KR102270959B1 - 금속 소결 필름 조성물 - Google Patents
금속 소결 필름 조성물 Download PDFInfo
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- KR102270959B1 KR102270959B1 KR1020207019199A KR20207019199A KR102270959B1 KR 102270959 B1 KR102270959 B1 KR 102270959B1 KR 1020207019199 A KR1020207019199 A KR 1020207019199A KR 20207019199 A KR20207019199 A KR 20207019199A KR 102270959 B1 KR102270959 B1 KR 102270959B1
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- South Korea
- Prior art keywords
- composition
- metal
- film
- binder
- sintering
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000005245 sintering Methods 0.000 title claims abstract description 56
- 239000011230 binding agent Substances 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 32
- 150000002739 metals Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 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
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000011888 foil Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 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
- 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 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- -1 alkali metal salts Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
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- 239000004065 semiconductor Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- XHQZJYCNDZAGLW-UHFFFAOYSA-N 3-methoxybenzoic acid Chemical compound COC1=CC=CC(C(O)=O)=C1 XHQZJYCNDZAGLW-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 2
- QQMBHAVGDGCSGY-UHFFFAOYSA-N [Ti].[Ni].[Ag] Chemical compound [Ti].[Ni].[Ag] QQMBHAVGDGCSGY-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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Classifications
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- 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
-
- 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
- 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
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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
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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
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- 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
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- H—ELECTRICITY
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Abstract
임의로 고체 또는 반-고체 유기 결합제를 사용하여 하나 이상의 금속, 하나 이상의 금속 합금, 또는 하나 이상의 금속 및 하나 이상의 금속 합금의 블렌드를 포함하는 소결 필름을 제조한다. 유기 결합제는 플럭싱 작용성을 가질 수 있고; 유기 결합제는 조성물 중의 금속 또는 금속 합금의 소결 시에 부분적으로 또는 완전히 분해되는 것일 수 있다. 한 실시양태에서, 규소 다이 또는 웨이퍼, 또는 금속 회로 기판 또는 호일과 같은 최종 사용 기판 상에 소결 필름이 제공되거나, 또는 금속 메쉬와 같은 캐리어 상에 소결 필름이 제공된다. 금속 또는 금속 합금을 결합제와 함께 또는 결합제 없이 적절한 용매에 분산시키고, 조성물을 고온에 노출시켜 용매를 증발 제거하고, 금속 또는 금속 합금을 부분적으로 소결함으로써 제조가 달성된다.
Description
다양한 산업에서 결합 응용에 유용한 금속 필름이 제공된다. 금속 필름은 반도체 산업에서 사용하기에 특히 적절하고, 이 응용에서 승온 조건에 노출될 경우 필름이 소결되고 이것이 적용된 2개 기판 사이에서 전기적 상호연결을 형성한다.
전통적으로, 집적 회로 장치 및 그의 기판을 기계적으로 부착하고 이들 간에 전기적 및/또는 열적 전도도를 발생시키기 위하여, 접착성 수지 및 전도성 충전제를 포함하는 전도성 접착 조성물이 반도체 패키지 및 마이크로전자 장치의 제작 및 조립에서 사용되어 왔다. 이들은 페이스트 조성물이고, 큰 결합 면적에 걸쳐 사용될 때 경화 동안에 공극을 생성하고 필렛 부위에서 잔류물과 함께 수지가 방출되는 것으로 관찰되었다. 공극의 존재는 접착제의 신뢰도를 저하시킨다.
그 결과, 필름 포맷에서 감소된 공극 형성이 관찰되어야 하고, 결합 선 두께의 개선된 평면도를 유지할 수 있고, 다이 또는 필렛 부위의 가장자리에서 수지의 방출 또는 잔류물의 축적을 제거하거나 또는 적어도 감소시킬 수 있기 때문에, 필름 형성에서 전도성 접착 조성물을 제공하는 것이 유리하다. 추가로, 최종 사용자들은 더욱 용이한 적용 및 사용 시의 유출 또는 오염 기회의 감소로부터 이익을 얻을 것이다.
