CN105473257B - 金属烧结膜组合物 - Google Patents
金属烧结膜组合物 Download PDFInfo
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- CN105473257B CN105473257B CN201480045035.5A CN201480045035A CN105473257B CN 105473257 B CN105473257 B CN 105473257B CN 201480045035 A CN201480045035 A CN 201480045035A CN 105473257 B CN105473257 B CN 105473257B
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- sintering
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 66
- 239000002184 metal Substances 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000005245 sintering Methods 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 claims abstract description 29
- 239000000853 adhesive Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000011888 foil Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
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- 229910052763 palladium Inorganic materials 0.000 claims description 8
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
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- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
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- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 2
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- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 26
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- 239000002585 base Substances 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 20
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
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- 229910052783 alkali metal Inorganic materials 0.000 description 5
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- 239000000523 sample Substances 0.000 description 5
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- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 4
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- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
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- XHQZJYCNDZAGLW-UHFFFAOYSA-N 3-methoxybenzoic acid Chemical compound COC1=CC=CC(C(O)=O)=C1 XHQZJYCNDZAGLW-UHFFFAOYSA-N 0.000 description 2
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- 229910000679 solder Inorganic materials 0.000 description 1
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- 238000007614 solvation Methods 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1035—Liquid phase sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0233—Sheets, foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
- B23K35/3066—Fe as the principal constituent with Ni as next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/12—Intermetallic matrix material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/44—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/38 - H01L21/428
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Abstract
任选地使用固体或半固体有机粘合剂制备包含一种或多种金属、一种或多种金属合金、或一种或多种金属和一种或多种金属合金的混合物的烧结膜。该有机粘合剂可以具有助熔官能团;该有机粘合剂可以为在组合物中的金属或金属合金烧结时会部分或完全分解的有机粘合剂。在一个实施方式中,该烧结膜被提供于最终用途基材上,例如硅芯片或晶圆、或金属电路板或箔,或该烧结膜被提供于载体上,例如金属网。制备是通过以下完成的:在有或没有粘合剂情况下,在合适的溶剂中分散金属或金属合金,并且将该组合物暴露于高温下以蒸发掉该溶剂以及部分地烧结该金属或金属合金。
Description
背景
技术领域
提供了用于在多个工业中粘接应用的金属膜。该金属膜尤其适用于半导体工业中的应用,其中在应用中,该膜当被暴露于升高的温度条件时烧结并在两个其上应用该膜的基材之间形成电性连接。
相关技术的简要说明
传统上,包含粘合剂树脂和导电性填充剂的导电性粘合剂组合物被用在半导体封装和微电子装置的制造和组装中以在集成电路装置和其基材之间机械地附着并产生导电性和/或导热性。这些为糊状组合物,当被用于大的粘接区域之上时,观察到在固化期间会产生气孔并在角区渗出树脂残余物。气孔的存在会降低粘合剂的可靠性。
因此,提供膜形式的导电性粘合剂组合物将会是有利的,因为以膜形式,观察到气孔的减少,可维持改善的粘合线厚度的平整性,并且可以达到消除或至少减少树脂渗出或者残余物在芯片或角区的边缘的累积。另外,最终使用者将受益于更简单的应用和减少的溢出或污染机会。
概述
在本文中提供一种包含一种或多种金属和/或一种或多种金属合金的组合物,其中该一种或多种金属和/或一种或多种金属合金以高熔点相和低熔点相存在,其中该低熔点相在低于约300℃的温度时熔化。
当暴露于高于50℃但低于约300℃的温度时,该低熔点相熔化并与该高熔点相形成金属间化合物。通常,该金属间化合物以低于100%的水平形成于该组合物中。在一些情况下,可能希望与待结合的表面形成金属间连接。
该低熔点相基于该组合物以至少5重量%,例如30重量%的量存在。
期望地,该组合物为烧结膜形式。
