino group, diphenylamino group; Heterocyclic-containing amino groups such as picolyl group, aminotriazyl group, furfurylamino group, morpholino group; Alkoxy groups such as methoxy group, ethoxy group,
- the silicon-containing compound represented by the formula (D1) is obtained by a method in which an isocyanate compound is reacted with a silicon compound having an amino group, a method in which an amine, alcohol, or thiol is reacted with a silicon compound having an isocyanate group.
- the compounding amount of the silicon-containing compound represented by the formula (D1) is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. From the viewpoint of improving heat resistance and adhesion, it is more preferably 0.5 to 10 parts by mass.
- By blending the silicon-containing compound represented by the formula (D1) with 0.1 part by mass or more with respect to 100 parts by mass of the (A) resin, the (AX) photosensitive polyimide precursor, or the (AY) polyimide precursor it is excellent. Adhesion is ensured, and excellent heat resistance is maintained by blending at 20 parts by mass or less.
- Examples of the silicon-containing compound represented by the formula (D2) include 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropylethoxydimethoxysilane, 3-ureidopropyldiethoxymethoxysilane, 3 -Ureidopropylmethyldiethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3-ureidopropylethyldiethoxysilane, 3-ureidopropylethyldimethoxysilane, 3-ureidopropylethyldimethoxysilane, 3-ureidopropyldimethylethoxysilane, 3-ureidopropyldimethylmethoxysilane, etc. And mixtures thereof.
- the compounding amount of the silicon-containing compound represented by the formula (D2) is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. From the viewpoint of improving heat resistance and adhesion, it is more preferably 0.5 to 10 parts by mass.
- a silicon-containing compound represented by the formula (D2) is further added to the resin composition. By doing so, the resolution can be improved while improving the adhesion and heat resistance of the relief pattern to be obtained.
- examples of the C 1 -C 20 organic group include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group, a benzyl group, and the like.
- examples include methoxysilylpropyl group, triethoxysilylpropyl group, methyldimethoxysilylpropyl group, methyldiethoxysilylpropyl group, triethoxysilylethyl group and the like.
- R 35 for example, Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-hexylamino group, n-octylamino group, isopropylamino group, isobutylamino group, t-butylamino group, isoamylamino group, Mono- and dialamino groups such as cyclopentyl group, cyclohexylamino group, dimethylamino group, diethylamino group, dibutylamino group, dicyclohexylamino group; Aromatic ring-containing amino groups such as phenylamino group, benzylamino group, diphenylamino group; Heterocyclic-containing amino groups such as picolyl group, aminotriazyl group, furfurylamino group, morpholino group; Alkoxy groups such as methoxy group, ethoxy
- the compounding amount of the sulfur-containing compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. From the viewpoint of improving heat resistance and adhesion, the content is more preferably 0.5 to 10 parts by mass.
- (E) By mixing the sulfur-containing compound with 0.1 part by mass or more with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor, excellent adhesion can be obtained. By being blended and blended at 20 parts by mass or less, excellent heat resistance is maintained.
- the fat composition of the present invention may further contain components other than the components (A) to (E).
- a solvent can be used.
- the varnish-like negative photosensitive resin composition can be obtained by dissolving the components (A) to (E) in a solvent.
- a polar organic solvent is preferably used from the viewpoint of solubility in the (A) resin, the (AX) photosensitive polyimide precursor, or the (AY) polyimide precursor.
- N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone, ⁇ -Acetyl- ⁇ -butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like are used. These can be used alone or in combination of two or more.
- the solvent is, for example, 30 to 1500 masses per 100 mass parts of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor, depending on the desired coating thickness and viscosity of the resin composition. In the range of 100 parts by weight, preferably in the range of 100 to 1000 parts by weight.
- a solvent containing an alcohol is preferable.
- alcohols include alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond, and specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol.
- Alkyl alcohols such as n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol; lactic acid esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether Propylene glycol monoalkyl ethers such as propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether; Glycol methyl ether, ethylene glycol ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether; 2-hydroxyisobutyric acid esters, ethylene glycol, and dialcohols such as propylene glycol.
- lactic acid esters such as ethyl lactate
- propylene glycol-1-methyl ether propylene glycol-2-methyl ether
- alkyl alcohols lactic acid esters, propylene glycol monoalkyl ethers, and 2-hydroxyisobutyric acid esters are preferable.
- alkyl alcohol ethyl alcohol is preferable. More preferred are ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1- (n-propyl) ether.
- the content of the alcohol having no olefinic double bond in the entire solvent is preferably 5 to 50% by mass, More preferably, it is 10 to 30% by mass.
- the storage stability of the resin composition is good, and when it is 50% by mass or less, (A) resin, (AX) The solubility of the photosensitive polyimide precursor or (AY) polyimide precursor is good.
- the resin composition of the present invention may further contain a resin component other than the above-mentioned (A) resin, (AX) photosensitive polyimide precursor, and (AY) polyimide precursor.
- a resin component other than the above-mentioned (A) resin, (AX) photosensitive polyimide precursor, and (AY) polyimide precursor examples include an epoxy resin, a siloxane resin, and an 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 (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. .
- the resin composition of the present invention may contain a photosensitive agent other than the components (B1) and (B2) described above, and a photosensitive agent other than the components (B1) and (B2).
- a photopolymerization initiator usually used for UV curing can be arbitrarily selected.
- the photopolymerization initiator usually used is not limited, but for example, Benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl- ⁇ -methoxyethyl acetal; Benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2- (o-me
- the blending amount of the photosensitive agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor, From the viewpoint of the above, it is preferably 2 to 15 parts by mass.
- hardenability can be obtained by mix
- a sensitizer can be arbitrarily mix
- the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal).
- the amount of the sensitizer is (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor.
- the amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the body.
- a monomer having a photopolymerizable unsaturated bond different from the component (C) can be blended in the resin composition.
- a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not limited, but ethylene glycol represented by diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc.
- the amount of the monomer is (A) resin, (AX It is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor or (AY) polyimide precursor.
- an adhesion assistant can be blended in the resin composition.
- Adhesion aids 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] phthalamic acid, benzophenone-3,3′-bis (N- [3-[3-[3- (triethoxysilyl) propyl]
- the compounding amount of the adhesion assistant is based on 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor. , Preferably in the range of 0.5 to 25 parts by mass.
- thermal polymerization inhibitors 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-N-phenylhydroxylamine ammonium salt, N-
- the blending amount of the thermal polymerization inhibitor in the photosensitive resin composition is 0.005 to 12 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. It is preferable that it is the range of these.
- a crosslinking agent may be added to the resin composition.
- the crosslinking agent may crosslink the (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor when the relief pattern formed using the resin composition of the present invention is heat-cured. Or the crosslinking agent itself can form a crosslinked network.
- the crosslinking agent 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 more preferably used.
- Particularly preferred crosslinking agents are alkoxymethylated urea compounds and alkoxymethylated melamine compounds. Examples thereof include MX-290 (manufactured by Nippon Carbide), UFR-65 (manufactured by Nippon Cytec Co., Ltd.), and MW-390 (Manufactured by Nippon Carbide Corporation).
- the blending amount of the crosslinking agent in the resin composition is (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide.
- the amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the precursor. When the amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when it is 20 parts by mass or less, the storage stability is excellent.
- an azole compound can be added to the resin composition in order to suppress discoloration of the substrate surface.
- the azole compound 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5 -Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (
- the compounding amount of the azole compound in the resin composition is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor.
- the amount is preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity.
- the resin composition of the present invention is made of copper or When formed on a copper alloy, discoloration of the copper or copper alloy surface is suppressed, and when it is 10 parts by mass or less, the photosensitivity is excellent.
- a hindered phenol compound can be added to the resin composition.
- hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4.
- 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are preferred.
- the blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. From the viewpoint of sensitivity, it is more preferably 0.5 to 10 parts by mass.
- the blending amount of the hindered phenol compound with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor is 0.1 parts by mass or more, for example, on copper or copper alloy
- the resin composition of the present invention is formed, discoloration / corrosion of copper or a copper alloy is prevented, and when it is 20 parts by mass or less, the photosensitivity is excellent.
- the photosensitive resin composition of this invention is 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 photosensitive resin composition can be dried.
- a drying method methods such as air drying, heat drying with an oven or a hot plate, and vacuum drying are used.
- drying of the coating film causes modification of (A) resin in the photosensitive resin composition, or imidization of (AX) photosensitive polyimide precursor, (AY) polyimide precursor (polyamic acid ester). It is desirable to perform under such conditions. 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 above is exposed through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.
- an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.
- direct exposure is performed with an ultraviolet light source or the like.
- 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 range of baking conditions is preferably a temperature of 40 to 120 ° C. and a time of 10 seconds to 240 seconds, but is not limited to this range as long as the various characteristics of the photosensitive resin composition of the present invention are not impaired.
- 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 the conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, etc. A 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 is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent.
- the good solvent N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, etc. are preferable.
- As the solvent toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable.
- the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition.
- two or more of each solvent for example, several types may be used in combination.
- Step of forming a relief pattern by subjecting the relief pattern to heat treatment the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) resin, (AX) The photosensitive polyimide precursor or (AY) polyimide precursor is converted into a cured relief pattern by heat curing.
- a method of heat curing various methods such as a method using a hot plate, a method using an oven, and 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.
- As the atmospheric gas at the time of heat curing air may be used, or an inert gas such as nitrogen or argon may be used.
- a semiconductor device provided with the hardening relief pattern obtained by the manufacturing method of the hardening relief pattern demonstrated above can also be provided. More specifically, it is possible to provide a semiconductor device having a base material that is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method.
- the present invention can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a base material and including the above-described method for manufacturing a cured relief pattern as part of the process.
- the semiconductor device of the present invention has a cured relief pattern having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure by the method for producing a cured relief pattern described above. It can be formed as a protective film of a semiconductor device and can be manufactured by combining a method for manufacturing a cured relief pattern and a known method for manufacturing a semiconductor device.
- the component (A) contained in the resin film may be the same as the resin described as the component (A) contained in the photosensitive resin composition or the resin composition.
- the component (A) includes polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and At least one resin selected from the group consisting of polybenzothiazole is preferred.
- the component (A) is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more, based on the total mass of all the components constituting the resin film. If necessary, a resin other than the component A may be contained in the resin film.
- the weight average molecular weight of the resin contained in the resin film is preferably 1,000 or more in terms of polystyrene by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties after heat treatment, and is 5,000 or more. It is more preferable that The upper limit of the weight average molecular weight is preferably 100,000 or less.
