WO2015190476A1 - 感光性樹脂組成物、レジスト積層体及びそれらの硬化物(11) - Google Patents
感光性樹脂組成物、レジスト積層体及びそれらの硬化物(11) Download PDFInfo
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- WO2015190476A1 WO2015190476A1 PCT/JP2015/066592 JP2015066592W WO2015190476A1 WO 2015190476 A1 WO2015190476 A1 WO 2015190476A1 JP 2015066592 W JP2015066592 W JP 2015066592W WO 2015190476 A1 WO2015190476 A1 WO 2015190476A1
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- resin composition
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- epoxy
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- FQYUMYWMJTYZTK-UHFFFAOYSA-N C(C1OC1)Oc1ccccc1 Chemical compound C(C1OC1)Oc1ccccc1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
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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
Definitions
- the present invention relates to a photosensitive resin composition and a cured product thereof. More specifically, the present invention relates to a photosensitive resin excellent in image forming property with excellent side wall shape and resolution, small residual stress of the cured product, preventing warping of the substrate, and excellent in substrate adhesion after the wet heat test.
- the present invention relates to a composition and a cured product thereof.
- the photosensitive resin composition of the present invention having such excellent characteristics and its cured product are MEMS (microelectromechanical system) parts, ⁇ -TAS (micrototal analysis system) parts, microreactor parts, capacitors, inductors, etc.
- photoresists those that can be processed by photolithography are called photoresists, and are widely used for semiconductors, MEMS / micromachine applications, and the like.
- photolithography is achieved by patterning exposure on a substrate and then developing with a developer to selectively remove exposed or non-exposed areas.
- the positive part is that the exposed part is dissolved in the developer, while the negative part is that which is insoluble.
- advanced technology electro-package applications and MEMS applications not only the ability to form a uniform spin coating film, but also a high aspect ratio, a vertical sidewall shape in a thick film, a high adhesion to a substrate, and the like are required.
- the aspect ratio is an important characteristic calculated by resist film thickness / pattern line width and showing the performance of photolithography.
- the composition mainly composed of bisphenol A novolak type epoxy resin disclosed in Patent Document 1 and Non-Patent Document 1 has a very high resolution, and by using the composition, high aspect ratio photosensitive image formation is achieved. In addition, it is possible to form a cured photosensitive resin.
- the resin cured product obtained using the composition has a very high residual stress value, so that the substrate is greatly warped after photolithography processing using a silicon wafer or the like as a substrate, damaging the manufactured device or increasing the yield. There was a problem that would decrease. Further, since the residual stress is high, cracking (crazing) may occur during development, and peeling may easily occur between the substrate and the cured resin.
- Patent Document 2 describes that a resin composition containing a bisphenol-type epoxy resin, an alicyclic epoxy resin, and a photocationic polymerization initiator is excellent in adhesion to a Ni / Si wafer.
- Patent Document 3 a photosensitive resin composition containing an epoxy resin having a specific epoxy equivalent and a softening point, a phenolic curing agent having a specific hydroxyl equivalent, and a photoacid generator is used for adhesion to a silicon wafer. It is described that it is excellent.
- Patent Document 4 describes that a photosensitive resin composition containing a bisphenol-type epoxy resin, a phenol novolac epoxy resin having a specific structure, and a photocationic polymerization initiator is excellent in adhesion to a silicon wafer.
- Patent Document 5 discloses a comb-shaped electrode in which a plurality of metal films are stacked on a piezoelectric substrate such as lithium tantalate (LT), and an organic film that can be subjected to photolithography as an insulating film on the electrode.
- LT lithium tantalate
- a technique is described in which a frequency filter element can be manufactured in a small size and at low cost by using a resin.
- polyimide requires high-temperature curing conditions, causing damage to the device, and epoxy resin can be cured at low temperatures, but the residual stress of the cured product is high, so the substrate warps, film cracks, after wet heat treatment There are disadvantages such as easy adhesion deterioration on the Pt film and the LT substrate.
- the present invention has been made in view of the above circumstances, and is an epoxy resin composition that is cured by photocationic polymerization in the field of semiconductor and MEMS / micromachine applications, and the residual stress of the cured product is extremely low. It aims at providing the resin composition excellent in adhesiveness with metal substrates, such as Pt, LT, and Ta after a wet heat test, and / or its laminated body, and its hardened
- metal substrates such as Pt, LT, and Ta after a wet heat test, and / or its laminated body, and its hardened
- the present inventors have solved the above problems by using a photosensitive resin composition containing an epoxy resin having a specific structure, a compound having a phenolic hydroxyl group having a specific structure, and a photocationic polymerization initiator. I found that it can be solved.
- the weighted average epoxy equivalent of the epoxy resin is 300 g / eq. That's it, 20% by mass or more of the epoxy resin (A) is represented by the following formula (1)
- m is an average value and represents a real number in the range of 3 to 35
- Epoxy resin The compound (B) having a phenolic hydroxyl group is represented by the following formulas (2), (4), (5) and (6).
- n is an average value and represents a real number in the range of 1 to 10.
- Each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- q is an average value and represents a real number in the range of 1 to 10.
- z is an average value and represents a real number in the range of 1 to 10.
- y is an average value and represents a real number in the range of 1 to 10.
- R 8 and R 9 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
- the said photosensitive resin composition containing the 1 or more types of phenolic compound chosen from the group which consists of the phenolic compound represented. [2].
- the epoxy resin is represented by the following formula (3)
- a is an average value and represents a real number in the range of 2 to 30.
- X independently represents a hydrogen atom or a glycidyl group, and at least one of a plurality of Xs is a glycidyl group.
- B a compound having a phenolic hydroxyl group per equivalent of epoxy resin. [4].
- the photosensitive resin composition of the present invention can form a fine and vertical sidewall shape pattern by photolithography.
- the cured product has characteristics such as high resolution, high sensitivity, and excellent adhesion to a metal substrate such as Pt, LT and Ta after a wet heat test. Therefore, by using the photosensitive resin composition of the present invention, it is necessary for semiconductor and MEMS / micromachine application fields, in particular, for MEMS devices, semiconductor devices, frequency filter device package parts, microreactor forming parts, and inkjet printhead parts. Permanent resists and cured products having the characteristics as described above can be obtained.
- the photosensitive resin composition of the present invention has a weighted average epoxy equivalent of 300 g / eq.
- the above (A) epoxy resin is contained.