발명의 요약
하나 이상의 금속 및/또는 하나 이상의 금속 합금을 포함하는 물질의 조성물이 본원에 제공되고, 여기서 하나 이상의 금속 및/또는 하나 이상의 금속 합금은 고 융점 상 및 저 융점 상에 존재하고, 저 융점 상은 약 300℃ 미만의 온도에서 용융된다.
저 융점 상은 50℃ 초과 내지 약 300℃ 미만의 온도에 노출될 경우 용융되고 고 융점 상과 금속간 화합물을 형성한다. 금속간 화합물은 보통 조성물에서 100% 미만의 수준으로 형성된다. 일부 경우에, 접합되는 표면과 함께 금속간 연결을 형성하는 것이 바람직할 수도 있다.
저 융점 상은 물질의 조성물의 적어도 5 중량%, 예컨대 30 중량%의 양으로 존재한다.
바람직하게는, 물질의 조성물은 소결 필름의 형태이다.
대안적인 실시양태에서, 금속 또는 금속 합금 및 분해가능한 유기 결합제를 포함하는 물질의 조성물이 제공되고, 이것은 50℃ 초과의 온도에 노출될 경우, 금속이 소결되고 필름의 형태이다. 여기서, 금속은 조성물에서 100% 미만의 수준으로 소결되어야 한다.
사용 시에, 물질의 조성물은 필름 형태일 때 반도체 칩과 회로 기판 또는 캐리어 기판 사이에 배치되어야 한다. 바람직하게는, 물질의 조성물은 필름 형태일 때 규소 웨이퍼의 표면 상에 배치되어야 하고, 여기서 규소 웨이퍼의 표면이 금속화 층을 함유한다.
사용 이전에, 물질의 조성물은 소결 필름의 형태일 때 캐리어, 예컨대 캐리어 필름, 금속 호일 또는 세라믹 지지체 상에 배치된 소결 필름을 갖는 상업용 물품으로 간주될 수도 있다.
실제로, 바람직한 기판 상에 일단 배치된 소결 필름을 필름의 추가 소결을 유발하기에 충분한 승온 조건으로 처리할 것이다. 추가의 소결은 그 사이에 필름이 위치하는 2개 기판의 접합을 가능하게 해야 한다. 기판이 금속, 금속 산화물 또는 기타 전도성 물질로부터 만들어지거나, 또는 이러한 금속, 금속 산화물 또는 물질로 코팅되거나 적층되거나 또는 패턴화된다면, 2개 기판 사이에서 전기적 상호연결이 형성된다.
또한, (a) 금속 및/또는 금속 합금을 결합제와 함께 또는 결합제 없이 적절한 용매에 분산시켜 소결 페이스트를 형성하고, (b) 소결 페이스트를 기판에 적용하고, (c) 소결 페이스트를 가열하여 이것을 소결 필름으로 건조시키는 것을 포함하는, 소결 필름의 제조 방법이 본원에 제공된다. 소결 페이스트를 가열하여 이것을 필름으로 건조하는 것을 본원에서 B-단계 처리라고 일컫는다.
소결 필름은 이것이 유동가능한 전도성 조성물에 비하여 더 깨끗하고 사용이 더 용이하기 때문에 경제적 장점을 제공한다.
상기 기재된 바와 같이, 하나 이상의 금속 및/또는 하나 이상의 금속 합금을 포함하는 물질의 조성물이 본원에서 제공되고, 여기서 하나 이상의 금속 및/또는 하나 이상의 금속 합금이 고 융점 상 및 저 융점 상에 존재하고, 여기서 저 융점 상이 약 300℃ 미만의 온도에서 용융된다.