- the crosslink density is the number of moles of chemically cross-linked functional groups contained in 1 cm 3 of the resin film.
- Crosslinking is a method in which a monomer having a crosslinkable functional group is copolymerized in component (A), and these crosslinkable functional groups are reacted with each other; (A) component is chemically crosslinked with component (A).
- the storage elastic modulus above the glass transition temperature increases according to the crosslinking density.
- the crosslink density can be obtained by measuring the storage elastic modulus above the glass transition temperature of the resin film.
- the storage elastic modulus above the glass transition temperature can be measured using, for example, a dynamic viscoelasticity measuring apparatus.
- this relational expression does not necessarily hold strictly between the crosslinking density and the storage elastic modulus.
- the number of crosslinkable functional groups contained in the resin film and the reaction rate thereof were confirmed while using a dynamic viscoelasticity measuring device, for example, to confirm that the storage elastic modulus above the glass transition temperature was increased.
- the crosslinking density can be calculated therefrom.
- the crosslink density of the resin film used in the present invention is 1.0 ⁇ 10 ⁇ 4 mol / cm 3 or more, 3.0 ⁇ 10 ⁇ 3 mol / cm 3 or less, preferably 3.0 ⁇ 10 ⁇ 4 mol / cm 3. 3 or more and 2.0 ⁇ 10 ⁇ 3 mol / cm 3 or less.
- the crosslinking density is less than 1.0 ⁇ 10 ⁇ 4 mol / cm 3 , the adhesion between the resin film and the polybenzoxazole resin is not sufficient.
- the resin film becomes brittle and is not suitable for uses such as a passivation film, a buffer coat film, and an interlayer insulating film assumed in the present invention.
- the 5% weight loss temperature is obtained by raising the temperature at a rate of 10 ° C./min using a thermogravimetric measuring device under nitrogen.
- the 5% weight loss temperature is less than 250 ° C., the heat resistance is too low, and it is not suitable for applications such as a passivation film, a buffer coat film, and an interlayer insulating film assumed in the present invention.
- the 5% weight loss temperature exceeds 400 ° C., the adhesion with the polybenzoxazole resin is not sufficient.
- the resin film can be obtained by, for example, applying a solution in which a component that is a precursor of the resin film is dissolved on the base material and heating at a temperature of 250 ° C. or lower. There may be an exposure step before heating. At this time, by setting the heating temperature to 250 ° C. or lower, the resin film is formed on a base material including a resin substrate having a glass transition temperature of 250 ° C. or lower, or the heating temperature is set to 200 ° C. or lower. Thereby, the said resin film can be formed on the base material containing the resin substrate whose glass transition temperature is 200 degrees C or less, and a laminated body can be obtained.
- the resin composition of the present invention is useful for applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper-clad plates, solder resist films, and liquid crystal alignment films, in addition to application to semiconductor devices as described above. is there.
- Weight average molecular weight The weight average molecular weight (Mw) of resin was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement was Shodex (trade name) 805M / 806M series manufactured by Showa Denko KK, Shodex STANDARD SM-105 manufactured by Showa Denko KK was selected as the standard monodisperse polystyrene, and the developing solvent was N-methyl. -2-Pyrrolidone, and Shodex (trade name) RI-930 manufactured by Showa Denko was used as a detector.
- a resin film precursor or a photosensitive resin composition is spin-coated on a 6-inch silicon wafer coated and cured with a polybenzoxazole resin, and dried to a thickness of about 10 ⁇ m.
- This coating film was exposed by irradiating 1500 mJ / cm 2 energy with an i-line stepper NSR2005i8A (manufactured by Nikon Corporation) using a reticle with a test pattern.
- the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and uncoated.
- the exposed portion was developed and removed to obtain a relief pattern of the resin film precursor or the photosensitive resin composition.
- the wafer with the relief pattern formed thereon is heat-treated at 200 to 300 ° C. for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan) to obtain polybenzo
- VF-2000 type manufactured by Koyo Lindberg Co., Ltd., Japan
- the film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor).
- the pattern shape and the width of the pattern portion were observed under an optical microscope and evaluated according to the following criteria: Good: The area of the opening of the obtained 20 ⁇ m pattern is 1 ⁇ 2 or more of the corresponding pattern mask opening area, and there is no peeling. Defect: The area of the opening is less than 1/2 of the corresponding pattern mask opening area, or there is peeling.
- the photosensitive resin composition was spin-coated on a 6-inch silicon wafer and dried to form a 8.5 ⁇ m thick coating film.
- This coating film was irradiated with energy of 500 mJ / cm 2 by Prisma GHI (manufactured by Ultratech, USA) through a mask with a test pattern.
- the irradiated coating film is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and unexposed areas. was removed by development to obtain a relief pattern.
- D-SPIN636 type manufactured by Dainippon Screen Mfg. Co., Ltd.
- the taper angle was evaluated by a method including the following steps 1 to 5: 1. Drawing the upper and lower sides of the opening (FIG. 1A); 2. Determining the height of the opening (FIG. 1B); 3. Draw a straight line (center line) parallel to the upper and lower sides through the central part of the height (FIG. 1C); 4). 4. Find the intersection (center point) between the center line and the opening pattern (FIG. 1D); A tangent line is drawn in accordance with the inclination of the pattern at the center point, and an angle formed by the tangent line and the lower side is regarded as a taper angle (FIG. 1E).
- the above wafer was heated on a silicon wafer at 200 to 390 ° C. for 2 hours in a nitrogen atmosphere using a temperature rising programmed curing furnace (VF-2000, manufactured by Koyo Lindberg, Japan).
- VF-2000 temperature rising programmed curing furnace
- a cured relief pattern having a thickness of about 4 to 5 ⁇ m was obtained.
- the relief pattern was subjected to film thickness measurement using a Tencor P-15 type step gauge (manufactured by KLA Tencor), and the taper angle of the line and space (1: 1) portion was determined in the same manner as described above.
- the resin composition was spin-coated on a 6-inch silicon wafer and dried to form an 8.5 ⁇ m thick coating film.
- This coating film was irradiated with energy of 500 mJ / cm 2 by Prisma GHI (manufactured by Ultratech, USA) using a mask with a test pattern.
- the irradiated coating film is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and unexposed areas. was removed by development to obtain a relief pattern.
- D-SPIN636 type manufactured by Dainippon Screen Mfg. Co., Ltd.
- the wafer on which this relief pattern was formed was heat-treated at 200 to 390 ° C. for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Japan).
- VF-2000 type manufactured by Koyo Lindberg Co., Japan
- a cured relief pattern of polyimide having a thickness of about 4 to 5 ⁇ m was obtained on a silicon wafer and a copper substrate, respectively.
- the film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor). About the pattern obtained on Si, the pattern shape and the width
- Tg glass transition temperature
- a resin composition was spin-coated on a sputtered body obtained by sputtering 400 nm-thick Cu in this order so that the film thickness after curing was about 4 to 5 ⁇ m.
- energy of 500 mJ / cm 2 was irradiated by a parallel light mask aligner PLA-501FA (manufactured by Canon Inc., Japan). This irradiation was not performed when the resin composition was not photosensitive.
- the cured film was obtained by heating at 200 to 390 ° C. for 2 hours in a nitrogen atmosphere and thermosetting.
- the obtained cured film was peeled from the wafer to obtain a cured tape.
- the obtained cured tape was measured with a thermomechanical test apparatus (TMA-50 manufactured by Shimadzu Corporation) at a load of 200 g / mm 2 , a temperature rising rate of 10 ° C./min, and a temperature range of 20 to 500 ° C.
- Tg glass transition temperature
- the cured film was obtained by heating and curing at 200 ° C. to 390 ° C. for 2 hours in a nitrogen atmosphere.
- the adhesion of the obtained cured film to Si or Cu was evaluated by a cross-cut test (JIS K5400). That is, scratches with a cutter knife so that 100 squares of 1 mm square can be formed on the coating film, a cellophane (registered trademark) tape is applied from above, and the cellophane is adhered until it is free from bubbles, and then peeled off. Evaluation was performed by counting the number of squares that remained on the substrate without adhering to the (registered trademark) tape.
- thermogravimetric measuring device TGA-50 manufactured by Shimadzu Corporation. The temperature at which the weight was reduced by 5% from the initial value was determined.
- 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 (polyimide precursor A (hereinafter referred to as “polymer A”). Also called))).
- polyimide precursor A hereinafter referred to as “polymer A”. Also called
- the photosensitive resin composition was prepared with the following method using the polyimide precursor A (polymer A) and the polyimide precursor B (polymer B), and the prepared composition was evaluated.
- component (A) polymer A50g and polymer B50g, as component (B), Adekaoptomer NCI831 (manufactured by ADEKA, trade name, 0.001 wt% solution g-line, h-line, and i-line absorbance are respectively (0), 0.13, and 0.22), 2 g of (C), 10 g of 4,4′-bismaleimide diphenylmethane, 4 g of hexamethoxymethylmelamine, and 8 g of tetraethylene glycol dimethacrylate, (D) As components, 3 g of silicon-containing compound D-1 and 0.05 g of 2-nitroso-1-naphthol were dissolved in a mixed solvent consisting of 80 g of N-methylpyrrolidone (hereinafter
- the viscosity of the resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.
- Polybenzoxazole (PBO) resin when the composition is applied to a silicon wafer according to the method for evaluating adhesion to (2) polybenzoxazole resin, dried, exposed, developed, and thermally cured at 200 ° C. The adhesion on the substrate was “good”.
- Example 2 A negative photosensitive resin composition was prepared by changing the blending amount of 4,4′-bismaleimide diphenylmethane as the component (C) in Example 1 into 20 g in Example 1, and the same evaluation as in Example 1 was performed. went. It was "good” as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Example 3 the photosensitive resin composition was prepared by changing the component (C) in the present invention to bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and evaluated in the same manner as in Example 1. went. It was "good” as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Example 4 A photosensitive resin composition was prepared by changing the blending amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane as component (C) in Example 3 into 20 g in Example 3. Evaluation similar to 3 was performed. It was "good” as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Example 5 A photosensitive resin composition was prepared by changing the component (C) of Example 1 to N-phenylmaleimide in the present invention, and the same evaluation as in Example 1 was performed. It was "good” as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Example 6 the photosensitive resin composition was prepared by changing the component (C) in the present invention to N, N ′, N ′′-[nitrilotris (ethylene)] tris (maleimide). The same evaluation was performed. It was "good” as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Example 7 In Example 2, the component (C) in the present invention is changed to isocyanuric acid triacrylate, which is a polyfunctional methacrylate whose homopolymer has a glass transition temperature of 200 ° C. or higher, to prepare a photosensitive resin composition, The same evaluation as in Example 2 was performed. It was "good” as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Example 1 a negative photosensitive resin composition was prepared by removing 4,4′-bismaleimide diphenylmethane as the component (C) in the present invention, and the same evaluation as in Example 1 was performed. As a result of evaluating the adhesion on the PBO resin base material, it was “defective”. However, the thermosetting temperature of this composition was 200 degreeC at this time.