- the weighted average epoxy equivalent referred to here means the average epoxy equivalent of all the epoxy resin components contained in (A) the epoxy resin.
- the epoxy equivalent is 100 g / eq. 2 mol of epoxy resin and an epoxy equivalent of 400 g / eq.
- the epoxy equivalent in the present invention means a measured value obtained according to JIS K-7236.
- the weighted average epoxy equivalent is more preferably 400 g / eq. That's it.
- the (A) epoxy resin contained in the photosensitive resin composition of the present invention contains a bifunctional epoxy resin generally represented by the above formula (1) and called a bisphenol F type epoxy resin (compound).
- m is an average value and represents a real number in the range of 3 to 35.
- the “average value” here means the average number of repetitions.
- the epoxy resin represented by the formula (1) contained in the photosensitive composition of the present invention has m in the formula (1) of 0 or more and less than 3 as long as the average value m is in the range of 3 to 35. Or an epoxy resin (epoxy compound) corresponding to one having m exceeding 35 may be used in combination.
- the epoxy equivalent of the epoxy resin represented by the formula (1) is usually 500 to 4500 g / eq. It is. 700 to 3000 g / eq. In terms of sensitivity and developability of the photosensitive resin composition and strength and durability of the cured product. It is more preferable that The average value m of the epoxy resin represented by the formula (1) having such a preferable epoxy equivalent is 4 to 22.
- bisphenol F type epoxy resins having an average value m of 3 to 35 include jER4004P (m in Formula (1) of about 5.3 to 6.4, epoxy equivalent of 840 to 975 g / eq. ), JER4005P (m in formula (1) is about 6.2 to 8.2, epoxy equivalent is 950 to 1200 g / eq.) And jER4007P (m in formula (1) is about 14.4 to 18.3, epoxy equivalent) 2000 to 2500 g / eq.), JER4010P manufactured by Mitsubishi Chemical Corporation (m in the formula (1) is about 28.5 to 34.7, epoxy equivalent is 3800 to 4600 g / eq.), And the like.
- the photosensitive resin composition of the present invention has a weighted average epoxy equivalent of 300 g / eq. If it is in the range used as the above, you may use together 1 type, or multiple types, such as epoxy resins (compound) other than the epoxy resin represented by Formula (1), and a reactive epoxy monomer.
- epoxy resins compound
- a reactive epoxy monomer Commercially available products of bisphenol F type epoxy resins having an average value m of less than 3 that can be used in combination include YDF-8170C manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
- a bisphenol F type epoxy resin having three or more epoxy groups in one molecule represented by the above formula (3) is preferably used in combination.
- a is an average value and represents a real number in the range of 2 to 30.
- the “average value” here means the average number of repetitions.
- the epoxy resin represented by Formula (3) can be obtained by glycidylating the alcoholic hydroxyl group of the polycondensate of bisphenol F and epichlorohydrin using epichlorohydrin.
- the ratio of the alcoholic hydroxyl group to be glycidylated is not particularly limited, but considering the balance of physical properties, about 50 to 80% of the alcoholic hydroxyl group of the polycondensate of bisphenol F and epichlorohydrin is glycidylated.
- An epoxy resin is preferable.
- Specific examples of commercially available epoxy resins represented by formula (3) include NER-7604 and NER-7403 (both are trade names, manufactured by Nippon Kayaku Co., Ltd.).
- the epoxy equivalent of the epoxy resin represented by the formula (3) is 250 to 400 g / eq.
- the softening point is preferably 60 to 85 ° C.
- epoxy resins examples include Epicoat 157 (trade name, bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 180 to 250 g / eq., Softening point of 80 to 90 ° C.), EPON SU -8 (trade name, bisphenol A novolac type epoxy resin, manufactured by Momentive, epoxy equivalent of 195 to 230 g / eq.), NC-3000 (trade name, biphenyl-phenol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent) 270 to 300 g / eq.), NER-1302 (trade name, bisphenol A type epoxy resin partially epoxidized with alcoholic hydroxyl group, Nippon Kayaku Co., Ltd., epoxy equivalent 200 to 500 g / eq.), EOCN- 1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 190-210 / Eq.), NC-6300H (trade name,
- reactive epoxy monomers that can be used in combination include diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (ADEKA, ED506), trimethylolpropane triglycidyl ether. (ADEKA, ED505), trimethylolpropane triglycidyl ether (low chlorine type, Nagase ChemteX, EX321L), pentaerythritol tetraglycidyl ether, and the like.
- the proportion of the epoxy resin represented by formula (1) in the entire epoxy resin (A) is usually 20% by mass or more, preferably 35 It is at least mass%.
- the compound (B) having a phenolic hydroxyl group contained in the photosensitive resin composition of the present invention is selected from the group consisting of phenol compounds represented by the above formulas (2), (4), (5) and (6). Containing one or more phenolic compounds.
- the “average value” that n, q, z, and y in the formulas (2), (4), (5), and (6) mean the average number of repetitions.
- Examples of the phenol compound represented by the formula (2) include phenol novolak and cresol novolak, and phenol novolak is preferably used because the photosensitive resin composition is excellent in coatability.
- the phenol compound represented by the formula (2) preferably has a softening temperature of 50 ° C. or higher and 150 ° C.
- phenol novolak having a softening temperature of 50 ° C. or higher and 150 ° C.
- PN-152 (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 50 ° C., hydroxyl group equivalent 105 g / eq.)
- H-1 (trade name) , Manufactured by Meiwa Kasei Co., Ltd., softening point 80 ° C., hydroxyl group equivalent 104 g / eq.)
- TD-2131 (trade name, manufactured by DIC, softening point 80 ° C., hydroxyl group equivalent 105 g / eq.)
- KA-1160 (trade name, DIC Corporation, softening point 81 ° C., hydroxyl group equivalent 117 g / eq.) And the like.
- the hydroxyl group equivalent of phenol novolac is 80 to 200 g / eq. From the viewpoint of compatibility with (A) epoxy resin and low moisture permeability of the cured product. In the range of 80 to 130 g / eq. Is more preferably in the range of 100 to 120 g / eq. More preferably, it is the range.
- (B) A compound having a phenolic hydroxyl group may be used in combination with a plurality of phenol compounds represented by the formula (2).
- Examples of the phenol compound represented by the formula (4) include bisphenol A type novolak. Specific examples thereof include VH-4150 (trade name, manufactured by DIC, softening point 85 ° C., hydroxyl equivalent weight 118 g / eq.), VH-4170 (trade name, manufactured by DIC, softening point 103 ° C., hydroxyl equivalent weight 118 g / eq.). eq.), MEP-6309E (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 81 ° C., hydroxyl group equivalent 116 g / eq.) and the like.