저 융점 상은 50℃ 초과 내지 약 300℃ 미만의 온도에 노출될 경우 용융되고 고 융점 상과 금속간 화합물을 형성한다. 금속간 화합물은 보통 조성물에서 100% 미만의 수준으로 형성된다. 일부 경우에, 접합되는 표면과 함께 금속간 연결을 형성하는 것이 바람직할 수도 있다.
저 융점 상은 물질의 조성물의 적어도 5 중량%, 예컨대 30 중량%의 양으로 존재한다.
바람직하게는, 물질의 조성물은 소결 필름의 형태이다.
또한, 상기 기재된 바와 같이, 대안적인 실시양태에서, 금속 또는 금속 합금 및 분해가능한 유기 결합제를 포함하는 물질의 조성물이 제공되고, 이것은 50℃ 초과의 온도에 노출될 경우, 금속이 소결되고 필름의 형태이다. 여기서, 금속은 조성물에서 100% 미만의 수준으로 소결되어야 한다.
사용 시에, 물질의 조성물은 필름 형태일 경우 반도체 칩과 회로 기판 또는 캐리어 기판 사이에 배치되어야 한다. 바람직하게는, 물질의 조성물은 필름 형태일 경우 규소 웨이퍼의 표면 상에 배치되어야 하고, 여기서 규소 웨이퍼의 표면은 금속화 층을 함유한다.
사용 이전에, 물질의 조성물은 소결 필름의 형태일 경우 캐리어, 예컨대 캐리어 필름, 금속 호일 또는 세라믹 지지체 상에 배치된 소결 필름을 갖는 상업용 물품으로 간주될 수도 있다.
소결 필름을 어느 정도까지 소결한다 (소결의 상대 량은 필름을 형성하기 위해 사용되는 성분들의 정확한 성질에 의존하여 변할 수 있다). 상기 나타낸 바와 같이, 금속은 100% 미만의 수준으로 소결된다.
실제로, 바람직한 기판 상에 일단 배치된 소결 필름을 필름의 추가 소결을 유발하기에 충분한 승온 조건으로 처리할 것이다. 추가의 소결은 그 사이에 필름이 위치하는 2개 기판의 접합을 가능하게 해야 한다. 기판이 금속, 금속 산화물 또는 기타 전도성 물질로부터 만들어지거나, 또는 이러한 금속, 금속 산화물 또는 기타 전도성 물질로 코팅되거나 적층되거나 또는 패턴화된다면, 2개 기판 사이에서 전기적 상호연결이 형성된다.
하나 초과의 금속 또는 하나 초과의 금속 합금이 사용되는 실시양태에서, 금속의 하나 또는 금속 합금의 하나가 다른 것들보다 더 낮은 융점 상을 가질 것이다.
또 다른 실시양태에서, 소결 필름은 고체 또는 반-고체 유기 결합제를 추가로 포함하고; 유기 결합제는 플럭싱(fluxing) 작용성을 또한 가질 수도 있다. 유기 결합제는 조성물 중의 금속 또는 금속 합금의 소결 시에 적어도 부분적으로 분해되는 것이 바람직하다.
또 다른 실시양태에서, 소결 필름이 캐리어, 예컨대 이형 라이너 상에 제공되어 제조 물품을 형성한다. 또 다른 실시양태에서, 소결 필름이 최종 사용 기판, 예컨대 규소 다이 또는 웨이퍼, 또는 금속 회로 기판 또는 호일 상에 제공된다. 추가의 실시양태에서, 소결 조성물이 캐리어, 예컨대 전도성 금속 또는 중합체 메쉬, 또는 다공성 기판, 예컨대 소결된 매트릭스에 혼입될 수도 있거나 또는 소결 동안에 연소될 수 있는 금속, 세라믹 또는 중합체 기판 내에 함침된다. 여기서, 소결 필름이 기판 상에 배치되고, 이것은 폴리에스테르의 시트 또는 실리콘-코팅된 종이를 포함할 수도 있다.