在替代的实施方式中,提供一种包含金属或金属合金和可分解有机粘合剂的组合物,该组合物当暴露于高于50℃的温度时,其中该金属烧结并成为膜形式。此处,该金属在该组合物中应以低于100%的水平烧结。
在使用中,该组合物当以膜形式时被配置于半导体芯片和电路板或载体基材之间。期望地,该组合物当以膜形式时被配置于硅晶圆的表面上,其中该硅晶圆的表面包含金属化层。
使用前,该组合物当以烧结膜形式时可以被认为是一种具有设置在载体上的烧结膜的商品,所述载体例如载体膜、金属箔或陶瓷支撑体。
实际上,一旦被配置于期望的基材上,该烧结膜将经受足以引起该膜进一步烧结的升高的温度条件。该进一步烧结使得其间放置该膜的两个基材的结合。此处基材由金属、金属氧化物或其他导电性材料,或用这些金属、金属氧化物或导电性材料涂覆、成层或图案化构成,在该两个基材间形成电性互连。
在本文中也提供一种制备烧结膜的方法,包括(a)在有或没有粘合剂情况下,在合适的溶剂中分散该金属和/或金属合金,以形成烧结糊状物,(b)将该烧结糊状物施用于基材上,和(c)加热该烧结糊状物以使其干燥形成烧结膜。加热该烧结糊状物以使其干燥形成膜在本文中被称作B-阶段化。
该烧结膜提供经济优势,因为其比可流动的导电组合物更清洁并且更容易使用。
详细说明
如上文所述,在本文中提供一种包含一种或多种金属和/或一种或多种金属合金的组合物,其中该一种或多种金属和/或一种或多种金属合金以高熔点相和低熔点相存在,其中该低熔点相在低于约300℃的温度时熔化。
当被暴露于高于50℃但低于约300℃的温度时,该低熔点相熔化并与该高熔点相形成金属间化合物。通常,该金属间化合物以低于100%的水平形成于该组合物中。在一些情况下,期望与待结合的表面形成金属间连接。
该低熔点相基于该组合物以至少5重量%,例如30重量%的量存在。
期望地,该组合物为烧结膜形式。
也如上文所述,在替代的实施方式中,提供一种包含金属或金属合金和可分解有机粘合剂的组合物,该组合物当被暴露于高于50℃的温度时,其中该金属烧结并成为膜形式。此处,该金属在该组合物中应以低于100%的水平烧结。
在使用中,该组合物当以膜形式时被配置于半导体芯片和电路板或载体基材之间。期望地,该组合物当以膜形式时被配置于硅晶圆的表面上,其中该硅晶圆的表面包含金属化层。
使用前,该组合物当以烧结膜形式时可以被认为是一种具有设置在载体上的烧结膜的商品,所述载体例如载体膜、金属箔或陶瓷支撑体。
该烧结膜被烧结到一定程度(烧结的相对量可以基于用于制备膜的成分的确切性质改变)。如上文所述,金属以低于100%的水平烧结。
实际上,一旦被配置于期望的基材上,该烧结膜将经受足以引起该膜进一步烧结的升高的温度条件。该进一步烧结使得其间放置该膜的两个基材的结合。此处基材由金属、金属氧化物或其他导电性材料,或用这些金属、金属氧化物或导电性材料涂覆、成层或图案化构成,在该两个基材间形成电性互连。
在使用多于一种金属或多于一种金属合金的实施方式中,该金属中的一种或该金属合金中的一种将具有与其它相比更低的熔点相。
在其它实施方式中,该烧结膜进一步包含固体或半固体有机粘合剂;该有机粘合剂也可以具有助熔官能团。期望该有机粘合剂为在组合物中的金属或金属合金烧结时至少部分分解的有机粘合剂。
在其它实施方式中,该烧结膜被提供于载体上,例如剥离衬垫,以形成制品。在另外实施方式中,该烧结膜被提供于最终用途基材上,例如硅芯片或晶圆、或金属电路板或箔。在进一步的实施方式中,该烧结组合物被灌注入可被引入烧结后基质中或可在烧结过程中被烧尽的载体(例如导电金属或聚合物网)或多孔基材(例如金属、陶瓷或聚合物基材)中。此处,该烧结膜被配置于基材上,该基材可以包括聚酯片或涂覆聚硅氧烷的纸。
该烧结膜视情况而定被形成为期望的厚度,以适用于目前的商业应用。例如,当铺设于载体上时,该烧结膜可以形成0.5-3mil的厚度。一旦将由此所形成的烧结膜应用于该载体,该膜可以优选通过模切被切割至所需形状和尺寸,并且容易地被从该载体上移走或者剥落并被放置在期望的界面位置上。在这方面,该膜可以视情况而定被预切割以用于给定的商业应用。
该烧结膜可以被形成作为被切割为规定尺寸的膜以快速准确地应用于给定的基材,例如剥离衬垫,如由聚酯剥离基材或涂覆聚硅氧烷的基材制备的剥离衬垫。该烧结膜能够被应用于这些基材上并且随后可以被运输至期望的地点,没有变畸形或其他变形。
有利地,由于其以膜形式被运输的能力,因此该烧结膜处于有助于成为商品的状态,由此它们在一个地点被制备,包装并运输到另一个地点以应用于给定的基材。