- a compound having a phenolic hydroxyl group may be used in combination with a plurality of phenol compounds represented by the formula (4).
- Biphenylphenol novolac is mentioned as a phenolic compound represented by Formula (5).
- a phenolic compound represented by Formula (5) Specific examples thereof include KAYAHARD GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point 65 ° C., hydroxyl group equivalent 200 g / eq.) And the like.
- a compound having a phenolic hydroxyl group may be used in combination with a plurality of phenol compounds represented by the formula (5).
- the phenol compound represented by the formula (6) include phenol aralkyl resins. Specific examples thereof include Milex XLC-3L (trade name, manufactured by Mitsui Chemicals, softening point 77 ° C., hydroxyl group equivalent 176 g / eq.
- a compound having a phenolic hydroxyl group may be used in combination with a plurality of phenol compounds represented by formula (6).
- the compound having a phenolic hydroxyl group is one or more phenolic compounds selected from the group consisting of phenol compounds represented by formulas (2), (5) and (6). contains.
- the content of the compound (B) having a phenolic hydroxyl group in the photosensitive resin composition of the present invention is such that (B) the hydroxyl group equivalent of the compound having a phenolic hydroxyl group is equivalent to 1 equivalent of the epoxy group of the epoxy resin.
- the amount is usually 0.1 to 0.9 equivalent, preferably 0.2 to 0.5 equivalent.
- each compound which has a phenolic hydroxyl group represented by Formula (2), (4), (5) and (6), each compound which has a phenolic hydroxyl group
- the ratio of use is not particularly limited as long as the sum of the blend ratios of (B) the phenolic compound having a phenolic hydroxyl group with respect to the mass of (A) the epoxy resin is within the above range.
- the photosensitive resin composition of the present invention has a phenolic hydroxyl group other than the phenolic compound represented by formula (2), (4), (5) or (6) as long as the effects of the present invention are not impaired. You may use together the compound which has this.
- the compound having a phenolic hydroxyl group that can be used in combination include, but are not limited to, the phenol compounds described as the raw material of the epoxy resin in the section of the epoxy resin that can be used in combination.
- the photocationic polymerization initiator (C) contained in the photosensitive resin composition of the present invention generates cations upon irradiation with ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays and electron beams.
- the cation is a compound that can be a polymerization initiator for the epoxy resin (A).
- An onium complex salt is mentioned as a photocationic polymerization initiator.
- Typical examples of onium complex salts include aromatic iodonium complex salts and aromatic sulfonium complex salts.
- aromatic iodonium complex salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, tolyl Miliodonium tetrakis (pentafluorophenyl) borate (Rhodia, trade name Rhodosyl PI2074), di (4-tert-butyl) iodonium tris (trifluoromethanesulfonyl) methanide (BASF, trade name CGI BBI-C1), etc. Can be mentioned.
- aromatic sulfonium complex salt examples include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by Sun Apro, trade name CPI-101A), thiophenyldiphenylsulfonium tris (pentafluoroethyl) trifluoro Phosphate (trade name CPI-210S, manufactured by San Apro), 4- ⁇ 4- (2-chlorobenzoyl) phenylthio ⁇ phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (trade name SP-172, manufactured by ADEKA)
- a mixture of aromatic sulfonium hexafluoroantimonate containing 4-thiophenyldiphenylsulfonium hexafluoroantimonate ACETO Corporate USA, trade name CPI-6976
- Phenylsulfonium tris trifluoromethane
- the hexafluoroantimonate salt type is inexpensive, but is easy to generate hydrogen fluoride upon decomposition, and is therefore suitable for applications that do not directly contact metals.
- the metide salt type and borate salt type do not generate hydrogen fluoride, and thus can be suitably used for all applications including those in contact with metals. These can be used alone or in combination of two or more.
- the content of the (C) photocationic polymerization initiator in the photosensitive resin composition of the present invention means the solid content of the photosensitive resin composition of the present invention (the total of all components excluding the solvent). Used) is usually 0.3 to 15% by mass, preferably 0.5 to 10% by mass.
- the photosensitive resin composition of the present invention may further contain (D) an epoxy group-containing silane compound.
- an epoxy group-containing silane compound By using an epoxy group-containing silane compound, in the step of using the composition of the present invention, the adhesion to the substrate and the interlayer adhesion when a multilayer structure is formed by the composition of the present invention improves.
- Specific examples of the epoxy group-containing silane compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4) -Epoxycyclohexyl) Epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane.
- the content of the (D) epoxy group-containing silane compound in the photosensitive resin composition of the present invention is usually 15% by mass or less, preferably 1 to 10% by mass, based on the solid content of the photosensitive resin composition.
- the solvent can be used for the photosensitive resin composition of this invention, in order to reduce the viscosity of a resin composition and to improve coating-film property.
- the solvent is an organic solvent that is usually used for ink, paint, etc., and can dissolve each constituent component of the photosensitive resin composition and does not cause a chemical reaction with the constituent component.
- Specific examples of the solvent (E) include ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone and cyclopentanone, aromatic hydrocarbons such as toluene, xylene and methoxybenzene, dipropylene glycol dimethyl ether and dipropylene glycol.
- substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C1-C4 alkyl group, sulfonic acid alkyl ester group, carboxylic acid alkyl ester group and the like.
- alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include C1-C4 alkyl.
- the substitution position of these substituents is preferably the 2-position.
- thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like.
- 2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd., trade name Kayacure DETX-S
- 2-isopropylthioxanthone are preferable.
- Examples of the 9,10-dialkoxyanthracene derivative include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dimethoxy-2.
- sensitizers can be used singly or in combination of two or more, but the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene is most preferable. Since the sensitizer component exhibits an effect in a small amount, the content of the sensitizer in the photosensitive resin composition of the present invention is usually 30% by mass with respect to the content of the (C) photocationic polymerization initiator. Hereinafter, it is preferably 20% by mass or less.
- an ion catcher may be added as necessary.
- the ion catcher include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxyaluminum and trisbutoxyaluminum and other alkoxyaluminums, trisphenoxyaluminum and trisparamethylphenoxyaluminum and other phenoxyaluminums, tris Acetoxyaluminum, trisstearatoaluminum, trisbutyratealuminum, trispropionatoaluminum, trisacetylacetonatoaluminum, tristrifluoroacetylacetonatoaluminum, trisethylacetoacetatoaluminum, diacetylacetonatodipi
- the antifoaming agent examples include silicone-based, fluoroalkyl-based, and polymer-based antifoaming agents.