가까운 장래의 상업적 응용을 위해 적절하다면 소결 필름을 원하는 두께로 형성해야 한다. 예를 들어, 캐리어 상에 놓일 때, 소결 필름을 0.5 내지 3 mil의 두께로 형성할 수도 있다. 일단 이렇게 형성된 소결 필름을 캐리어에 적용하면, 필름을 다이 컷팅에 의하여 원하는 형태 및 치수로 바람직하게 절단할 수도 있고, 캐리어로부터 쉽게 제거하거나 박리할 수도 있고, 원하는 계면의 위치에 배치할 수도 있다. 이러한 측면에서, 필름을 주어진 상업적인 응용을 위해 적절하게 사전-절단할 수도 있다.
소결 필름을 주어진 기판, 예컨대 폴리에스테르 이형 기판 또는 실리콘-코팅된 기판으로부터 제조된 것과 같은 이형 라이너에 빠르고 정확하게 적용하기 위해 규정된 치수로 절단된 필름으로서 형성할 수도 있다. 소결 필름을 이러한 기판에 적용할 수 있고 그 후에 일그러지거나 달리 변형되지 않은 채로 원하는 장소로 옮길 수 있다.
유리하게는, 필름 형태로 옮길 수 있는 능력에 기인하여, 소결 필름은 상업용 물품에 도움이 되는 상태로 있고, 이에 의해 이것을 한 장소에서 제조하고, 포장하여 주어진 기판에 적용하기 위해 다른 장소로 옮긴다.
이형 기판 상에 형성된 소결 필름을 원하는 치수로 사전-절단할 수도 있고, 그 결과 다수의 필름 단편이 형성되고, 이들 각각을 기판으로부터 제거하고 원하는 계면에 선택적으로 위치시킬 수도 있다.
소결 필름을 위해 적절한 금속은 임의의 전도성 금속 및/또는 금속 합금일 수 있다. 다양한 실시양태에서, 금속 및 금속 합금이 은, 구리, 니켈, 주석 및 그들의 합금으로 이루어진 군으로부터 선택된다. 특히 유용한 합금은 구리-주석, 구리-아연, 구리-니켈-아연; 철-니켈 합금; 주석-비스무트 합금, 주석-은 합금, 주석-은-구리 합금; 은-코팅된 구리-아연 합금, 은-코팅된 구리-니켈-아연 합금, 은-코팅된 구리-주석 합금, 주석-코팅된 구리, 및 공융 Sn:Bi-코팅된 구리로부터 선택된다. 추가의 적절한 금속은 금속-코팅된 질화붕소, 금속-코팅된 유리, 금속-코팅된 흑연 및 금속-코팅된 세라믹으로부터 선택된다. 이들 및 유사한 금속 및 금속 합금이 통상적으로 입수가능하다.
금속- 또는 금속-합금 코팅된 입자가 또한 사용될 수도 있다. 예를 들어, 주석-비스무트-코팅된 구리, 주석-코팅된 구리, 및 은-코팅된 질화붕소는 단지 몇 개의 예이다. 금속- 또는 금속 합금-코팅된 입자가 금속 또는 금속 합금-코팅된 코어로서 간주될 수도 있다.
금속 또는 금속 합금은 임의의 적절한 형태, 예컨대 분말, 박편, 구, 튜브 또는 와이어일 수 있다.
추가의 실시양태에서, 추가의 전도성 입자, 예컨대 그래핀, 탄소 나노튜브, 또는 유기 전도성 중합체가 포함될 수 있다.
결합제가 사용될 경우, 결합제는 고체 또는 반-고체 화합물일 것이다. 한 실시양태에서, 결합제는 플럭싱 작용성을 가질 것이고; 일부 실시양태에서 플럭싱 작용성은 히드록실, 카르복실, 무수물, 에스테르, 아민, 아미드, 티올, 티오에스테르 및 포스페이트 에스테르 기로부터 선택된 군으로부터이다.