形成于剥离基材上的烧结膜可以被预切割至所需尺寸,以致于形成多个膜片段,其中每个膜片段可以被从基材上除去并选择性地置于期望的界面上。
适用于该烧结膜的金属可以为任何的导电金属和/或金属合金。在不同的实施方式中,该金属和金属合金选自由银、铜、镍、锡和它们的任意合金组成的组。特别有用的合金选自铜-锡、铜-锌、铜-镍-锌;铁-镍合金;锡-铋合金、锡-银合金、锡-银-铜合金;涂覆银的铜-锌合金、涂覆银的铜-镍-锌合金、涂覆银的铜-锡合金、涂覆锡的铜和涂覆共熔锡:铋的铜。进一步合适的金属选自涂覆金属的氮化硼、涂覆金属的玻璃、涂覆金属的石墨和涂覆金属的陶瓷。这些和类似的金属和金属合金为商业上可购得的。
也可以使用涂覆金属或金属合金的颗粒。例如,涂覆锡铋的铜,涂覆锡的铜和涂覆银的氮化硼,仅为一些例子。涂覆金属或金属合金的颗粒可以被视为涂覆金属或金属合金的核。
该金属或金属合金可以为任何合适的形式,例如,粉末、薄片、球形、管材或线材。
在进一步的实施方式中,可包括附加的导电颗粒,例如,石墨烯、碳纳米管或有机导电聚合物。
当使用粘合剂时,该粘合剂为固体或半固体的化合物。在一个实施方式中,该粘合剂具有助熔官能团;在一些实施方式中,该助熔官能团为来自选自羟基、羧基、酸酐基团、酯基团、胺基团、酰胺基团、硫醇基团、硫酯基团及磷酸酯基团的基团。
在一个实施方式中,该粘合剂为软化点低于50℃的化合物;这样的低软化点使得制备的烧结膜低温层压至期望的基材。这些粘合剂可具有或不具有可聚合的官能团。合适的粘合剂包括Sekicui S-LEC AS C-4丙烯酸树脂,用于本说明书的实施例1中,和ISPGanex V-220烷基化聚乙烯基吡咯烷酮。
软化点低于50℃的粘合剂化合物也包括那些具有助熔官能团的那些。在一个实施方式中,该粘合剂为聚合物,例如用羧酸或马来酸酐官能化以加入助熔官能团的丙烯酸类树脂。这种类型的示例粘合剂包括用于实施例2中的ISP I-REZ 160共聚物异丁烯-马来酸酐树脂;和带有环氧化物的BASFQPAC-40聚碳酸亚烷基酯共聚物。通常,合适的粘合剂包括,但不限于,酸酐-酸官能化的粘合剂和天然存在的松香粘合剂。
粘合剂化合物也包括那些在温度≤350℃,例如≤275℃时热分解的那些。典型地,对于制备的膜,分解将通过温度斜升到分解温度和/或在分解温度下保持时间实现。合适的化合物包括Sekicui S-LEC AS C-4丙烯酸树脂和ISP I-REZ 160异丁烯与马来酸酐树脂的共聚物。
此外,可热分解的粘合剂化合物也包括那些具有助熔官能团的那些。这些化合物具有选自包括,但不限于,羟基、羧基、酸酐基团、酯基团、胺基团、酰胺基团、硫醇基团、硫酯基团和磷酸酯基团的基团的助熔官能团。
对于某些应用,该烧结组合物将进一步包含选自碱金属、碱金属盐、过渡金属和过渡金属盐(其中该盐为与有机酸配位的碱金属或过渡金属)的烧结助剂。该烧结助剂以该烧结膜的组分的≤5重量%的水平存在。该碱金属和过渡金属以及它们的盐典型地用于改善银的烧结以及使得铜薄片和合金-42薄片在≤350℃的温度的烧结。
合适的金属选自Li、Na、K、Rb、Be、Mg、Ca、Sr、Ba、Ti、Zr、V、Nb、Ta、Cr、Mo、W、Mn、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、B、Al、Ga、In、Si、Ge、Sn、Pb、N、P、As、Sb和Bi。合适的与金属配位的有机酸选自甲酸、乙酸、丙烯酸、甲基丙烯酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、亚油酸、亚麻酸、环己烷羧酸、苯乙酸、苯甲酸、邻甲苯甲酸、间甲苯甲酸、对甲苯甲酸、邻氯苯甲酸、间氯苯甲酸、对氯苯甲酸、邻溴苯甲酸、间溴苯甲酸、对溴苯甲酸、邻硝基苯甲酸、间硝基苯甲酸、对硝基苯甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、水杨酸、对羟基苯甲酸、邻氨基苯甲酸、间氨基苯甲酸、对氨基苯甲酸、邻甲氧基苯甲酸、间甲氧基苯甲酸、对甲氧基苯甲酸、草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、连苯三酸、偏苯三酸、均苯三酸、苹果酸和柠檬酸,这些酸的支链同分异构体和这些酸的卤代衍生物。