- the content is 10% by mass or less based on the solid content of the photosensitive resin composition of the present invention excluding the solvent. Depending on, it can be increased or decreased as appropriate.
- the photosensitive resin composition of the present invention includes, for example, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, montmorillonite, mica powder, etc.
- Any inorganic filler, and any organic filler such as polymethyl methacrylate, rubber, fluoropolymer, polyurethane powder can be used.
- the content of these inorganic and / or organic fillers is 60% by mass or less based on the solid content of the photosensitive resin composition of the present invention, but depending on the purpose of use and the required function of the cured film, It can be increased or decreased as appropriate.
- the photosensitive resin composition of the present invention is preferably used in a liquid form to which a solvent is added for coating on a substrate.
- the spin coating method comprising a step of dropping the photosensitive resin composition of the present invention diluted to a desired viscosity with a solvent onto a substrate, accelerating the substrate to a constant rotational speed, and maintaining the rotational speed constant, It can apply
- the photosensitive resin composition may be applied to the substrate by other coating methods such as roller coating, doctor knife coating, slot coating, dip coating, gravure coating, and spray coating. it can. After coating, dry baking is performed to evaporate the solvent. Dry bake conditions are selected to form a semi-cured dry film of the photoresist.
- the substrate is in contact with or close to the surface of the surface of the hot plate. Heating is performed at 65 ° C. for 1 to 15 minutes, followed by 90 to 125 ° C. for 5 to 120 minutes. Alternatively, the dry bake can be performed in a convection oven.
- the dried photosensitive resin composition layer is passed through a photomask on which a desired mask pattern is drawn, exposed to near-ultraviolet light from an intermediate-pressure or ultrahigh-pressure mercury lamp, 300 to 500 nm emission line, or from a synchrotron radiation source.
- a photosensitive image can be formed by irradiating energy beam with X-ray radiation or irradiating electron beam radiation directly or through patterned exposure. For mask exposure, close contact, proximity, or projection printing can be used. Subsequent to exposure, post-exposure baking is performed to accelerate the polymerization reaction by acid catalysis of the exposed areas on the photosensitive resin composition layer. Typical conditions are 1 to 5 minutes at 65 ° C. and then 1 to 60 minutes at 95 ° C., depending on the thickness of the coating on the hot plate and the thermal conductivity and thickness of the substrate.
- the film is typically immersed in an organic solvent developer for 2 to 30 minutes depending on the thickness of the coating film and the solvent titer of the developer solvent. Further, the developed image is rinsed by applying a rinsing solvent, and the developer adhering to the cured film is removed.
- the attached developer contains a dissolved photoresist component, and when dried, it becomes a residue on the photosensitive image and is likely to cause contamination, so it must be removed.
- the developer solvent may be applied by spraying using either an explosion-proof atomizing spray nozzle or an explosion-proof micro shower head spray nozzle.
- a method of applying a developer using a paddle method can be mentioned.
- Developers include, but are not limited to, propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, acetone, cyclopentanone, diacetone alcohol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, anisole, and ethyl lactate. It is preferable to use propylene glycol monomethyl ether acetate having good solubility in the unexposed area and relatively inexpensive.
- the rinsing liquid include the developer solvent described above, methanol, ethanol, isopropanol, and n-butyl acetate. Of these, acetone, ethanol, and isopropanol are particularly preferable because they can be washed quickly and dried quickly.
- a heat treatment is performed at 130 to 200 ° C. to thermally cure the film, thereby obtaining a permanent protective film satisfying various characteristics.
- Substrate materials that can be used for the photosensitive resin composition of the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, Examples include steel, copper-silicon alloy, indium-tin oxide-coated glass, organic films such as polyimide and polyester, metal, semiconductor, and any substrate containing a patterning region of an insulating material. Since the photosensitive resin composition of this invention is excellent in adhesiveness with substrates, such as Pt, LT, Au, and Ta, it is preferable to use for these metal substrates or a board
- the photosensitive resin composition of the present invention can be sandwiched between substrates and used as a resist laminate.
- a photosensitive resin composition diluted with a solvent using a roll coater, die coater, knife coater, bar coater, gravure coater, etc. on a base film (base material)
- the temperature is set to 45 to 100 ° C.
- the resist laminate can be obtained by removing the solvent with a drying oven and laminating a cover film (base material) or the like as necessary.
- the thickness of the resist on the base film is adjusted to 2 to 100 ⁇ m.
- films, such as polyester, a polypropylene, polyethylene, TAC, a polyimide are used, for example.
- a film subjected to a release treatment with a silicone-type release treatment agent, a non-silicone-type release treatment agent, or the like may be used as necessary.
- the cover film is peeled off and transferred to a substrate at a temperature of 40 to 100 ° C. and a pressure of 0.05 to 2 MPa by a hand roll, a laminator, etc., and the liquid photosensitive resin is used. Similar to the composition, exposure, post-exposure baking, development, and heat treatment may be performed.
- the photosensitive resin composition of the present invention is applied to a substrate, dried, and then a first layer photosensitive resin. Form a coating film.
- the first layer is exposed and baked after exposure.
- the second layer is exposed and baked after exposure. It is possible to form a complicated multilayer structure pattern by repeating this process and finally performing development and hard baking at the end.
- the first layer is developed, hard baked, the second layer is applied and dried, alignment exposure is performed through a photomask, and development and hard baking are repeated to form a multilayer structure pattern.
- Each photosensitive resin layer may be formed by laminating a dry film resist.
- the “package” is a sealing method or a sealed one used to block the ingress of gas or liquid in the outside air in order to maintain the stability of the substrate, wiring, elements, and the like.
- the package described in the present invention is performed in order to prevent deterioration of a package having a driving unit such as a MEMS, a hollow package for packaging a vibrator such as a SAW device, a semiconductor substrate, a printed wiring board, wiring, or the like.
- “Wafer level package” means that the protective film, terminals, wiring processing, and package are performed in the state of the wafer, and then cut into chips and separated into individual pieces.
- the orifice plate for fine micro or nano channels and inkjet nozzles Represents a method of three-dimensionally processing in a wafer.
- the photosensitive resin composition of the present invention By using the photosensitive resin composition of the present invention, it is possible to form a fine and vertical sidewall shape pattern by photolithography.