한 실시양태에서, 결합제는 50℃ 미만의 연화점을 갖는 화합물이다; 이 저 연화점은 제조된 소결 필름을 원하는 기판에 저온 적층하는 것을 가능하게 한다. 이러한 결합제는 중합가능한 작용성을 가질 수도 있거나 갖지 않을 수도 있다. 적절한 결합제는 본 명세서의 실시예 1에서 사용된 세키쿠이(Sekicui) S-LEC AS C-4 아크릴 수지 및 ISP 가넥스(Ganex) V-220 알킬화 폴리비닐피롤리돈을 포함한다.
50℃ 미만의 연화점을 갖는 결합제 화합물은 또한 플럭싱 작용성을 갖는 것을 포함한다. 한 실시양태에서, 결합제는 플럭싱 작용성을 첨가하기 위해 카르복실 산 또는 말레산 무수물로 작용화된 중합체, 예컨대 아크릴 수지일 것이다. 이러한 유형의 일례의 결합제는 실시예 2에서 사용된 ISP I-REZ 160 공중합체 이소부틸렌-말레산 무수물 수지; 및 에폭시드를 이용한 BASF QPAC-40 폴리-(알킬렌 카르보네이트) 공중합체를 포함한다. 일반적으로, 적절한 결합제는 이에 한정되지 않지만 무수물-산 작용성 결합제 및 천연 발생 로진 결합제를 포함한다.
결합제 화합물은 ≤350℃, 예컨대 ≤275℃의 온도에서 열적으로 분해되는 것을 또한 포함한다. 분해는 전형적으로 분해 온도까지의 온도 경사 및/또는 분해 온도에서의 유지 시간에 의해 제조된 필름에 대해 달성될 것이다. 적절한 화합물은 세키쿠이 S-LEC AS C-4 아크릴 수지 및 이소부틸렌 및 말레산 무수물 수지의 ISP I-REZ 160 공중합체를 포함한다.
추가로, 열적으로 분해가능한 결합제 화합물은 플럭싱 작용성을 갖는 것을 또한 포함한다. 이러한 화합물은 이에 한정되지 않지만 히드록실, 카르복실, 무수물, 에스테르, 아민, 아미드, 티올, 티오에스테르 및 포스페이트 에스테르 기를 포함한 군으로부터의 플럭싱 작용성을 갖는다.
일부 응용을 위하여, 소결 조성물은 알칼리 금속, 알칼리 금속 염, 전이 금속 및 전이 금속 염 (여기서, 염은 유기 산과 배위된 알칼리 또는 전이 금속이다)으로부터 선택된 소결 보조제를 추가로 포함할 것이다. 소결 보조제는 소결 필름의 성분의 ≤5.0 중량%의 수준으로 존재한다. 알칼리 및 전이 금속 및 그들의 염은 전형적으로 은의 소결을 개선하기 위해 그리고 ≤350℃의 온도에서 구리 박편 및 합금-42 박편의 소결을 가능하도록 하기 위해 사용된다.
적절한 금속은 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 및 Bi로부터 선택된다. 금속과 배위하기에 적절한 유기 산은 포름산, 아세트산, 아크릴산, 메타크릴산, 프로피온산, 부티르산, 발레르산, 카프로산, 카프릴산, 카프르산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 올레산, 리놀레산, 리놀렌산, 시클로헥산카르복실산, 페닐아세트산, 벤조산, o-톨루산, m-톨루산, p-톨루산, o-클로로벤조산, m-클로로벤조산, p-클로로벤조산, o-브로모벤조산, m-브로모벤조산, p-브로모벤조산, o-니트로벤조산, m-니트로벤조산, p-니트로벤조산, 프탈산, 이소프탈산, 테레프탈산, 살리실산, p-히드록시벤조산, 안트라닐산, m-아미노벤조산, p-아미노벤조산, o-메톡시벤조산, m-메톡시벤조산, p-메톡시벤조산, 옥살산, 말론산, 숙신산, 글루타르산, 아디프산, 피멜산, 수베르산, 아젤라산, 세바스산, 말레산, 푸마르산, 헤미멜리트산, 트리멜리트산, 트리메신산, 말산 및 시트르산, 이러한 산의 분지쇄 이성질체, 및 이러한 산의 할로겐-치환된 유도체로부터 선택된다.