这些羧酸为商业上可购得的或者为本领域技术人员可容易合成的。这些羧酸的金属盐通常为固体材料,其能够被研磨为细粉以被引入选择的树脂组合物中。该金属盐以该配制物的0.05重量%-10重量%的负载量加入该树脂组合物中。在一个实施方式中,负载量为约0.1重量%-0.5重量%。
在各种实施方式中,该烧结助剂选自乙酸锂、乙酰丙酮锂、苯甲酸锂、磷酸锂、钯、甲基丙烯酸钯、乙酰丙酮钯(II)以及2-乙基己酸锡(II)。
该烧结膜可以通过下述方法制备,该方法包括在有或没有粘合剂情况下,在合适的溶剂中分散一种或多种金属和/或一种或多种金属合金,以形成烧结糊状物;将烧结糊状物施用于基材上,并且加热该烧结糊状物以使其干燥形成烧结膜。该金属和金属合金如前所述。该粘合剂如前所述。随着该烧结糊状物干燥成为尺寸稳定的膜,溶剂被蒸发。干燥的典型条件为在≤150℃的温度下≤60分钟的时间,尽管在某些实施方式中,该温度可以为≤260℃。对于包含两种或更多种不同金属或金属合金的组合的组合物,该过程发生在高于金属或金属合金中的一种的熔点的温度。
溶剂用于分散或者溶剂化一种或多种金属或一种或多种金属氧化物,和粘合剂(当存在时)。一些溶剂也为助熔剂。合适的溶剂为氧化的溶剂和可接受氢键合和缺少酸性氢的非质子溶剂。在不同的实施方式中,溶剂选自乙酸丁酯、己二醇、碳酸丙二酯、N-甲基-2-吡咯烷酮、乙酰丙酮、2-乙基-1,3-己二醇、2-(2-乙氧基乙氧基)-乙酸乙酯、丙酮、乙酸乙酯、二乙二醇单丁醚乙酸酯、2-丁酮、间1,4-二噁烷、N-乙基吡咯烷酮、二甲基甲酰胺、环辛酮、二苯醚、2-苯基-3-丁炔-2-醇、二环戊二烯及四氢糠醇。
在一些实施方式中,该烧结膜可在B-阶段化后被压缩以提高膜密度和减少气孔。压缩过程将在≤300℃,优选≤250℃,以及更优选≤150℃的温度和≤15mPa的压力下进行。该过程可以为连续过程(优选的)或为分批处理过程。
需要时,B-阶段化后的该烧结膜可以在用作粘接粘合剂之前通过应用助熔剂再活化。
干燥膜可以通过在≤260℃和≤50Mpa,并且期望地低于15Mpa的热压方法印刷至期望的基材上而进一步被加工。
因此,在进一步的实施方式中,提供一种制备烧结膜的方法,包括(a)在有或没有粘合剂情况下,在溶剂中分散一种或多种金属和/或一种或多种金属合金,以形成烧结糊状物;(b)将该烧结糊状物应用于基材上,和(c)加热该烧结糊状物以使其干燥形成烧结膜。在进一步的步骤中,该方法包括(d)在≤300℃的温度和≤15Mpa的压力下压缩该膜,和/或(e)将该膜层压至基材。
该烧结膜时常被用于金属-金属粘接应用中,尤其用于电子工业中,但也应用于其他需要金属-金属粘接的工业应用中。
在电子工业中,这些烧结膜可以被用作导电晶圆背面涂层或者用作芯片附着粘合剂,其中加工温度范围为约175℃到350℃。在一些实施方式中,该烧结膜被配置于期望的基材例如硅晶圆上(当该烧结膜被用作晶圆背面涂层时)或者层合剥离衬底上(当该烧结膜被用作导电芯片附着粘合剂时)。
在其他最终用途应用中,该烧结膜可以被印刷到载体膜、金属箔或陶瓷支撑体上。该载体膜可以为聚合物,例如,聚酯、聚丙烯酸酯或聚酰亚胺。该载体膜也可以为紫外透明胶带。当该载体膜为金属箔时,该烧结膜可以被印刷在该箔的一面或者两面上并进行B-阶段化。对于某些用途,该组合的厚度典型地为小于100微米,但可小于50微米。
在其他实施方式中,可以将该烧结膜注入到泡沫或者网状物中,其中该泡沫或网状物由金属、聚合物或陶瓷组成。替代地,该烧结膜可以被应用于载体上,例如载体膜,金属箔或陶瓷支撑体。
以下实施例有助于阐述但不限制本发明。
实施例
在以下实施例中,烧结膜由银与可分解粘合剂制备,并评价如下。
测试载具为所述的在铜或银基材上金属化(钛-镍-银)的硅芯片。
在兆欧姆桥上用四点探针测量导电率,以体积电阻率测量。
通过用激光脉冲方法使用Netzsch工具测量热导率。
在Dage芯片抗剪切测试器上使用用钛-镍-银金属化的硅芯片和裸铜或涂覆银的铜基材测量芯片抗剪切强度(DSS)。
对于该实施例中所用的样品,通过人工附着或热压附着实现芯片附着。样品被两次暴露在500mj/平方厘米的紫外光下持续30秒,以及然后使用Toray Engineering FC-100固晶机在≤275℃下以10N至150N范围内的压头力(bonding head force),根据样品持续0.1秒至15分钟,附着于选定的基材。采用后芯片附着烧结过程进行完全烧结,典型的在≤250℃下≤60分钟。
测量几个配制物中的每一个的电阻、热导率和芯片抗剪切,并且结果记录于以下实施例中。TGA为热重分析。
实施例1.