- the cured product has characteristics of low stress, low warpage, and excellent heat and humidity resistance. Permanent resists and cured products that satisfy the characteristics required for semiconductor and MEMS / micromachine application fields, especially for MEMS devices, semiconductor devices, frequency filter device package parts, microreactor forming parts, and inkjet printhead parts, can be obtained. It is very useful in these fields.
- Examples 1 to 10 and Comparative Examples 1 to 4 (Preparation of photosensitive resin composition solution (liquid resist))
- D) The epoxy group-containing silane compound is diluted with cyclopentanone so that the concentration becomes 65% by mass, and stirred and dissolved in a flask with a stirrer at 80 ° C. for 3 hours. After standing to cool, the pore size is 1.0 ⁇ m. Filtration was performed with a membrane filter to obtain a photosensitive resin composition solution (liquid resist) for comparison with the present invention.
- PEB post-exposure baking
- SU-8 Developer trade name, manufactured by Microchem Corp., main component of propylene glycol monomethyl ether acetate
- the resin film cures and shrinks, it becomes a compressive stress, and the stress of the cured film increases the warpage of the substrate with the magnitude of the stress, and the film itself also generates cracks such as crazing and cracks. As the internal stress is smaller, the warpage of the substrate is reduced and the crack of the film itself is also eliminated.
- a silicon wafer having a Pt metal vapor deposition of 200 nm, an LT substrate, and a silicon wafer having a Ta vapor deposition of 100 nm were prepared, and the liquid resists obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were formed on these substrates as described above. Coated.
- the optimal exposure dose of each composition obtained in the sensitivity evaluation test was irradiated through a photomask provided with a test pattern for adhesion strength evaluation.
- the PEB and subsequent hard baking steps were the same as the stress evaluation test steps described above, and a resin pattern cured on the silicon wafer was obtained.
- (A-1) to (D) are as follows. Moreover, the weighted average epoxy equivalent was calculated
- ⁇ (A) component epoxy resin> (A-1) jER4004P (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin having an average number of repetitions m ⁇ 5.6 in the formula (1), epoxy equivalent of 868 g / eq.) (A-2) jER4005P (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin having an average number of repetitions m ⁇ 7.0 in the formula (1), epoxy equivalent of 1046 g / eq.) (A-3) jER4007P (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin having an average number of repetitions m ⁇ 16.1 in formula (1), epoxy equivalent of 2218 g / eq.) (A-5) YDF-8170C (trade name, manufactured by Nippon Steel & Sumikin Chemical Co.,
- ⁇ (B) component a compound having a phenolic hydroxyl group> (B-1) PN-152 (trade name, manufactured by Meiwa Kasei Co., Ltd., phenol compound represented by formula (2), hydroxyl group equivalent: 105 g / eq.) (B-2) H-1 (trade name, manufactured by Meiwa Kasei Co., Ltd., phenol compound represented by formula (2), hydroxyl group equivalent: 104 g / eq.) (B-3) KAYAHARD GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., phenol compound represented by formula (5), hydroxyl group equivalent: 200 g / eq.) (B-4) XL-225-3L (trade name, manufactured by Mitsui Chemicals, phenol compound represented by formula (6), hydroxyl group equivalent: 172 g / eq.) ⁇ (C) component: Photocationic polymerization initiator> (C-1) Irgacure PAG
- the characteristics of the composition obtained from each example are as follows: the optimum exposure amount is small and the sensitivity is high; the resolution dimension of the photosensitive pattern is high; the internal stress is low; It did not occur, and it was found that the adhesion after wet heat was maintained.
- Example 11 resist laminate comprising the photosensitive resin composition of the present invention
- ethylene glycol dimethyl ether was further added to the composition ratio of Example 1 in Table 1, and the mixture was stirred and dissolved in a flask with a stirrer at 50 ° C. for 1 hour, and diluted so that the solution viscosity at 25 ° C. was 2 Pa ⁇ s.
- membrane filtration with a pore size of 1.0 ⁇ m was performed to obtain a lacquer for dry film resist of the photosensitive resin composition of the present invention.
- This lacquer was uniformly applied on a base film (made of polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness: 38 ⁇ m), and dried by a hot air convection dryer at 65 ° C. for 5 minutes and at 80 ° C. for 15 minutes. Thereafter, a cover film (made of polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness: 38 ⁇ m) is laminated on the exposed surface, and a resist laminate (photosensitive resin composition laminate) formed by sandwiching a dry film resist with a film thickness of 20 ⁇ m is sandwiched. Obtained.
- the photosensitive resin composition of the present invention can form a fine and vertical sidewall shape pattern by a photolithography technique.
- the cured product has excellent heat and moisture resistance and high adhesion properties. Permanent resists and cured products having characteristics required for semiconductor and MEMS / micromachine application fields, in particular, MEMS device, semiconductor device, frequency filter device package parts, microreactor forming parts, and inkjet printhead parts can be obtained.