- Adekaoptomer NCI831 (trade name, manufactured by ADEKA)
- C1 4,4′-bismaleimide diphenylmethane
- C2 Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane
- C3 N-phenylmaleimide
- C4 N, N ′, N ′′-[nitrilotris (ethylene ]]
- C5 Isocyanuric acid triacrylate
- D1 Silicon-containing compound D-1
- Example 8 As the (AX) component, polymer A 50 g and polymer B 50 g, as the component (B) Irgacure OXE03 (trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution are 0, 0, 2 g), tetraethylene glycol dimethacrylate 8 g and 2-nitroso-1-naphthol 0.05 g, and diphenylacetamide 5 g, N- (3- (triethoxysilyl) propyl) phthalamic acid 0.8 g.
- Irgacure OXE03 trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution are 0, 0, 2 g
- tetraethylene glycol dimethacrylate 8 g and 2-nitroso-1-naphthol 0.05 g tetraethylene glycol dimethacrylate 8 g and 2-nitroso-1-nap
- Example 9 Polymer (A) 50 g and Polymer B 50 g as component (AX), Irgacure OXE03 2 g as component (B), 16 g of 4,4′-bismaleimide diphenylmethane, 8 g of tetraethylene glycol dimethacrylate and 2-nitroso-1-naphtho as component (C) 0.05 g of diphenylacetamide, 5 g of diphenylacetamide, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid, and benzophenone-3,3′-bis (N- (3-triethoxysilyl) propylamide ) 0.5 g of -4,4'-dicarboxylic acid was dissolved in a mixed solvent (mass ratio 8: 2) consisting of N-methylpyrrolidone and ethyl lactate, and the amount of the solvent was adjusted so that the viscosity was about 35 poise.
- a mixed solvent
- Example 10 In Example 9, instead of 2 g of Irgacure OXE03 as component (B), Adekaoptomer NCI831 (manufactured by ADEKA, trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution is 0, A photosensitive resin composition solution was prepared in the same manner as in Example 9 except that 2 g (0.13 and 0.22) were used. This composition was evaluated in the same manner as in Example 8.
- Adekaoptomer NCI831 manufactured by ADEKA, trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution is 0
- a photosensitive resin composition solution was prepared in the same manner as in Example 9 except that 2 g (0.13 and 0.22) were used. This composition was evaluated in the same manner as in Example 8.
- Example 11 In Example 9, as component (B), TR-PBG340 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution was 0.04, 0, respectively. A photosensitive resin composition solution was prepared in the same manner as in Example 9 except that 2 g (0.06 and 0.04) were used. This composition was evaluated in the same manner as in Example 8.
- Example 8 As an alternative component of the component (B), TR-PBG304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd., trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution was 0, respectively.
- a photosensitive resin composition was prepared in the same manner as in Example 8, except that 4 g) were used. This composition was evaluated in the same manner as in Example 8.
- Component- B1 Irgacure OXE03 (trade name, manufactured by BASF)
- B2 Adekaoptomer NCI831 (made by ADEKA, trade name)
- B3 TR-PBG340 (Changzhou Power Electronics New Materials Co., Ltd., trade name)
- -Component (C)- C1 4,4'-Bismaleimide diphenylmethane-Alternative component-
- B4 TR-PBG304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd., trade name)
- AY Polymer C 100 g as component (B), Irgacure OXE03 (trade name) manufactured by BASF as component (B), and 3 g of silicon-containing compound D-1 as component (D), a mixed solvent comprising N-methylpyrrolidone and ethyl lactate (A resin composition was obtained by adjusting the amount of the solvent so that it was dissolved in a mass ratio of 8: 2) and the viscosity was about 35 poise. The resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Tg glass transition temperature
- Example 13 ⁇ Example 13> (AY) component A 50 g and polymer B 50 g, (B) component Irgacure OXE03 (trade name) 4 g, (D) component silicon-containing compound D-1 3 g, tetraethylene glycol dimethacrylate 8 g, 2- 0.05 g of nitroso-1-naphthol and 5 g of diphenylacetamide are dissolved in a mixed solvent composed of N-methylpyrrolidone and ethyl lactate (mass ratio 8: 2), and the viscosity is about 35 poise.
- the resin composition was obtained by adjusting the amount of.
- the resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Example 14 ⁇ Example 14> (AY) component A 50 g and polymer B 50 g, (B) component Irgacure OXE3 (trade name, manufactured by BASF) 4 g, (D) component silicon-containing compound D-1 3 g and A-1160 (3-ureido 3 g of a 50% by mass solution of propyltriethoxysilane (manufactured by Momentive) as a methanol solution, 8 g of tetraethylene glycol dimethacrylate, 0.05 g of 2-nitroso-1-naphthol, and 5 g of diphenylacetamide were added to N-methylpyrrolidone.
- AY component A 50 g and polymer B 50 g
- component Irgacure OXE3 trade name, manufactured by BASF 4 g
- D component silicon-containing compound D-1 3 g and A-1160 (3-ureido 3 g of a 50% by mass solution of propyltriethoxysi
- the resin composition was obtained by adjusting the quantity of a solvent so that it might melt
- the resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Example 15 a cured film was formed and evaluated in the same manner as in Example 14 except that the heating temperature for curing was changed from 200 ° C to 390 ° C.
- Example 17 A resin composition was obtained in the same manner as in Example 16 except that the component (C) was changed from 4,4′-bismaleimide diphenylmethane to bis (3-ethyl-5-methyl-4-maleimidophenyl) methane in Example 16. Got. The resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Tg glass transition temperature
- Example 18 a resin composition was obtained in the same manner as in Example 16 except that 3 g of dicyclohexylthiourea was used as the (E) component instead of the (D) component.
- the resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Example 12 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid and benzophenone-3,3′-bis (N- (3-triethoxysilyl) propyl are used as alternative components for component (D).
- a resin composition was obtained in the same manner as in Example 12 except that 0.5 g of amide) -4,4′-dicarboxylic acid was used.
- the resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Example 14 As an alternative component of component (D), 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid and benzophenone-3,3′-bis (N- (3-triethoxysilyl) A resin composition was obtained in the same manner as in Example 14 except that 0.5 g of propylamide) -4,4′-dicarboxylic acid was used. The resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Tg glass transition temperature
- Example 15 As an alternative component of component (D), 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid and benzophenone-3,3′-bis (N- (3-triethoxysilyl) A resin composition was obtained in the same manner as in Example 15 except that 0.5 g of propylamide) -4,4′-dicarboxylic acid was used. The resin composition was evaluated by (5) measurement of glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.
- Tg glass transition temperature
- B1 Irgacure OXE03 (trade name, manufactured by BASF)
- B2 Adekaoptomer NCI831 (made by ADEKA, trade name)
- C1 4,4′-bismaleimide diphenylmethane
- C2 Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane
- D1 Silicon-containing compound D-1
- D2 Silicon-containing compound D-1 / A-1160 (50% solution of 3-ureidopropyltriethoxysilane, manufactured by Momentive)
- D3 N- (3- (triethoxysilyl) propyl) phthalamic acid / benzophenone-3,3′-bis (N- (3-triethoxysilyl) propylamide) -4,4′-dicarboxylic acid
- Example 19 As component (A), 50 g of polymer A and 50 g of polymer B were added to Adekaoptomer NCI831 (trade name, 0.001 wt% solution g-line, h-line, and i-line absorbance were 0, 0.13, and 0.22), 10 g of 4,4′-bismaleimide diphenylmethane, 3 g of silicon-containing compound D-1 and 0.05 g of 2-nitroso-1-naphthol, together with N-methylpyrrolidone (hereinafter referred to as NMP) )
- NMP N-methylpyrrolidone
- the viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.
- the composition was applied to a silicon wafer according to the method for evaluating adhesion to the polybenzoxazole resin described in (2) above, dried, exposed, developed, and thermally cured at 200 ° C. to obtain a resin film.
- the adhesion on the polybenzoxazole (PBO) resin substrate was “good”.
- the above-mentioned (7) crosslinking density was determined to be 7.0 ⁇ 10 ⁇ 4 mol / cm 3 from the reaction rate, composition, and density of maleimide by IR.
- the storage elastic modulus in 110 Hz and 300 degreeC was 0.08 GPa, and the above-mentioned (8) 5% weight reduction
- decrease temperature was 340 degreeC.
- Example 20 A photosensitive resin composition was prepared in the same manner as in Example 19 except that the amount of 4,4′-bismaleimide diphenylmethane added was changed to 20 g in Example 19.
- the composition was applied to a silicon wafer according to the method for evaluating adhesion to the polybenzoxazole resin described in (2) above, dried, exposed, developed, and thermally cured at 200 ° C. to obtain a resin film.
- the adhesion on the polybenzoxazole (PBO) resin substrate was “good”.
- the above-mentioned (7) crosslinking density was determined to be 1.4 ⁇ 10 ⁇ 3 mol / cm 3 from the reaction rate, composition and density of maleimide by IR.
- the storage elastic modulus in 110 Hz and 300 degreeC was 0.16 GPa, and the above-mentioned (8) 5% weight reduction
- decrease temperature was 370 degreeC.
- Example 6 A resin composition was prepared in the same manner as in Example 19 except that 4,4′-bismaleimide diphenylmethane was not added in Example 19, and a thermosetting resin film of the composition was obtained.
- the adhesion on the polybenzoxazole (PBO) resin base material evaluated according to the method for evaluating the adhesion with the polybenzoxazole resin (2) described above was “poor”.
- the above-mentioned (7) crosslinking density was determined to be 0 mol / cm 3 from the reaction rate, composition, and density of maleimide by IR.