이러한 카르복실산은 통상적으로 입수가능하거나 통상의 기술자에 의해 쉽게 합성될 수 있다. 이러한 카르복실산의 금속 염은 일반적으로 선택된 수지 조성물에 혼입하기 위해 미분말로 분쇄될 수 있는 고체 물질이다. 금속 염을 제제의 0.05 중량% 내지 10 중량%의 부하량으로 수지 조성물에 부하할 것이다. 한 실시양태에서, 부하량은 대략 0.1 중량% 내지 0.5 중량%이다.
다양한 실시양태에서, 소결 보조제는 리튬 아세테이트, 리튬 아세틸아세토네이트, 리튬 벤조에이트, 리튬 포스페이트, 팔라듐, 팔라듐 메타크릴레이트, 팔라듐(II) 아세틸아세토네이트 및 주석(II) 2-에틸 헥사노에이트로부터 선택된다.
소결 필름은 하나 이상의 금속 및/또는 하나 이상의 금속 합금을 결합제와 함께 또는 결합제 없이 적절한 용매에 분산시켜 소결 페이스트를 형성하고; 소결 페이스트를 기판에 적용하고, 소결 페이스트를 가열하여 이것을 소결 필름으로 건조시키는 것을 포함하는 방법에 의해 제조될 수도 있다. 금속 및 금속 합금은 앞서 기재된 것과 같다. 결합제는 앞서 기재된 것과 같다. 소결 페이스트가 치수 안정성 필름으로 건조될 때 용매가 증발한다. 일부 실시양태에서 온도가 ≤260℃일 수도 있긴 하지만, 건조를 위해 전형적인 조건은 ≤60분의 기간 동안 ≤150℃의 온도이다. 2 이상의 상이한 금속 또는 금속 합금의 조합을 함유하는 조성물을 위하여, 금속 또는 금속 합금의 하나의 융점보다 높은 온도에서 공정을 수행한다.
금속(들) 또는 금속 산화물(들) 및 존재한다면 결합제를 분산 또는 용매화하기 위해 용매가 사용된다. 일부 용매는 또한 플럭싱제(fluxing agent)이다. 적절한 용매는 수소 결합을 수용할 수 있고 산성 수소가 부족한 산소화 용매 및 비양성자성 용매이다. 다양한 실시양태에서, 용매는 부틸 아세테이트, 헥산디올, 프로필렌 카르보네이트, N-메틸-2-피롤리돈, 아세틸아세톤, 2-에틸-1,3-헥산디올, 2-(2-에티옥시에톡시)-에틸아세테이트, 아세톤, 에틸 아세테이트, 디에틸렌 글리콜 모노부틸 에테르 아세테이트, 2-부타논, m-1,4-디옥산, N-에틸 피롤리돈, 디메틸 포름아미드, 시클로옥타논, 디페닐 옥시드, 2-페닐-3-부틴-2-올, 디시클로펜타디엔, 및 테트라히드로푸르푸릴 알콜로부터 선택된다.
일부 실시양태에서, 필름 밀도를 개선하고 공극을 감소시키기 위해 B-단계 처리 후에 소결 필름을 압축시킬 수 있다. 압축 공정은 ≤300℃, 바람직하게는 ≤250℃, 더욱 바람직하게는 ≤150℃의 온도에서 ≤15 MPa의 압력에서 일어날 것이다. 공정은 연속 (바람직하게는) 또는 회분 공정일 수 있다.