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Abstract
Description
[1].(A)エポキシ樹脂、(B)フェノール性水酸基を有する化合物及び(C)光カチオン重合開始剤を含有する感光性樹脂組成物であって、
(A)エポキシ樹脂の加重平均エポキシ当量が300g/eq.以上であり、
該(A)エポキシ樹脂の20質量%以上が、下記式(1)
該(B)フェノール性水酸基を有する化合物が、下記式(2)、(4)、(5)及び(6)
[2].(A)エポキシ樹脂が、下記式(3)
[3].(A)エポキシ樹脂1当量に対して(B)フェノール性水酸基を有する化合物を0.1~0.9当量含有する上記[1]又は[2]項に記載の感光性樹脂組成物。
[4].(C)光カチオン重合開始剤がオニウム錯塩系の光カチオン重合開始剤である上記[1]~[3]項のいずれか一項に記載の感光性樹脂組成物。
[5].(D)エポキシ基含有シラン化合物を含有する上記[1]~[4]項のいずれか一項に記載の感光性樹脂組成物。
[6].(E)溶剤を含有する上記[1]~[5]項のいずれか一項に記載の感光性樹脂組成物。
[7].上記[1]~[6]項のいずれか一項に記載の感光性樹脂組成物の硬化物。
[8].上記[1]~[6]項のいずれか一項に記載の感光性樹脂組成物を基材で挟み込んで得られるレジスト積層体。
[9].上記[8]項に記載のレジスト積層体から得られるドライフィルムレジストの硬化物。
本発明の感光性樹脂組成物は、加重平均エポキシ当量が300g/eq.以上の(A)エポキシ樹脂を含有する。ここで言う加重平均エポキシ当量とは、(A)エポキシ樹脂に含有される全てのエポキシ樹脂成分の平均エポキシ当量を意味し、例えばエポキシ当量が100g/eq.のエポキシ樹脂を2モルとエポキシ当量が400g/eq.のエポキシ樹脂を1モル含有する場合の加重平均エポキシ当量は、(100×2モル+400×1モル)/(2モル+1モル)=200g/eq.となる。尚、本発明におけるエポキシ当量は、JIS K-7236に準じて得られた測定値を意味する。加重平均エポキシ当量は、より好ましくは400g/eq.以上である。
式(1)中、mは平均値であり、3~35の範囲にある実数を表す。ここで言う「平均値」とは、平均繰り返し数を意味する。例えば、式(1)におけるmが2の構造の化合物を1モル、mが3の構造の化合物を2モル、mが4の構造の化合物を3モル及びmが5の構造の化合物を1モル含むエポキシ樹脂の平均値mは、(2×1モル+3×2モル+4×3モル+5×1モル)/(1モル+2モル+3モル+1モル)≒3.57となる。同様に、mが0の構造の化合物を2モル、mが5の構造の化合物を3モル、mが6の構造の化合物を3モル、mが7の構造の化合物を3モル及びmが32の構造の化合物を1モル含むエポキシ樹脂の平均値mは、(0×2モル+5×3モル+6×3モル+7×3モル+32×1モル)/(2モル+3モル+3モル+3モル+1モル)≒7.17となる。即ち、本発明の感光性組成物が含有する式(1)で表されるエポキシ樹脂は、平均値mが3~35の範囲でありさえすれば、式(1)におけるmが0以上3未満に相当する化合物やmが35を超えるものに相当するエポキシ樹脂(エポキシ化合物)を併用していてもよい。
併用し得る平均値mが3未満のビスフェノールF型エポキシ樹脂の市販品としては、新日鉄住金化学社製のYDF-8170C(式(1)におけるmが0~0.1程度、エポキシ当量155~165g/eq.)、三菱化学社製のjER806(式(1)におけるmが0~0.1程度、エポキシ当量160~170g/eq.)及びjER807(式(1)におけるmが0~0.2程度、エポキシ当量160~175g/eq.)、DIC社製のEPICLON EXA830CRP(式(1)におけるmが0~0.1程度、エポキシ当量155~163g/eq.)及びEPICLON EXA835LV(式(1)におけるmが0~0.1程度、エポキシ当量160~170)等が挙げられる。
式(3)中、aは平均値であり、2~30の範囲にある実数を表す。ここで言う「平均値」とは、平均繰り返し数を意味する。
式(3)で表されるエポキシ樹脂は、ビスフェノールFとエピクロロヒドリンとの重縮合物が有するアルコール性水酸基を、更にエピクロロヒドリンを用いてグリシジル化することにより得ることができる。更にグリシジル化するアルコール性水酸基の割合は特に限定されないが、諸物性のバランスを考慮した場合、ビスフェノールFとエピクロロヒドリンとの重縮合物が有するアルコール性水酸基の50~80%程度をグリシジル化したエポキシ樹脂であることが好ましい。
式(3)で表されるエポキシ樹脂の市販品の具体例としては、NER-7604及びNER-7403(いずれも商品名、日本化薬社製)等が挙げられる。式(3)で表されるエポキシ樹脂のエポキシ当量は250~400g/eq.であることが好ましく、また軟化点は60~85℃であることが好ましい。
式(1)で表されるエポキシ樹脂以外のエポキシ樹脂を併用する場合、(A)エポキシ樹脂全体に占める式(1)で表されるエポキシ樹脂の割合は、通常20質量%以上、好ましくは35質量%以上である。
式(2)で表されるフェノール化合物としては、フェノールノボラック、クレゾールノボラック等が挙げられ、感光性樹脂組成物が塗布性に優れることからフェノールノボラックが好ましく用いられる。式(2)で表されるフェノール化合物としては、軟化温度が50℃以上150℃以下であるものが好ましく、50℃以上100℃以下であるものがより好ましく、70℃以上100℃以下であるものがさらに好ましい。軟化温度が50℃以上150℃以下であるフェノールノボラックの具体例としては、PN-152(商品名、明和化成社製、軟化点50℃、水酸基当量105g/eq.)、H-1(商品名、明和化成社製、軟化点80℃、水酸基当量104g/eq.)、TD-2131(商品名、DIC社製、軟化点80℃、水酸基当量105g/eq.)、KA-1160(商品名、DIC社製、軟化点81℃、水酸基当量117g/eq.)等が挙げられる。又、フェノールノボラックの水酸基当量は、(A)エポキシ樹脂との相溶性や硬化物の低透湿性の点から80~200g/eq.の範囲であることが好ましく、80~130g/eq.の範囲であることがより好ましく、100~120g/eq.の範囲であることがさらに好ましい。
(B)フェノール性水酸基を有する化合物には、式(2)で表されるフェノール化合物を複数併用してもよい。
(B)フェノール性水酸基を有する化合物には、式(4)で表されるフェノール化合物を複数併用してもよい。
(B)フェノール性水酸基を有する化合物には、式(5)で表されるフェノール化合物を複数併用してもよい。
式(6)で表されるフェノール化合物としては、フェノールアラルキル樹脂が挙げられ、その具体例としては、ミレックスXLC-3L(商品名、三井化学社製、軟化点77℃、水酸基当量176g/eq.)等が挙げられる。