- the storage elastic modulus in 110 Hz and 300 degreeC was 0.02 GPa, and the above-mentioned (8) 5% weight reduction
- the resin composition and resin film 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
[1]
以下の成分:
(A)ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂;
(B)感光剤;並びに
(C)多官能(メタ)アクリレート及び分子量1000未満の低分子量イミド化合物から成る群より選ばれる少なくとも1種;
を含む感光性樹脂組成物。
[2]
前記(A)成分が、ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、及びポリベンゾチアゾールから成る群より選ばれる少なくとも1種の樹脂である、[1]に記載の感光性樹脂組成物。
[3]
前記(C)成分が、前記分子量1000未満の低分子量イミド化合物である、[1]又は[2]に記載の感光性樹脂組成物。
[4]
前記(A)成分が、下記一般式(A1):
で表されるポリイミド前駆体であり、かつ
前記(C)成分が、下記一般式(C1):
で表されるマレイミドを含む、[1]~[3]のいずれか1項に記載の感光性樹脂組成物。
[5]
前記(A)成分が、下記一般式(A2):
で表される1価の有機基、又は炭素数1~4の飽和脂肪族基である。但し、R6及びR7の両者が同時に水素原子であることはない。}
で表されるポリイミド前駆体である、[1]~[4]のいずれか1項に記載の感光性樹脂組成物。
[6]
前記(C)成分が、下記一般式(C2):
で表されるマレイミドを含む、[1]~[5]のいずれか1項に記載の感光性樹脂組成物。
[7]
前記(B)成分が、オキシム系光重合開始剤である、[1]~[6]のいずれか1項に記載の感光性樹脂組成物。
[8]
前記(B)成分が、下記(B1)及び(B2)成分:
(B1)0.001wt%溶液のi線吸光度が0.15~0.5であり、かつ0.001wt%溶液のg線吸光度及びh線吸光度が0.2以下である、オキシムエステル化合物;及び
(B2)0.001wt%溶液のi線吸光度が0.1以下であり、かつ0.001wt%溶液のg線吸光度又はh線吸光度が0.05以上である、オキシムエステル化合物;
から成る群より選択される少なくとも1種を含む、[1]~[7]のいずれか1項に記載の感光性樹脂組成物。
[9]
前記(B1)成分の0.001wt%溶液のi線吸光度が、0.15~0.35である、[8]に記載の感光性樹脂組成物。
[10]
前記(B1)成分が、下記一般式(B11)及び(B12):
で表されるオキシムエステル化合物から成る群より選択される少なくとも1種を含む、[8]又は[9]に記載の感光性樹脂組成物。
[11]
上記(A)~(C)成分に加えて、
(D)下記一般式(D1):
で表されるシリコン含有化合物を含む、[1]~[10]のいずれか1項に記載の感光性樹脂組成物。
[12]
前記(D)成分として、前記式(D1)で表されるシリコン含有化合物に加えて、下記一般式(D2):
で表されるシリコン含有化合物を更に含む、[11]に記載の感光性樹脂組成物。
[13]
上記(A)~(C)成分に加えて、
(E)下記一般式(E1):
で表されるイオウ含有化合物を含む、[1]~[10]のいずれか1項に記載の感光性樹脂組成物。
[14]
前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;及び
前記(C)成分1~40質量部;
を含む、[1]~[10]のいずれか1項に記載の感光性樹脂組成物。
[15]
前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;及び
前記(C)成分10~35質量部;
を含む、[1]~[10]のいずれか1項に記載の感光性樹脂組成物。
[16]
前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分1~40質量部;及び
前記(D)成分0.1~20質量部;
を含む、[11]又は[12]に記載の感光性樹脂組成物。
[17]
前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分10~35質量部;及び
前記(D)成分0.1~20質量部;
を含む、[11]又は[12]に記載の感光性樹脂組成物。
[18]
前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分1~40質量部;及び
前記(E)成分0.1~20質量部;
を含む、[13]に記載の感光性樹脂組成物。
[19]
前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分10~35質量部;及び
前記(E)成分0.1~20質量部;
を含む、[13]に記載の感光性樹脂組成物。
[20]
以下の成分:
(AX)感光性ポリイミド前駆体と;
下記(B1)及び(B2)成分:
(B1)0.001wt%溶液のi線吸光度が0.15~0.5であり、かつ0.001wt%溶液のg線吸光度及びh線吸光度が0.2以下である、オキシムエステル化合物、及び
(B2)0.001wt%溶液のi線吸光度が0.1以下であり、かつ0.001wt%溶液のg線吸光度又はh線吸光度が0.05以上である、オキシムエステル化合物、
から成る群より選択される少なくとも1種と;
を含む、感光性樹脂組成物。
[21]
前記(AX)成分が、下記一般式(A2):
で表される1価の有機基、又は炭素数1~4の飽和脂肪族基である。但し、R6及びR7の両者が同時に水素原子であることはない。}
で表されるポリイミド前駆体である、[20]に記載の感光性樹脂組成物。
[22]
前記(B1)成分の0.001wt%溶液のi線吸光度が0.15~0.35である、[20]又は[21]に記載の感光性樹脂組成物。
[23]
前記(B1)成分が、下記一般式(B11)及び(B12):
で表されるオキシムエステル化合物より成る群から選択される少なくとも1種を含む、[20]~[22]のいずれか1項に記載の感光性樹脂組成物。
[24]
前記(AX)成分100質量部に対する前記(B1)成分及び(B2)成分の合計含有量が、0.1~10質量部である、[20]~[23]のいずれか1項に記載の感光性樹脂組成物。
[25]
前記(AX)成分100質量部に対する前記(B1)成分及び(B2)成分の合計含有量が0.5~5質量部である、[20]~[24]のいずれか1項に記載の感光性樹脂組成物。
[26]
以下の成分:
(AY)ポリイミド前駆体;及び
(D)下記一般式(D1):
で表されるシリコン含有化合物;
を含む、樹脂組成物。
[27]
前記(D)成分として、前記式(D1)で表されるシリコン含有化合物に加えて、下記一般式(D2):
で表されるシリコン含有化合物を更に含む、[26]に記載の樹脂組成物。
[28]
以下の成分:
(AY)ポリイミド前駆体;及び
(E)下記一般式(E1):
で表されるイオウ含有化合物;
を含む、樹脂組成物。
[29]
前記(AY)成分が、下記一般式(A2):
で表される1価の有機基、又は炭素数1~4の飽和脂肪族基である。但し、R6及びR7の両者が同時に水素原子であることはない。}
で表されるポリイミド前駆体である、[26]~[28]のいずれか1項に記載の樹脂組成物。
[30]
前記(AY)成分100質量部に対して、
前記(D1)成分0.1~20質量部;及び
前記(D2)成分0.1~20質量部;
を含む、[27]に記載の樹脂組成物。
[31]
前記(AY)成分100質量部に対して、前記(E)成分0.1~20質量部を含む、[28]又は[29]に記載の樹脂組成物。
[32]
(B)感光剤を更に含有する、[26]~[31]のいずれか1項に記載の樹脂組成物。
[33]
以下の:
(1)[1]~[25]のいずれか1項に記載の感光性樹脂組成物又は[32]に記載の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に供して、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。
[34]
[33]に記載の製造方法により得られる硬化レリーフパターンを備える、半導体装置。
[35]
以下の成分:
(A)ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂、
を含み、
架橋密度が1.0×10-4mol/cm3以上、3.0×10-3mol/cm3以下であり、かつ
5%重量減少温度が250℃以上400℃以下である、
樹脂膜。
[36]
前記架橋密度が、3.0×10-4mol/cm3以上、2.0×10-3mol/cm3以下である、[35]に記載の樹脂膜。
[37]
前記(A)成分が、ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、及びポリベンゾチアゾールから成る群より選ばれる少なくとも1種の樹脂である、[35]又は[36]に記載の樹脂膜。
[38]
[35]~[37]のいずれか1項に記載の樹脂膜が、ガラス転移温度が200℃以下の樹脂基板上に積層されている積層体。
[39]
[35]~[37]のいずれか1項に記載の樹脂膜が、ガラス転移温度が250℃以下の樹脂基板上に積層されている積層体。
(A)ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂;
(B)感光剤;及び
(C)多官能(メタ)アクリレート及び分子量1000未満の低分子量イミド化合物から成る群より選ばれる少なくとも1種;
を含む樹脂組成物について説明する。
本組成物中で用いられる(A)成分は、ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂である。中でも、ポリベンゾオキサゾール樹脂との密着性の観点から、ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾールから成る群より選ばれる少なくとも1種の樹脂が好ましい。
本発明の樹脂組成物において、耐熱性及び感光性の観点から、(A)樹脂、(AX)感光性ポリイミド前駆体及び(AY)ポリイミド前駆体の一つは、好ましくは、下記一般式(A1):
で表わされる構造を有するポリアミドであり、より好ましくは、下記一般式(A2):
で表される1価の有機基、又は炭素数1~4の飽和脂肪族基である。但し、R6及びR7の両者が同時に水素原子であることはない。}
で表される構造を有するポリアミドである。
(A)樹脂、(AX)感光性ポリイミド前駆体、又は(AY)ポリイミド前駆体は、加熱(例えば180℃以上)環化処理によって、ポリイミドに変換される。
で表される構造が挙げられるが、これらに限定されるものではない。また、Y2の構造は1種でも2種以上の組み合わせでもよい。
エステル結合型のポリイミド前駆体は、まず、前述の4価の有機基X2を含むテトラカルボン酸二無水物と、光重合性の不飽和二重結合を有するアルコール類及び任意に飽和脂肪族アルコール類とを反応させて、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)を調製した後、これと、前述の2価の有機基Y2を含むジアミン類とをアミド重縮合させることにより得られる。
エステル結合型のポリイミド前駆体を調製するために好適に用いられる、4価の有機基X2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が、これらに限定されるものではない。これらは単独で又は2種以上の混合物として使用されることができる。
アシッド/エステル体(典型的には、反応溶媒中の溶液)に、氷冷下、適当な脱水縮合剤、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し、混合してアシッド/エステル体をポリ酸無水物に変換する。その後、好ましい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溶液又は分散体を、ポリ酸無水物に滴下し、アミド重縮合させることにより、目的の感光性樹脂を得ることができる。
(B)感光剤としては、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。(B)感光剤として好適に使用できる化合物としては、例えば、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(benzil)、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、これらの1種を使用しても2種以上の混合物を使用してもよい。これらの中では、特に光感度の観点から、オキシム類がより好ましい。
(B1)0.001wt%溶液について、g線吸光度及びh線吸光度が0.2以下であり、かつi線吸光度が0.15~0.5であるオキシムエステル化合物;及び
(B2)0.001wt%溶液について、g線吸光度又はh線吸光度が0.05以上であり、かつi線吸光度が0.1以下であるオキシムエステル化合物;
から成る群より選択される少なくとも1種であることが好ましい。