根据表1中的重量配方制备膜。当用丙烯酸类粘合剂时,过氧化物并未加入到该配方中;这阻止该丙烯酸类在B-阶段化过程中交联。在150℃下,加热烧结组合物1小时以除去溶剂并稳定该组合物形成烧结膜。将该膜用于上述的测试载具中。数据也被记录在表1中并且说明可以用可分解的粘合剂制备烧结膜。
表1
实施例2.
在这个实施例中使用交替的异丁烯和马来酸酐基团的线性共聚物作为粘合剂。该共聚物具有助熔官能团,软化点为37℃,以及分子量为78000-94000。在所述的银和铜基材上进行芯片剪切。结果记录于表2中并显示对于含有共聚物粘合剂的样品具有改善的粘着性以及低温层合性和芯片附着。
表2
组分 | C | D |
银粉末(DOWA AG-SAB-136) | 60.0 | 60.0 |
银薄片(DOWA FA-DAB-195) | 40.0 | 40.0 |
异丁烯-马来酸酐共聚物(助熔树脂)(ISP I-REZ 160) | 3.2 | |
2-乙基-1,3-己二醇(溶剂) | 12.0 | |
碳酸丙二酯(溶剂) | 8.4 | |
N-甲基-2-吡咯烷酮(溶剂) | 8.4 | |
乙酰丙酮(助熔剂) | 3.0 | 3.0 |
二叔丁基过氧化物 | 1.0 | 1.0 |
体积电阻(Ω-cm) | 0.7×10-5 | 1.3×10-5 |
DSS/银基材(kg/mm2) | 1.5 | 2.2 |
DSS/铜基材(kg/mm2) | 1.5 | 1.7 |
实施例3.
在这个实施例中,添加碱金属锂和过渡金属钯至烧结组合物中以增强烧结。银的烧结曲线为30分钟斜升至250℃并在250℃保持60分钟。铜和合金-42的烧结斜升为350℃并在350℃保持60分钟。充分烧结银以制造金属间连接从而在金属粘接表面之间具有粘合强度。烧结铜和合金,但是不具有其他金属化以改善粘合性。结果记录在表3中。
表3
实施例4.
在这个实施例中,从表4中含有合金组合的组合物制备烧结膜。该膜通过以下制备:在聚酰亚胺基材上印刷该组合物的2mil的膜,该组合物在260℃的峰值焊料回焊过程中进行B-阶段化,在两个聚酰亚胺膜间热压(在约0.65-0.75MPa(100-110psi)和200℃下)2分钟,将烧结膜曝光,将该烧结膜浸渍于15%壬二酸的四氢糠醇溶液中,以及然后用该膜在5N和240℃下持续30秒将芯片粘接到铜基材上。在粘接前,应用助熔溶液用于再活化膜表面。在粘接前,应用压力用于改善膜密度。结果记录于表4中。
表4
组分 | H |
铜-银复合薄片大约50%银(Metalor P300-4) | 36.0 |
96.5锡/3.0银/0.5铜合金粉末(SAC 305类型3 97SCDAP)粒度45-25μm | 45.9 |
96.5锡/3.0银/0.5铜合金粉末(SAC 305类型7 97SCDAP)粒度10-1μm | 8.1 |
四氢糠醇(溶剂) | 8.7 |
壬二酸(助熔剂) | 1.3 |
室温DSS/铜基材(kg/mm2) | 5.2 |
实施例5.