(B)フェノール性水酸基を有する化合物には、式(6)で表されるフェノール化合物を複数併用してもよい。
本発明の好ましい一態様では、(B)フェノール性水酸基を有する化合物は、式(2)、(5)及び(6)で表されるフェノール化合物からなる群より選ばれる一種以上のフェノール性化合物を含有する。
なお、式(2)、(4)、(5)及び(6)で表されるフェノール性水酸基を有する化合物からなる群より選択される複数を併用する場合のそれぞれのフェノール性水酸基を有する化合物の使用割合は、(A)エポキシ樹脂の質量に対する(B)フェノール性水酸基を有するフェノール化合物の配合割合の合計が上記の範囲内であれば特に限定されない。
併用し得るフェノール性水酸基を有する化合物としては、併用し得るエポキシ樹脂の項に、エポキシ樹脂の原料として記載したフェノール化合物等が挙げられるが、これらに限定されるものではない。
本発明の感光性樹脂組成物における(D)エポキシ基含有シラン化合物の含有量は、感光性樹脂組成物の固形分に対して通常15質量%以下、好ましくは1~10質量%である。
本発明の感光性樹脂組成物における(E)溶剤の含有量は、溶剤を含む感光性樹脂組成物中において、通常95質量%以下であり、好ましくは10~90質量%である。
9,10-ジアルコキシアントラセン誘導体としては、例えば9,10-ジメトキシアントラセン、9,10-ジエトキシアントラセン、9,10-ジプロポキシアントラセン、9,10-ジブトキシアントラセン、9,10-ジメトキシ-2-エチルアントラセン、9,10-ジエトキシ-2-エチルアントラセン、9,10-ジプロポキシ-2-エチルアントラセン、9,10-ジメトキシ-2-クロロアントラセン、9,10-ジメトキシアントラセン-2-スルホン酸メチルエステル、9,10-ジエトキシアントラセン-2-スルホン酸メチルエステル、9,10-ジメトキシアントラセン-2-カルボン酸メチルエステル等を挙げることができる。
別法として、防爆型霧化用噴霧ノズル、又は防爆型微小シャワーヘッド噴霧ノズルのいずれかを使用して、吹付けにより現像液溶媒を塗布してもよい。更に、他の現像方法としては、パドル法を使用して現像液を塗布する方法が挙げられる。
濯ぎ液としては、上記の現像液溶媒、並びにメタノール、エタノール、イソプロパノール、及び酢酸n-ブチル等が挙げられる。この内、速やかに洗浄ができ急速に乾燥させることができる、アセトン、エタノール、及びイソプロパノールが特に好ましい。最後に、基板の耐熱性に応じて、130~200℃で加熱処理を施し、膜を熱硬化させることにより、諸特性を満足する永久保護膜が得られる。
本発明のレジスト積層体によって、感光性樹脂組成物をドライフィルムレジストとして使用すれば、支持体又は基板上への塗布、および乾燥の工程を省略することが可能であり、より簡便に本発明の感光性樹脂組成物を用いた微細パターンの形成が可能となる。
(感光性樹脂組成物溶液(液状レジスト)の調製)
表1に記載の配合量(単位は質量部、溶媒を除く固形分の質量のみ記載した)に従って、(A)エポキシ樹脂、(B)フェノール性水酸基を有する化合物、(C)光カチオン重合開始剤及び(D)エポキシ基含有シラン化合物を、シクロペンタノンで濃度が65質量%となるように希釈し、攪拌機付きフラスコで80℃、3時間攪拌混合溶解し、放冷後、孔径1.0μmのメンブランフィルターによって濾過を施し、本発明及び比較用の感光性樹脂組成物溶液(液状レジスト)を得た。
実施例1~10及び比較例1~4で得られた各液状レジストを、シリコンウエハ上にスピンコーターで塗工後、95℃のホットプレートにより10分間のプレベークを行い、塗工後乾燥膜厚20μmの感光性樹脂組成物層を得た。その後、エッジビードを除去乾燥後、i線露光装置(マスクアライナー:ウシオ電機社製)を用いて解像性評価用グレースケール付きフォトマスクを介して、露光量700mJ/cm2(ソフトコンタクト、i線)を照射した。続いて、95℃のホットプレートにより5分間の露光後ベーク(以下「PEB」と記載する)を行った。次にSU-8 Developer(商品名、マイクロケム社製、プロピレングリコールモノメチルエーテルアセテート主成分)によって23℃で3分間浸漬現像し、2-プロパノールでリンス洗浄、乾燥を経て、シリコンウエハ上に硬化した樹脂パターンを得た。マスク転写精度が最良となる露光量を最適露光量とし、そのときの解像寸法値を解像度として感度・解像度評価を行った。結果を下記表1に示した。
触針式表面形状測定器を用いて3点支持されたシリコンウエハ(結晶方位100、直径100mm、厚み0.5mm)の膜形成前と膜形成後の基板の反り量を測定し、前後の反り量の変化を応力に換算した値である。一般に、膜の応力は、膜を形成される基材の形状・材質によって影響されるものではないので、シリコンウエハ上に膜を形成し、形成前後の基板反り量を測定して得られたものが、内部応力を示す。樹脂膜が硬化収縮する場合は圧縮応力となり、その応力の大きさにつれて、硬化膜のストレスが基板の反りを増大させ、膜自体もクレイジングやクラックなどの亀裂を生じる。内部応力が小さいほど、基板の反りも低減し、膜自体の亀裂も解消する。
Pt金属を200nm蒸着したシリコンウェハ、LT基板、Taを100nm蒸着したシリコンウェハを準備し、実施例1~10及び比較例1~4で得られた各液状レジストをこれら各基板上に上述のように塗工した。密着強度評価用テストパターンの配されたフォトマスクを介し、上記の感度評価試験で得られた各組成の最適露光量を照射した。PEB以降ハードベークの工程は上記の応力評価試験の工程と同じとし、シリコンウエハ上に硬化した樹脂パターンを得た。この樹脂パターン付きウエハを、純水の満たされたPTFE製密閉容器中(相対湿度100%)で、85℃、24時間、個別に浸漬させて湿熱試験に処した。試験前後の樹脂パターンの接着力を、シェア強度試験機にて測定し、接着力劣化無き場合を「○」、劣化の有った場合を「×」表記として、結果を表1に示した。
<(A)成分:エポキシ樹脂>
(A-1)jER4004P(商品名、三菱化学社製、式(1)における平均繰り返し数m≒5.6のエポキシ樹脂、エポキシ当量868g/eq.)
(A-2)jER4005P(商品名、三菱化学社製、式(1)における平均繰り返し数m≒7.0のエポキシ樹脂、エポキシ当量1046g/eq.)
(A-3)jER4007P(商品名、三菱化学社製、式(1)における平均繰り返し数m≒16.1のエポキシ樹脂、エポキシ当量2218g/eq.)
(A-5)YDF-8170C(商品名、新日鉄住金化学社製、エポキシ当量160g/eq.)
(A-6)NER7604(商品名、日本化薬社製、式(3)で表されるエポキシ樹脂、エポキシ当量345g/eq.)
(A-7)EPON SU-8(商品名、モメンティブ社製、エポキシ当量200g/eq.)
(A-8)セロキサイド2021P(商品名、ダイセル社製、エポキシ当量126g/eq.)