オキシムエステル化合物の吸光度は、該化合物をN-メチルピロリドンに0.001wt%の濃度で溶解させ、1cmの石英セル及び通常の分光光度計を用いて測定することができる。
で表されるオキシムエステル化合物から成る群より選択される少なくとも1種である。
(B2)成分のオキシムエステル化合物の吸光度は、(B1)成分のオキシムエステル化合物の場合と同様にして測定されることができる。
(C)成分は、多官能(メタ)アクリレート及び分子量1000未満の低分子量イミド化合物から成る群より選ばれる少なくとも1種である。「(メタ)アクリレート」は、アクリレート又はメタクリレートを意味する。(C)成分は、重合可能なモノマーでよい。(C)成分のみを重合することにより得られるホモポリマーのガラス転移温度は、200℃以上であることが好ましい。
で表されるマレイミドであることが好ましい。
式(C1)において、mは、2以上の整数又は3以上の整数でもよい。
で表されるマレイミドであることがより好ましい。
(D)成分は、下記一般式(D1):
で表されるシリコン含有化合物である。
メチルアミノ基、エチルアミノ基、n-プロピルアミノ基、n-ブチルアミノ基、n-ヘキシルアミノ基、n-オクチルアミノ基、イソプロピルアミノ基、イソブチルアミノ基、t-ブチルアミノ基、イソアミルアミノ基、シクロペンチル基、シクロヘキシルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基、ジシクロヘキシルアミノ基等のモノ及びジアルキアルアミノ基;
フェニルアミノ基、ベンジルアミノ基、ジフェニルアミノ基等の芳香環含有アミノ基;
ピコリル基、アミノトリアジル基、フルフリルアミノ基、モルホリノ基等の複素環含有アミノ基;
メトキシ基、エトキシ基、n-ブトキシ基、t-ブトキシ基、ヘキシルオキシ基、シクロヘシルオキシ基等のアルコキシ基;
フェノキシ基、ベンジルオキシ基、トリルオキシ基等のアルキルアリールオキシ基又はアリールアルキルオキシ基;
フルフリルアルコキシ基、2-ピリジニルエトキシ基等の複素環含有アルコキシ基;
メチルチオ基、エチルチオ基、n-ブチルチオ基、t-ブチルチオ基、ヘキシルチオ基、シクロヘキシルチオ基等のアルキルチオ基又はフェニルチオ基;
これらの混合物、等が挙げられる。
で表されるシリコン含有化合物を感光性樹脂組成物に更に加えることが好ましい。
(E)成分は、下記一般式(E1):
で表されるイオウ含有化合物である。
メチルアミノ基、エチルアミノ基、n-プロピルアミノ基、n-ブチルアミノ基、n-ヘキシルアミノ基、n-オクチルアミノ基、イソプロピルアミノ基、イソブチルアミノ基、t-ブチルアミノ基、イソアミルアミノ基、シクロペンチル基、シクロヘキシルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基、ジシクロヘキシルアミノ基等のモノ及びジアルキアルアミノ基;
フェニルアミノ基、ベンジルアミノ基、ジフェニルアミノ基等の芳香環含有アミノ基;
ピコリル基、アミノトリアジル基、フルフリルアミノ基、モルホリノ基等の複素環含有アミノ基;
メトキシ基、エトキシ基、n-ブトキシ基、t-ブトキシ基、ヘキシルオキシ基、シクロヘシルオキシ基等のアルコキシ基;
フェノキシ基、ベンジルオキシ基、トリルオキシ基等のアルキルアリールオキシ基又はアリールアルキルオキシ基;
フルフリルアルコキシ基、2-ピリジニルエトキシ基等の複素環含有アルコキシ基;
メチルチオ基、エチルチオ基、n-ブチルチオ基、t-ブチルチオ基、ヘキシルチオ基、シクロヘキシルチオ基等のアルキルチオ基又はフェニルチオ基;
等が挙げられる。
本発明の脂組成物は、(A)~(E)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、溶剤を使用することができる。その場合、(A)~(E)成分を溶剤に溶解して、ワニス状のネガ型感光性樹脂組成物を得ることができる。
溶剤としては、(A)樹脂、(AX)感光性ポリイミド前駆体又は(AY)ポリイミド前駆体に対する溶解性の観点から、極性の有機溶剤を用いることが好ましい。具体的には、N,N-ジメチルホルムアミド、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N,N-ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、シクロペンタノン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、テトラメチル尿素、1,3-ジメチル-2-イミダゾリノン、N-シクロヘキシル-2-ピロリドン等が使用される。これらは単独又は2種以上の組合せで用いることができる。
通常用いられている光重合開始剤としては、限定されるものではないが、例えば、
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、イルガキュアOXE01(BASF社製、商品名)、イルガキュアOXE02(BASF社製、商品名)、アデカオプトマーN-1919(ADEKA社製、商品名)、TR-PBG304(常州強力電子新材料有限公司製、商品名)、TR-PBG305(常州強力電子新材料有限公司製、商品名)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;
等が好ましい。
これらの1種又は2種以上の混合物を使用してよい。上記の感光剤の中では、光感度の観点から、オキシム類がより好ましい。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン等が挙げられる。これらは単独で又は例えば2~5種類の組合せで用いることができる。
本発明の樹脂組成物が感光性である場合、以下の工程:
(1)上述した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に供して、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を提供することができる。以下、各工程の典型的な態様について説明する。
本工程では、本発明の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。
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)樹脂、(AX)感光性ポリイミド前駆体又は(AY)ポリイミド前駆体を加熱硬化ことによって、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、ホットプレートを用いる方法、オーブンを用いる方法、温度プログラムを設定できる昇温式オーブンを用いる方法等の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。加熱硬化の際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てもよい。
上記で説明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備える、半導体装置を提供することもできる。より詳細には、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を提供することができる。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されることができる。本発明の半導体装置は、上記で説明した硬化レリーフパターンの製造方法により、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、かつ硬化レリーフパターンの製造方法と公知の半導体装置の製造方法と組合せることにより製造されることができる。
(A)成分として、ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂を含み、架橋密度が1.0×10-4mol/cm3以上、3.0×10-3mol/cm3以下であり、かつ5%重量減少温度が250℃以上400℃以下である樹脂膜も本発明の実施形態の1つである。
n=E’/3RT
{n:架橋密度、E’:貯蔵弾性率、R:気体定数、T:絶対温度}
が成立することが知られる。
樹脂の重量平均分子量(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、昭和電工株式会社製Shodex(商標名)805M/806M直列であり、標準単分散ポリスチレンとしては、昭和電工株式会社製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、そして検出器としては、昭和電工製Shodex(商標名)RI-930を使用した。
ポリベンゾオキサゾール樹脂を塗布、硬化した6インチシリコンウエハー上に、樹脂膜の前駆体又は感光性樹脂組成物をスピン塗布し、乾燥して約10μm厚の塗膜を樹脂膜前駆体又は感光性樹脂層として形成した。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NSR2005i8A(ニコン社製)により、1500mJ/cm2エネルギーを照射して露光した。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、日本国、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未露光部を現像除去し、樹脂膜前駆体又は感光性樹脂組成物のレリーフパターンを得た。
良好:得られた20μmパターンの開口部の面積が、対応するパターンマスク開口面積の1/2以上であり、かつ剥がれがない。
不良: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未満であるか、又は剥がれがある。
感光性樹脂組成物を6インチシリコンウエハー上に回転塗布し、乾燥して8.5μm厚の塗膜を形成した。この塗膜に、テストパターン付マスクを介して、プリズマGHI(米国、ウルトラテック社製)により500mJ/cm2のエネルギーを照射した。次いで、照射後の塗膜を、シクロペンタノンを用いて現像機(D-SPIN636型、日本国、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未露光部を現像除去することにより、レリーフパターンを得た。
1.開口部の上辺と下辺を引くこと(図1A);
2.開口部の高さを決めること(図1B);
3.高さの中央部分を通って上辺及び下辺に平行な直線(中央線)を引くこと(図1C);
4.中央線と開口部パターンとの交点(中央点)を求めること(図1D);及び
5.中央点におけるパターンの傾きに合せて接線を引き、その接線と下辺とが形成する角をテーパー角と見なすこと(図1E)。
このレリーフパターンについて、Tencor P-15型段差計(ケーエルエーテンコール社製)を用いて膜厚測定を行い、上記と同様にしてラインアンドスペース(1:1)部分のテーパー角を求めた。
樹脂組成物を6インチシリコンウエハー上に、回転塗布し、乾燥して8.5μm厚の塗膜を形成した。この塗膜に、テストパターン付マスクを用いて、プリズマGHI(米国、ウルトラテック社製)により、500mJ/cm2のエネルギーを照射した。次いで、照射後の塗膜を、シクロペンタノンを用いて現像機(D-SPIN636型、日本国、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未露光部を現像除去することにより、レリーフパターンを得た。
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。Si上に得られたパターンについては、パターン形状及びパターン部の幅を光学顕微鏡下で観察し、最少開口パターンのサイズを求めた。
基板となる6インチシリコンウエハー(日本国、フジミ電子工業株式会社製、厚み625±25μm)上に、及びこのシリコンウエハーに200nm厚のTi及び400nm厚のCuをこの順でスパッタしたスパッタ体の上に、それぞれ、硬化後の膜厚が約4~5μmとなるように樹脂組成物を回転塗布した。次いで、樹脂組成物が感光性である場合は、平行光マスクアライナーPLA-501FA(日本国、キヤノン社製)により、500mJ/cm2のエネルギーを照射した。樹脂組成物が感光性ではない場合には、この照射を行わなかった。
得られた硬化テープを、荷重200g/mm2、昇温速度10℃/分、20~500℃の範囲で熱機械試験装置(島津製作所製 TMA-50)により測定し、温度を横軸、変位量を縦軸に取った測定チャートにおける硬化テープの熱降伏点の接線交点をガラス転移温度(Tg)とした。
基板となる6インチシリコンウエハー(日本国、フジミ電子工業株式会社製、厚み625±25μm)上に、及びこのシリコンウエハーに200nm厚のTi及び400nm厚のCuをこの順でスパッタしたスパッタ体の上に、それぞれ、硬化後の膜厚が約4~5μmとなるように樹脂組成物を回転塗布した。次いで、樹脂組成物が感光性である場合は、平行光マスクアライナーPLA-501FA(日本国、キヤノン社製)により、500mJ/cm2のエネルギーを照射した。樹脂組成物が感光性ではない場合には、この照射を行わなかった。