필요하다면, 결합 접착제로서 사용하기 전에 플럭싱제의 적용에 의해 B-단계 처리 후의 소결 필름을 재활성화할 수 있다.
≤260℃ 및 ≤50 MPa에서, 바람직하게는 15 MPa 미만에서 열-압축 방법에 의해 원하는 기판에 인쇄함으로써 건조 필름을 추가로 가공할 수 있다.
즉, 추가의 실시양태에서, (a) 하나 이상의 금속 및/또는 하나 이상의 금속 합금을 결합제와 함께 또는 결합제 없이 용매에 분산시켜 소결 페이스트를 형성하고, (b) 소결 페이스트를 기판에 적용하고, (c) 소결 페이스트를 가열하여 이것을 소결 필름으로 건조시키는 것을 포함하는, 소결 필름의 제조 방법이 제공된다. 추가의 단계에서, 방법은 (d) 필름을 ≤300℃의 온도 및 ≤15 MPa의 압력에서 압축시키고/거나 (e) 필름을 기판에 적층하는 것을 포함한다.
소결 필름은 특히 전자 산업에서 금속 대 금속 결합 응용에서 뿐만 아니라 금속 대 금속 결합이 요구되는 다른 산업적 응용을 위해서 종종 사용된다.
전자 산업에서, 이러한 소결 필름은 전도성 웨이퍼 이면 코팅물로서 또는 가공 온도가 약 175℃ 내지 350℃의 범위인 다이 부착 접착제로서 사용될 수 있다. 일부 실시양태에서, 소결 필름을 원하는 기판, 예를 들어 소결 필름을 웨이퍼 이면 코팅물로서 사용하고자 할 경우 규소 웨이퍼, 또는 소결 필름을 전도성 다이 부착 접착제로서 사용하고자 할 경우 라미네이트 이형 라이너 상에 배치한다.
다른 최종 사용 응용에서, 소결 필름을 캐리어 필름, 금속 호일 또는 세라믹 지지체 상에 인쇄할 수 있다. 캐리어 필름은 중합체, 예컨대 폴리에스테르, 폴리아크릴레이트, 또는 폴리이미드일 수도 있다. 캐리어 필름은 또한 UV 투명성 테이프일 수도 있다. 캐리어 필름이 금속 호일일 경우, 소결 필름을 호일의 한 면 또는 양 면에서 인쇄하고 B-단계 처리할 수 있다. 일부 사용을 위하여, 조합된 두께는 전형적으로 100 마이크로미터 미만이지만 50 마이크로미터 미만일 수도 있다.
다른 실시양태에서, 소결 필름을 발포체 또는 메쉬에 주입할 수도 있고, 여기서 발포체 또는 메쉬는 금속, 중합체 또는 세라믹으로 구성된다. 대안적으로, 소결 필름을 캐리어, 예컨대 캐리어 필름, 금속 호일 또는 세라믹 지지체에 적용할 수도 있다.
하기 실시예는 본 발명을 예증하는 것을 돕지만 본 발명을 제한하지 않아야 한다.
실시예
하기 실시예에서, 분해가능한 결합제와 함께 은으로부터 소결 필름을 제조하고 다음과 같이 평가하였다.
시험 수단은 표시한 대로 구리 또는 은 기판 상의 금속화 (티타늄-니켈-은) 규소 다이였다.
부피 저항성으로서 측정되는 전기 전도도를 메그옴(Megohm) 브릿지 상의 4개 지점 프로브로 측정하였다.
네쯔쉬(Netzsch) 기기를 사용하여 레이저 플래시 방법에 의해 열 전도도를 측정하였다.
티타늄-니켈-은으로 금속화된 규소 다이 및 나 구리 또는 은-코팅된 구리 기판을 사용하여 데이지(Dage) 다이 전단 시험기 상에서 다이 전단 강도(DSS)를 측정하였다.