这个实施例说明向该烧结组合物中加入金属盐的益处。实施例I中不含金属盐并且该芯片抗剪切强度在商业上是可接受的。实施例J,确实含有金属盐,其显示了更高的芯片抗剪切强度,表明金属盐的加入可以改善组合物的芯片抗剪切强度。结果报告于表5中。
表5
组分 | I | J |
铜粉末(DOWA QCS-8) | 30 | 30 |
96.5锡/3.5银合金粉末(Gesick) | 60 | 60 |
2-乙基己酸锡(2+)(己酸的盐) | 0 | 1.5 |
四氢糠醇(溶剂) | 8.5 | 7.0 |
壬二酸(助熔剂) | 1.5 | 1.5 |
室温DSS/铜基材(kg/mm2) | 3.9 | 9.1 |
Claims (14)
1.一种组合物,包含银和烧结助剂,所述烧结助剂选自由乙酸锂、乙酰丙酮锂、苯甲酸锂、磷酸锂、钯、甲基丙烯酸钯、乙酰丙酮钯(II)和2-乙基己酸锡(II)组成的组。
2.如权利要求1所述的组合物,其为烧结膜形式。
3.如权利要求1所述的组合物,其进一步包含石墨烯、碳纳米管或导电性有机聚合物。
4.如权利要求1所述的组合物,其进一步包含固体或半固体有机粘合剂。
5.如权利要求4所述的组合物,其中该固体或半固体有机粘合剂具有助熔官能团。
6.如权利要求5所述的组合物,其中该助熔官能团为来自选自由羟基、羧基、酸酐基团、酯基团、胺基团、酰胺基团、硫醇基团、硫酯基团及磷酸酯基团组成的组的基团。
7.如权利要求4所述的组合物,其中该粘合剂为软化点低于50℃的化合物。
8.如权利要求7所述的组合物,其中该粘合剂为丙烯酸类树脂或烷基化聚乙烯基吡咯烷酮。
9.如权利要求7所述的组合物,其中该粘合剂具有助熔官能团。
10.如权利要求9所述的组合物,其中该粘合剂为经羧酸或马来酸酐官能化的丙烯酸类树脂、或异丁烯和马来酸酐的共聚物、或带有环氧化物的聚碳酸亚烷基酯共聚物。
11.如权利要求4所述的组合物,其中该粘合剂为在≤350℃的温度时热分解的化合物。
12.一种制备烧结膜的方法,包括
(a)在有或没有粘合剂情况下,在溶剂中分散银和烧结助剂以形成烧结糊状物,所述烧结助剂选自由乙酸锂、乙酰丙酮锂、苯甲酸锂、磷酸锂、钯、甲基丙烯酸钯、乙酰丙酮钯(II)和2-乙基己酸锡(II)组成的组;
(b)将该烧结糊状物施用于基材上;或者
(c)将该烧结糊状物注入到泡沫或者网状物中,以及
(d)加热该烧结糊状物以使其干燥形成烧结膜。
13.如权利要求12所述的方法,进一步包括
(e)在≤300℃的温度和≤15Mpa的压力下压缩该膜,和/或
(f)将该膜层合至基材。
14.如权利要求2所述的为烧结膜形式的组合物的用途,其被施用于基材上,其中该基材为载体膜、金属箔、硅芯片、硅晶圆、金属电路板或陶瓷支撑体。
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2014
- 2014-07-09 CN CN201480045035.5A patent/CN105473257B/zh active Active
- 2014-07-09 EP EP14842807.1A patent/EP3041627A4/en not_active Withdrawn
- 2014-07-09 JP JP2016540879A patent/JP6486369B2/ja active Active
- 2014-07-09 KR KR1020167005613A patent/KR20160051766A/ko not_active Application Discontinuation
- 2014-07-09 KR KR1020207019199A patent/KR102270959B1/ko active IP Right Grant
- 2014-07-09 WO PCT/US2014/045862 patent/WO2015034579A1/en active Application Filing
- 2014-07-25 TW TW103125600A patent/TWI695823B/zh active
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KR102270959B1 (ko) | 2021-07-01 |
TW201509869A (zh) | 2015-03-16 |
JP2016536467A (ja) | 2016-11-24 |
TWI695823B (zh) | 2020-06-11 |
JP6486369B2 (ja) | 2019-03-20 |
WO2015034579A1 (en) | 2015-03-12 |
CN105473257A (zh) | 2016-04-06 |
KR20200084920A (ko) | 2020-07-13 |
EP3041627A1 (en) | 2016-07-13 |
KR20160051766A (ko) | 2016-05-11 |
EP3041627A4 (en) | 2017-05-03 |
US20160151864A1 (en) | 2016-06-02 |
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