得られた硬化膜のSi又はCuに対する密着性を、碁盤目試験(JIS K5400)により評価した。すなわち、塗膜上に、1mm角の正方形100個ができるようにカッターナイフで傷を付け、上からセロハン(登録商標)テープを貼り付け、気泡がなくなるまで密着させた後、剥離した時、セロハン(登録商標)テープに付着せず基板上に残った正方形の数を数えることにより、評価した。
樹脂膜を基材から剥がした後、動的粘弾性測定装置 レオバイブロン モデルDDV-01FP(オリエンテック社製)を用いて、30℃から400℃まで、5℃/minで昇温しながら、3.5、11、35、110Hzの各周波数で、微小な振動を与えることで、各温度での貯蔵弾性率を求めた。また、380型FTIR(ニコレー社製)を用いて、樹脂膜中の架橋基の反応率を求め、それから架橋密度を計算した。
樹脂膜を基材から剥がした後、熱重量測定装置(島津製作所製 TGA-50)を用い、30℃から500℃まで、窒素下で10℃/minで昇温し、重量が初期値から5%減少する温度を求めた。
4,4’-オキシジフタル酸二無水物(ODPA)155.1g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)131.2g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4,4’-オキシジフタル酸二無水物155.1gに代えて、3,3’4,4’-ビフェニルテトラカルボン酸二無水物147.1g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、ポリイミド前駆体B(以下、「ポリマーB」ともいう)を得た。ポリイミド前駆体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22,000であった。
4,4’-ジアミノジフェニルエーテル(DADPE)93.0gを2リットル容量のセパラブルフラスコに入れ、N-メチルピロリドン400mlを加えて室温下で撹拌溶解した。その後、4,4’-オキシジフタル酸二無水物(ODPA)155.1gを加えて80℃で5時間反応させることにより、ポリマーC(ポリイミド前駆体であるポリアミド酸)の溶液を得た。ポリマーA-1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20,000であった。
500ml3つ口フラスコに、ヘキシルアミン10.2gを入れ、N-メチルピロリドン146.4gを加えて溶解させた後、滴下ロートから3-ウレイドプロピルトリエトキシシラン26.4gを滴下し、そのまま室温で5時間撹拌反応させることにより、シリコン含有化合物D-1の溶液を得た。
ポリイミド前駆体A(ポリマーA)及びポリイミド前駆体B(ポリマーB)を用いて以下の方法で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。(A)成分として、ポリマーA50g及びポリマーB50gを、(B)成分として、アデカオプトマーNCI831(ADEKA社製、商品名、0.001wt%溶液のg線、h線、及びi線吸光度は、それぞれ0、0.13、及び0.22である)2g、(C)成分として、4,4’-ビスマレイミドジフェニルメタン10g、更に、ヘキサメトキシメチルメラミン4g、及びテトラエチレングリコールジメタクリレート8g、(D)成分として、シリコン含有化合物D-1 3g、及び2-ニトロソ-1-ナフト-ル0.05gと共に、N-メチルピロリドン(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、感光性樹脂組成物とした。
該組成物を、前述の(2)ポリベンゾオキサゾール樹脂との密着性評価の方法に従ってシリコンウエハーに塗布して乾燥させ、露光、現像、200℃で熱硬化した時のポリベンゾオキサゾール(PBO)樹脂基材上での密着性は「良好」であった。
実施例1の、本発明における(C)成分としての4,4’-ビスマレイミドジフェニルメタンの配合量を20gに変更して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。PBO樹脂基材上での密着性を評価した結果「良好」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
実施例1の、本発明における(C)成分をビス(3-エチル-5-メチル-4-マレイミドフェニル)メタンに変更して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。PBO樹脂基材上での密着性を評価した結果「良好」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
実施例3の、本発明における(C)成分としてのビス(3-エチル-5-メチル-4-マレイミドフェニル)メタンの配合量を20gに変更して感光性樹脂組成物を調製し、実施例3と同様の評価を行った。PBO樹脂基材上での密着性を評価した結果「良好」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
実施例1の、本発明における(C)成分をN-フェニルマレイミドに変更して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。PBO樹脂基材上での密着性を評価した結果「良好」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
実施例1の、本発明における(C)成分をN,N’,N’’-[ニトリロトリス(エチレン)]トリス(マレインイミド)に変更して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。PBO樹脂基材上での密着性を評価した結果「良好」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
実施例2において、本発明における(C)成分を、単独重合体のガラス転移温度が200℃以上である多官能メタクリレートである、イソシアヌル酸トリアクリレートに変更して感光性樹脂組成物を調製し、実施例2と同様の評価を行った。PBO樹脂基材上での密着性を評価した結果「良好」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
実施例1の、本発明における(C)成分としての4,4’-ビスマレイミドジフェニルメタンを抜いて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。PBO樹脂基材上での密着性を評価した結果「不良」であった。但し、このとき該組成物の熱硬化温度は200℃とした。
B1:アデカオプトマーNCI831(ADEKA社製、商品名)
C1:4,4’-ビスマレイミドジフェニルメタン
C2:ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン
C3:N-フェニルマレイミド
C4:N,N’,N’’-[ニトリロトリス(エチレン)]トリス(マレインイミド)
C5:イソシアヌル酸トリアクリレート
D1:シリコン含有化合物D-1
(AX)成分として、ポリマーA50g及びポリマーB50g、(B)成分としてイルガキュアOXE03(BASF社製、商品名、0.001wt%溶液のg線、h線、及びi線吸光度は、それぞれ0、0、及び0.27である)2g、テトラエチレングリコールジメタクリレート8g及び2-ニトロソ-1-ナフト-ル0.05g、並びにジフェニルアセトアミド5g、N-(3-(トリエトキシシリル)プロピル)フタルアミド酸0.5g、及びベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸0.5gを、N-メチルピロリドン及び乳酸エチルから成る混合溶媒(重量比8:2)に溶解し、粘度が約35ポイズになるように溶媒の量を調整することにより、感光性樹脂組成物溶液を得た。
この組成物について、前述の(3)開口パターンのテーパー角度評価及び(4)最少開口パターンサイズ評価方法により評価した。
(AX)成分としてポリマーA50g及びポリマーB50gを、(B)成分としてイルガキュアOXE03 2g、(C)成分として4,4’-ビスマレイミドジフェニルメタン16g、テトラエチレングリコールジメタクリレート8g及び2-ニトロソ-1-ナフト-ル0.05g、並びにジフェニルアセトアミド5g、N-(3-(トリエトキシシリル)プロピル)フタルアミド酸0.5g、及びベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸0.5gを、N-メチルピロリドン及び乳酸エチルから成る混合溶媒(質量比8:2)に溶解し、粘度が約35ポイズになるように溶媒の量を調整することにより、感光性樹脂組成物溶液を得た。
この組成物について、実施例8と同様の方法により評価した。
実施例9において、(B)成分として、イルガキュアOXE03 2gの代わりにアデカオプトマーNCI831(ADEKA社製、商品名、0.001wt%溶液のg線、h線、及びi線吸光度は、それぞれ0、0.13、及び0.22である)2gを用いた他は、実施例9と同様にして感光性樹脂組成物溶液を調製した。
この組成物について、実施例8と同様の方法により評価した。
実施例9において、(B)成分としてTR-PBG340(常州強力電子新材料有限公司製、商品名、0.001wt%溶液のg線、h線、及びi線吸光度は、それぞれ0.04、0.06、及び0.04である)2gを用いた他は実施例9と同様にして感光性樹脂組成物溶液を調製した。
この組成物について、実施例8と同様の方法により評価した。
実施例8において、(B)成分の代替成分として、TR-PBG304(常州強力電子新材料有限公司製、商品名、0.001wt%溶液のg線、h線、及びi線吸光度は、それぞれ0、0、及び0.12である)4gを用いた他は、実施例8と同様に感光性樹脂組成物を調製した。
この組成物について、実施例8と同様の方法により評価した。
-(B)成分-
B1:イルガキュアOXE03(BASF社製、商品名)
B2:アデカオプトマーNCI831(ADEKA社製、商品名)
B3:TR-PBG340(常州強力電子新材料有限公司製、商品名)
-(C)成分-
C1:4,4’-ビスマレイミドジフェニルメタン
-代替成分-
B4:TR-PBG304(常州強力電子新材料有限公司製、商品名)
(AY)成分としてポリマーC100g、(B)成分としてイルガキュアOXE03(BASF社製、商品名)及び(D)成分としてシリコン含有化合物D-1 3gを、N-メチルピロリドン及び乳酸エチルから成る混合溶媒(質量比8:2)中に溶解し、粘度が約35ポイズになるように溶媒の量を調整することにより、樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
(AY)成分としてポリマーA50g及びポリマーB50g、(B)成分としてイルガキュアOXE03(BASF社製、商品名)4g、(D)成分としてシリコン含有化合物D-1 3g、テトラエチレングリコールジメタクリレート8g、2-ニトロソ-1-ナフト-ル0.05g、及びジフェニルアセトアミド5gを、N-メチルピロリドン及び乳酸エチルがから成る混合溶媒(質量比8:2)に溶解し、粘度が約35ポイズになるように溶媒の量を調整することにより、樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
(AY)成分としてポリマーA50g及びポリマーB50g、(B)成分として、イルガキュアOXE3(BASF社製、商品名)を4g、(D)成分としてシリコン含有化合物D-1 3g及びA-1160(3-ウレイドプロピルトリエトキシシランの50質量%溶液、モメンティブ社製)をメタノール溶液として3g、テトラエチレングリコールジメタクリレート8g、2-ニトロソ-1-ナフト-ル0.05g、及びジフェニルアセトアミド5gを、N-メチルピロリドン及び乳酸エチルから成る混合溶媒(質量比8:2)に溶解し、粘度が約35ポイズになるように溶媒の量を調整することにより、樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
実施例14において、硬化のための加熱温度を200℃から390℃に変えた他は、実施例14と同様にして硬化膜を形成して、評価した。
(AY)成分としてポリマーA50g及びポリマーB50g、(B)成分としてアデカオプトマーNCI831(ADEKA社製、商品名)4g、(C)成分として4,4’-ビスマレイミドジフェニルメタン16g、(D)成分としてシリコン含有化合物D-1 3g及びA-1160(3-ウレイドプロピルトリエトキシシランの50質量%溶液、モメンティブ社製)をメタノール溶液として3g、テトラエチレングリコールジメタクリレート8g、2-ニトロソ-1-ナフト-ル0.05g、及びジフェニルアセトアミド5gと共に、N-メチルピロリドン及び乳酸エチルから成る混合溶媒(質量比8:2)に溶解し、粘度が約35ポイズになるように溶媒の量を調整することにより、樹脂組成物っを得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
実施例16において、(C)成分を4,4’-ビスマレイミドジフェニルメタンからビス(3-エチル-5-メチル-4-マレイミドフェニル)メタンに変えた他は実施例16と同様にして樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