(A-9)EP828(商品名、三菱化学社製、エポキシ当量189g/eq.)
(A-10)XD-1000(商品名、日本化薬社製、エポキシ当量248g/eq.)
(B-1)PN-152(商品名、明和化成社製、式(2)で表されるフェノール化合物、水酸基当量105g/eq.)
(B-2)H-1(商品名、明和化成社製、式(2)で表されるフェノール化合物、水酸基当量104g/eq.)
(B-3)KAYAHARD GPH-65(商品名、日本化薬社製、式(5)で表されるフェノール化合物、水酸基当量200g/eq.)
(B-4)XL-225-3L(商品名、三井化学社製、式(6)で表されるフェノール化合物、水酸基当量172g/eq.)
<(C)成分:光カチオン重合開始剤>
(C-1)Irgacure PAG290(商品名、BASF社製)
(C-2)GSID-26-1(商品名、BASF社製)
(C-3)CPI-210S(商品名、サンアプロ社製)
<(D)成分:エポキシ基を有するシラン化合物>
(D)3-グリシドキシプロピルトリメトキシシラン
表1の実施例1の配合組成比に、更にエチレングリコールジメチルエーテルを追加配合し、攪拌機付きフラスコで50℃、1時間攪拌混合溶解して、25℃における溶液粘度が2Pa・sになるよう希釈し、放冷後、孔径1.0μmのメンブラン濾過を施し、本発明の感光性樹脂組成物ドライフィルムレジスト用ラッカーを得た。このラッカーを、ベースフィルム(ポリプロピレン製、三菱樹脂社製、膜厚38μm)上に均一に塗布し、温風対流乾燥機により65℃で5分間および80℃で15分間乾燥した。その後、露出面上にカバーフィルム(ポリプロピレン製、三菱樹脂社製、膜厚38μm)をラミネートして、膜厚20μmのドライフィルムレジストを挟んでなるレジスト積層体(感光性樹脂組成物積層体)を得た。
前記で得られた感光性樹脂組成物積層体からカバーフィルムを剥離し、ロール温度70℃、エアー圧力0.2MPa、速度0.5m/分でシリコンウエハ上にラミネートした後に、ベースフィルムを剥離し、20μmの感光性樹脂組成物層(ドライフィルムレジスト)を得た。この感光性樹脂組成物層に、i線露光装置(マスクアライナー:ウシオ電機社製)を用いてコンタクト露光を行った。その後、95℃ホットプレートで5分間のPEBを行い、SU-8 Developer(商品名、マイクロケム社製、プロピレングリコールモノメチルエーテルアセテート主成分)によって23℃で3分間浸漬現像し、2-プロパノールでリンス洗浄、乾燥させ、基板上に硬化した樹脂パターンを得た。最適露光量450mJ/cm2で、残渣及び亀裂がなく、細線密着パターン幅が6μmの垂直な側壁を有する硬化物が得られた。Pt、LT、Ta表面上の湿熱密着性も劣化なく良好であることが確認された。内部応力評価結果は、10MPa未満と低応力であることが確認された。
Claims (9)
- (A)エポキシ樹脂、(B)フェノール性水酸基を有する化合物及び(C)光カチオン重合開始剤を含有する感光性樹脂組成物であって、
(A)エポキシ樹脂の加重平均エポキシ当量が300g/eq.以上であり、
該(A)エポキシ樹脂の20質量%以上が、下記式(1)
(式(1)中、mは平均値であり、3~35の範囲にある実数を表す。)で表され、かつエポキシ当量が500~4500g/eq.のエポキシ樹脂であり、
該(B)フェノール性水酸基を有する化合物が、下記式(2)、(4)、(5)及び(6)
(式(2)中、nは平均値であり、1~10の範囲にある実数を表す。Rはそれぞれ独立に水素原子または炭素数1~4のアルキル基を表す。)
(式(4)中、qは平均値であり、1~10の範囲にある実数を表す。)
(式(5)中、zは平均値であり、1~10の範囲にある実数を表す。)
(式(6)中、yは平均値であり、1~10の範囲にある実数を表す。R8及びR9はそれぞれ独立に水素原子または炭素数1~4のアルキル基を表す。)で表されるフェノール化合物からなる群より選ばれる一種以上のフェノール化合物を含有する、上記感光性樹脂組成物。 - (A)エポキシ樹脂1当量に対して(B)フェノール性水酸基を有する化合物を0.1~0.9当量含有する請求項1又は2に記載の感光性樹脂組成物。
- (C)光カチオン重合開始剤がオニウム錯塩系の光カチオン重合開始剤である請求項1乃至3のいずれか一項に記載の感光性樹脂組成物。
- (D)エポキシ基含有シラン化合物を含有する請求項1乃至4のいずれか一項に記載の感光性樹脂組成物。
- (E)溶剤を含有する請求項1乃至5のいずれか一項に記載の感光性樹脂組成物。
- 請求項1乃至6のいずれか一項に記載の感光性樹脂組成物の硬化物。
- 請求項1乃至6のいずれか一項に記載の感光性樹脂組成物を基材で挟み込んで得られるレジスト積層体。
- 請求項8に記載のレジスト積層体から得られるドライフィルムレジストの硬化物。
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US20200292938A1 (en) * | 2017-12-06 | 2020-09-17 | Nipppon Kayaku Kabushiki Kaisha | Photosensitive Resin Composition, Dry Film Resist, And Cured Objects Obtained Therefrom |
US11809078B2 (en) * | 2017-12-06 | 2023-11-07 | Nippon Kayaku Kabushiki Kaisha | Photosensitive resin composition, dry film resist, and cured objects obtained therefrom |
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Also Published As
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EP3156845A4 (en) | 2017-11-22 |
SG11201610365TA (en) | 2017-01-27 |
TW201612232A (en) | 2016-04-01 |
CN106662814B (zh) | 2019-12-17 |
EP3156845B1 (en) | 2019-05-08 |
JPWO2015190476A1 (ja) | 2017-04-20 |
KR102357446B1 (ko) | 2022-01-28 |
US9857685B2 (en) | 2018-01-02 |
CN106662814A (zh) | 2017-05-10 |
US20170102614A1 (en) | 2017-04-13 |
TWI671353B (zh) | 2019-09-11 |
EP3156845A1 (en) | 2017-04-19 |
KR20170019351A (ko) | 2017-02-21 |
JP6461139B2 (ja) | 2019-01-30 |
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