実施例16において、(D)成分の代わりに、(E)成分として、ジシクロヘキシルチオウレア3gを用いた他は実施例16と同様にして樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
実施例12において、(D)成分の代替成分としてN-(3-(トリエトキシシリル)プロピル)フタルアミド酸0.5g及びベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸0.5gを用いた他は、実施例12と同様にして樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
実施例14において、(D)成分の代替成分として、N-(3-(トリエトキシシリル)プロピル)フタルアミド酸0.5g及びベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸0.5gを用いた他は、実施例14と同様にして樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
実施例15において、(D)成分の代替成分として、N-(3-(トリエトキシシリル)プロピル)フタルアミド酸0.5g及びベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸0.5gを用いた他は、実施例15と同様にして樹脂組成物を得た。
この樹脂組成物について、前述の(5)硬化膜のガラス転移温度(Tg)の測定、(6)硬化膜のSi、Cu密着性の測定、(4)最少開口パターンサイズ評価方法により評価した。
B1:イルガキュアOXE03(BASF社製、商品名)
B2:アデカオプトマーNCI831(ADEKA社製、商品名)
C1:4,4’-ビスマレイミドジフェニルメタン
C2:ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン
D1:シリコン含有化合物D-1
D2:シリコン含有化合物D-1/A-1160(3-ウレイドプロピルトリエトキシシランの50%溶液、モメンティブ社製)
D3:N-(3-(トリエトキシシリル)プロピル)フタルアミド酸/ベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸
(A)成分としてポリマーA50g及びポリマーB50gを、アデカオプトマーNCI831(ADEKA社製、商品名、0.001wt%溶液のg線、h線、及びi線吸光度は、それぞれ0、0.13、及び0.22である)2g、4,4’-ビスマレイミドジフェニルメタン10g、シリコン含有化合物D-1 3g、及び2-ニトロソ-1-ナフト-ル0.05gと共に、N-メチルピロリドン(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て溶液を得た。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、感光性樹脂組成物を得た。
該組成物を、前述の(2)ポリベンゾオキサゾール樹脂との密着性評価の方法に従ってシリコンウエハーに塗布して乾燥させ、露光、現像、200℃で熱硬化して樹脂膜を得た。このときポリベンゾオキサゾール(PBO)樹脂基材上での密着性は「良好」であった。
また、前述の(7)架橋密度については、IRによるマレイミドの反応率並びに組成、密度から7.0×10-4mol/cm3と求められた。また、110Hz、300℃における貯蔵弾性率は0.08GPaであり、前述の(8)5%重量減少温度は340℃であった。
実施例19において、4,4’-ビスマレイミドジフェニルメタンの添加量20gに変えた他は、実施例19と同様に感光性樹脂組成物を調合した。
該組成物を、前述の(2)ポリベンゾオキサゾール樹脂との密着性評価の方法に従ってシリコンウエハーに塗布して乾燥させ、露光、現像、200℃で熱硬化して樹脂膜を得た。このときポリベンゾオキサゾール(PBO)樹脂基材上での密着性は「良好」であった。
また、前述の(7)架橋密度については、IRによるマレイミドの反応率並びに組成、密度から1.4×10-3mol/cm3と求められた。また、110Hz、300℃における貯蔵弾性率は0.16GPaであり、前述の(8)5%重量減少温度は370℃であった。
実施例19において、4,4’-ビスマレイミドジフェニルメタンを添加しなかった他は、実施例19と同様に樹脂組成物を調合し、該組成物の熱硬化樹脂膜を得た。このとき、前述の(2)ポリベンゾオキサゾール樹脂との密着性評価の方法に従って評価した、ポリベンゾオキサゾール(PBO)樹脂基材上での密着性は「不良」であった。
また、前述の(7)架橋密度については、IRによるマレイミドの反応率並びに組成、密度から0mol/cm3と求められた。また、110Hz、300℃における貯蔵弾性率は0.02GPaであり、前述の(8)5%重量減少温度は320℃であった。
Claims (39)
- 以下の成分:
(A)ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂;
(B)感光剤;並びに
(C)多官能(メタ)アクリレート及び分子量1000未満の低分子量イミド化合物から成る群より選ばれる少なくとも1種;
を含む感光性樹脂組成物。 - 前記(A)成分が、ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、及びポリベンゾチアゾールから成る群より選ばれる少なくとも1種の樹脂である、請求項1に記載の感光性樹脂組成物。
- 前記(C)成分が、前記分子量1000未満の低分子量イミド化合物である、請求項1又は2に記載の感光性樹脂組成物。
- 前記(A)成分が、下記一般式(A1):
で表されるポリイミド前駆体であり、かつ
前記(C)成分が、下記一般式(C1):
で表されるマレイミドを含む、請求項1~3のいずれか1項に記載の感光性樹脂組成物。 - 前記(B)成分が、オキシム系光重合開始剤である、請求項1~6のいずれか1項に記載の感光性樹脂組成物。
- 前記(B)成分が、下記(B1)及び(B2)成分:
(B1)0.001wt%溶液のi線吸光度が0.15~0.5であり、かつ0.001wt%溶液のg線吸光度及びh線吸光度が0.2以下である、オキシムエステル化合物;及び
(B2)0.001wt%溶液のi線吸光度が0.1以下であり、かつ0.001wt%溶液のg線吸光度又はh線吸光度が0.05以上である、オキシムエステル化合物;
から成る群より選択される少なくとも1種を含む、請求項1~7のいずれか1項に記載の感光性樹脂組成物。 - 前記(B1)成分の0.001wt%溶液のi線吸光度が、0.15~0.35である、請求項8に記載の感光性樹脂組成物。
- 前記(B1)成分が、下記一般式(B11)及び(B12):
で表されるオキシムエステル化合物から成る群より選択される少なくとも1種を含む、請求項8又は9に記載の感光性樹脂組成物。 - 前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;及び
前記(C)成分1~40質量部;
を含む、請求項1~10のいずれか1項に記載の感光性樹脂組成物。 - 前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;及び
前記(C)成分10~35質量部;
を含む、請求項1~10のいずれか1項に記載の感光性樹脂組成物。 - 前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分1~40質量部;及び
前記(D)成分0.1~20質量部;
を含む、請求項11又は12に記載の感光性樹脂組成物。 - 前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分10~35質量部;及び
前記(D)成分0.1~20質量部;
を含む、請求項11又は12に記載の感光性樹脂組成物。 - 前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分1~40質量部;及び
前記(E)成分0.1~20質量部;
を含む、請求項13に記載の感光性樹脂組成物。 - 前記(A)成分100質量部に対して、
前記(B)成分0.1~20質量部;
前記(C)成分10~35質量部;及び
前記(E)成分0.1~20質量部;
を含む、請求項13に記載の感光性樹脂組成物。 - 以下の成分:
(AX)感光性ポリイミド前駆体と;
下記(B1)及び(B2)成分:
(B1)0.001wt%溶液のi線吸光度が0.15~0.5であり、かつ0.001wt%溶液のg線吸光度及びh線吸光度が0.2以下である、オキシムエステル化合物、及び
(B2)0.001wt%溶液のi線吸光度が0.1以下であり、かつ0.001wt%溶液のg線吸光度又はh線吸光度が0.05以上である、オキシムエステル化合物、
から成る群より選択される少なくとも1種と;
を含む、感光性樹脂組成物。 - 前記(B1)成分の0.001wt%溶液のi線吸光度が0.15~0.35である、請求項20又は21に記載の感光性樹脂組成物。
- 前記(B1)成分が、下記一般式(B11)及び(B12):
で表されるオキシムエステル化合物より成る群から選択される少なくとも1種を含む、請求項20~22のいずれか1項に記載の感光性樹脂組成物。 - 前記(AX)成分100質量部に対する前記(B1)成分及び(B2)成分の合計含有量が、0.1~10質量部である、請求項20~23のいずれか1項に記載の感光性樹脂組成物。
- 前記(AX)成分100質量部に対する前記(B1)成分及び(B2)成分の合計含有量が0.5~5質量部である、請求項20~24のいずれか1項に記載の感光性樹脂組成物。
- 前記(AY)成分100質量部に対して、
前記(D1)成分0.1~20質量部;及び
前記(D2)成分0.1~20質量部;
を含む、請求項27に記載の樹脂組成物。 - 前記(AY)成分100質量部に対して、前記(E)成分0.1~20質量部を含む、請求項28又は29に記載の樹脂組成物。
- (B)感光剤を更に含有する、請求項26~31のいずれか1項に記載の樹脂組成物。
- 以下の:
(1)請求項1~25のいずれか1項に記載の感光性樹脂組成物又は請求項32に記載の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に供して、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33に記載の製造方法により得られる硬化レリーフパターンを備える、半導体装置。
- 以下の成分:
(A)ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリオキサゾール前駆体となり得るポリヒドロキシアミド、ポリアミノアミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、ポリベンゾチアゾール、及びフェノール樹脂から成る群より選ばれる少なくとも1種の樹脂、
を含み、
架橋密度が1.0×10-4mol/cm3以上、3.0×10-3mol/cm3以下であり、かつ
5%重量減少温度が250℃以上400℃以下である、
樹脂膜。 - 前記架橋密度が、3.0×10-4mol/cm3以上、2.0×10-3mol/cm3以下である、請求項35に記載の樹脂膜。
- 前記(A)成分が、ポリイミド前駆体であるポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩、ポリアミド酸アミド、ポリアミド、ポリアミドイミド、ポリイミド、ポリベンゾオキサゾール、ポリベンゾイミダゾール、及びポリベンゾチアゾールから成る群より選ばれる少なくとも1種の樹脂である、請求項35又は36に記載の樹脂膜。
- 請求項35~37のいずれか1項に記載の樹脂膜が、ガラス転移温度が200℃以下の樹脂基板上に積層されている積層体。
- 請求項35~37のいずれか1項に記載の樹脂膜が、ガラス転移温度が250℃以下の樹脂基板上に積層されている積層体。
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0673003A (ja) * | 1992-08-28 | 1994-03-15 | Toshiba Corp | ビスマレイミド化合物及び感光性樹脂組成物 |
JPH0862847A (ja) * | 1994-08-17 | 1996-03-08 | Fuji Hanto Electron Technol Kk | ポジ型感光性組成物 |
JP2002099084A (ja) * | 2000-09-25 | 2002-04-05 | Toshiba Chem Corp | 感光性樹脂組成物およびその製造方法 |
JP2003084435A (ja) * | 2001-09-13 | 2003-03-19 | Hitachi Chemical Dupont Microsystems Ltd | ネガ型感光性樹脂組成物、パターンの製造法及び電子部品 |
JP2008058839A (ja) * | 2006-09-01 | 2008-03-13 | Asahi Kasei Electronics Co Ltd | 感光性樹脂組成物 |
JP2009251451A (ja) * | 2008-04-09 | 2009-10-29 | Hitachi Chem Co Ltd | 感光性樹脂組成物及び感光性エレメント |
JP2010090386A (ja) * | 1999-03-30 | 2010-04-22 | Asahi Kasei E-Materials Corp | 感光性樹脂組成物 |
JP2010096927A (ja) * | 2008-10-15 | 2010-04-30 | Hitachi Chemical Dupont Microsystems Ltd | 感光性樹脂組成物、該樹脂組成物を用いたパターン硬化膜の製造方法及び電子部品 |
JP2011059176A (ja) * | 2009-09-07 | 2011-03-24 | Hitachi Chem Co Ltd | 感光性樹脂組成物、永久レジスト用感光性フィルム、レジストパターンの形成方法、プリント配線板及びその製造方法、表面保護膜並びに層間絶縁膜 |
JP2011059656A (ja) * | 2009-06-04 | 2011-03-24 | Asahi Kasei E-Materials Corp | ネガ型感光性樹脂組成物、硬化レリーフパターン形成・製造方法、並びに半導体装置 |
JP2012091430A (ja) * | 2010-10-28 | 2012-05-17 | Toray Ind Inc | フィルム積層体 |
JP2013117669A (ja) * | 2011-12-05 | 2013-06-13 | Hitachi Chemical Co Ltd | 感光性樹脂組成物、並びにこれを用いた感光性フィルム、レジストパターンの形成方法及びプリント配線板 |
WO2014097594A1 (ja) * | 2012-12-21 | 2014-06-26 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体樹脂組成物 |
WO2014199800A1 (ja) * | 2013-06-12 | 2014-12-18 | Jsr株式会社 | 樹脂組成物、感光性樹脂組成物、絶縁膜およびその製法ならびに電子部品 |
WO2015046296A1 (ja) * | 2013-09-25 | 2015-04-02 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機el表示装置 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4329419A (en) * | 1980-09-03 | 1982-05-11 | E. I. Du Pont De Nemours And Company | Polymeric heat resistant photopolymerizable composition for semiconductors and capacitors |
US5925498A (en) * | 1997-06-16 | 1999-07-20 | Kodak Polychrome Graphics Llc | Photosensitive polymer composition and element containing photosensitive polyamide and mixture of acrylates |
JP4462679B2 (ja) * | 1999-03-30 | 2010-05-12 | 旭化成イーマテリアルズ株式会社 | シリコン系カップリング剤及びその用途 |
JP2001272777A (ja) * | 2000-03-24 | 2001-10-05 | Hitachi Chemical Dupont Microsystems Ltd | 感光性ポリイミド前駆体組成物及びそれを用いたパターンの製造法並びに電子部品 |
JP3809998B2 (ja) * | 2001-10-15 | 2006-08-16 | サンクス株式会社 | ガルバノスキャニング式レーザマーキング装置及びその投影像投射方法。 |
JP4046563B2 (ja) | 2002-01-25 | 2008-02-13 | 旭化成エレクトロニクス株式会社 | 高耐熱性感光性樹脂組成物 |
JP4789657B2 (ja) * | 2006-03-13 | 2011-10-12 | 旭化成イーマテリアルズ株式会社 | 感光性樹脂組成物 |
JP4695533B2 (ja) * | 2006-03-23 | 2011-06-08 | 三菱製紙株式会社 | ネガ型感光性平版印刷版 |
WO2009054487A1 (ja) * | 2007-10-26 | 2009-04-30 | Asahi Kasei Kabushiki Kaisha | ポリイミド前駆体及びポリイミド前駆体を含む感光性樹脂組成物 |
JP5758300B2 (ja) * | 2009-11-16 | 2015-08-05 | 旭化成イーマテリアルズ株式会社 | ポリイミド前駆体を含む感光性樹脂組成物、感光性フィルム、カバーレイ、及びフレキシブルプリント配線板並びにその積層体 |
JP2011204515A (ja) * | 2010-03-26 | 2011-10-13 | Toray Ind Inc | 感光性導電ペーストおよび導電パターンの製造方法 |
KR20120021488A (ko) * | 2010-08-03 | 2012-03-09 | 주식회사 동진쎄미켐 | 네가티브 감광성 수지 조성물 |
TWI430024B (zh) * | 2010-08-05 | 2014-03-11 | Asahi Kasei E Materials Corp | A photosensitive resin composition, a method for manufacturing a hardened bump pattern, and a semiconductor device |
JP2013114238A (ja) * | 2011-12-01 | 2013-06-10 | Toray Ind Inc | ポジ型感光性組成物、そのポジ型感光性組成物から形成された硬化膜、およびその硬化膜を有する素子。 |
JP2013205801A (ja) * | 2012-03-29 | 2013-10-07 | Sumitomo Bakelite Co Ltd | 感光性樹脂組成物及びその硬化膜、保護膜、絶縁膜並びに半導体装置及び表示体装置 |
JP6190805B2 (ja) * | 2012-05-07 | 2017-08-30 | 旭化成株式会社 | 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 |
-
2015
- 2015-03-16 CN CN201580013242.7A patent/CN106104381B/zh active Active
- 2015-03-16 WO PCT/JP2015/057678 patent/WO2015141618A1/ja active Application Filing
- 2015-03-16 JP JP2016508712A patent/JP6388640B2/ja active Active
- 2015-03-16 CN CN201911142158.1A patent/CN110941142B/zh active Active
- 2015-03-16 KR KR1020167022632A patent/KR101934171B1/ko active IP Right Grant
- 2015-03-17 TW TW104108538A patent/TWI548674B/zh active
-
2017
- 2017-07-18 JP JP2017139394A patent/JP6491704B2/ja active Active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0673003A (ja) * | 1992-08-28 | 1994-03-15 | Toshiba Corp | ビスマレイミド化合物及び感光性樹脂組成物 |
JPH0862847A (ja) * | 1994-08-17 | 1996-03-08 | Fuji Hanto Electron Technol Kk | ポジ型感光性組成物 |
JP2010090386A (ja) * | 1999-03-30 | 2010-04-22 | Asahi Kasei E-Materials Corp | 感光性樹脂組成物 |
JP2002099084A (ja) * | 2000-09-25 | 2002-04-05 | Toshiba Chem Corp | 感光性樹脂組成物およびその製造方法 |
JP2003084435A (ja) * | 2001-09-13 | 2003-03-19 | Hitachi Chemical Dupont Microsystems Ltd | ネガ型感光性樹脂組成物、パターンの製造法及び電子部品 |
JP2008058839A (ja) * | 2006-09-01 | 2008-03-13 | Asahi Kasei Electronics Co Ltd | 感光性樹脂組成物 |
JP2009251451A (ja) * | 2008-04-09 | 2009-10-29 | Hitachi Chem Co Ltd | 感光性樹脂組成物及び感光性エレメント |
JP2010096927A (ja) * | 2008-10-15 | 2010-04-30 | Hitachi Chemical Dupont Microsystems Ltd | 感光性樹脂組成物、該樹脂組成物を用いたパターン硬化膜の製造方法及び電子部品 |
JP2011059656A (ja) * | 2009-06-04 | 2011-03-24 | Asahi Kasei E-Materials Corp | ネガ型感光性樹脂組成物、硬化レリーフパターン形成・製造方法、並びに半導体装置 |
JP2011059176A (ja) * | 2009-09-07 | 2011-03-24 | Hitachi Chem Co Ltd | 感光性樹脂組成物、永久レジスト用感光性フィルム、レジストパターンの形成方法、プリント配線板及びその製造方法、表面保護膜並びに層間絶縁膜 |
JP2012091430A (ja) * | 2010-10-28 | 2012-05-17 | Toray Ind Inc | フィルム積層体 |
JP2013117669A (ja) * | 2011-12-05 | 2013-06-13 | Hitachi Chemical Co Ltd | 感光性樹脂組成物、並びにこれを用いた感光性フィルム、レジストパターンの形成方法及びプリント配線板 |
WO2014097594A1 (ja) * | 2012-12-21 | 2014-06-26 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体樹脂組成物 |
WO2014199800A1 (ja) * | 2013-06-12 | 2014-12-18 | Jsr株式会社 | 樹脂組成物、感光性樹脂組成物、絶縁膜およびその製法ならびに電子部品 |
WO2015046296A1 (ja) * | 2013-09-25 | 2015-04-02 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機el表示装置 |
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2018197863A (ja) * | 2015-08-21 | 2018-12-13 | 旭化成株式会社 | 感光性樹脂組成物、ポリイミドの製造方法および半導体装置 |
KR101857148B1 (ko) * | 2015-11-12 | 2018-05-11 | 삼성에스디아이 주식회사 | 신규한 가교제를 포함하는 감광성 수지 조성물 및 이를 이용한 유기막 |
WO2017099019A1 (ja) * | 2015-12-08 | 2017-06-15 | 富士フイルム株式会社 | 感放射線性樹脂組成物、硬化膜、パターン形成方法、固体撮像素子および画像表示装置 |
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JP2017219850A (ja) | 2017-12-14 |
CN106104381B (zh) | 2019-12-13 |
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JP6388640B2 (ja) | 2018-09-12 |
JPWO2015141618A1 (ja) | 2017-04-06 |
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CN110941142B (zh) | 2021-05-25 |
CN110941142A (zh) | 2020-03-31 |
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CN106104381A (zh) | 2016-11-09 |
KR20160110496A (ko) | 2016-09-21 |
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