실시예 내의 모든 샘플에 대하여, 수동 부착 또는 열 압축 부착으로 다이 부착을 달성하였다. 샘플을 30초 동안 500 mj/Sq-cm로 UV에 2회 노출시킨 다음, 토레이 엔지니어링(Toray Engineering) FC-100 다이 결합기로 ≤275℃에서 샘플에 의존하여 0.1초 내지 15분 동안 10N 내지 150N 범위의 결합 헤드 힘에서 선택된 기판에 부착하였다. 전형적으로 ≤250℃에서 ≤60분 동안 충분히 소결하기 위하여 후 다이 부착 소결 공정을 사용하였다.
각각의 몇몇 제형에 대하여 저항성, 열 전도도 및 다이 전단을 측정하였으며, 결과를 하기 실시예에 기록하였다. TGA는 열중량 분석이다.
실시예 1
표 1에서 중량 기준으로 제형에 따라 필름을 제조하였다. 아크릴 결합제가 사용될 경우, 퍼옥시드를 제형에 첨가하지 않는다; 이는 B-단계 처리 동안에 아크릴의 가교를 방해한다. 소결 조성물을 150℃에서 1시간 동안 가열하여 용매를 제거하고 조성물을 소결 필름에 안정화하였다. 상기 기재된 시험 수단에서 필름을 사용하였다. 데이터를 표 1에 또한 기록하고, 이는 분해가능한 결합제를 사용하여 소결 필름을 제조할 수 있음을 나타낸다.
실시예 2
이 실시예에서 교대하는 이소부틸렌 및 말레산 무수물 기의 선형 공중합체를 결합제로서 사용하였다. 공중합체는 플럭싱 작용성, 37℃의 연화점 및 78,000-94,000의 분자량을 갖는다. 표시한 대로 은 및 구리 기판에서 다이 전단을 수행하였다. 결과를 표 2에 기록하고, 이는 공중합체 결합제를 함유하는 샘플에 대하여 개선된 접착성 및 저온 적층 및 다이 부착을 나타낸다.
실시예 3
이 실시예에서, 소결을 증진시키기 위하여 리튬 알칼리 금속 및 팔라듐 전이 금속을 소결 조성물에 첨가한다. 은을 위한 소결 양상은 250℃까지의 30분 경사 + 250℃에서 60분이었다. 구리 및 합금-42를 위한 소결 경사는 350℃ + 350℃에서 60분이었다. 금속 결합 표면 간에 접착 강도를 갖도록 금속간 연결을 형성하기 위해 은이 충분히 소결되었다. 구리 및 합금이 소결되지만, 접착성을 개선하기 위해 다른 금속화를 사용하지 않는다. 결과를 표 3에 기록한다.
실시예 4
이 실시예에서, 합금 조합을 함유하는 표 4에서 조성물로부터 소결 필름을 제조하였다. 폴리이미드 기판 상에 조성물의 2 mil 필름을 인쇄하고, 260℃ 피크 솔더 리플로우(solder reflow) 공정에서 조성물을 B-단계 처리하고, 2개 폴리이미드 필름 간에 2분 동안 열 프레싱하고 (대략 0.65-0.75 MPa (100-110 psi) 및 200℃에서), 소결 필름을 노출하고, 소결 필름을 테트라히드로푸르푸릴 알콜 중의 15% 아젤라산 용액에 침지시킨 다음, 필름을 사용하여 5N 및 240℃에서 30초 동안 다이를 구리 기판에 결합시킨다. 결합 이전에, 필름 표면을 재-활성화하기 위해 플럭싱 용액의 적용을 사용하였다. 결합 이전에, 필름 밀도를 개선하기 위해 압력의 적용을 사용하였다. 결과를 표 4에 나타낸다.
실시예 5
이 실시예는 소결 조성물에 금속 염을 첨가하는 이점을 나타낸다. 실시예 I는 금속 염을 함유하지 않고 다이 전단 강도가 통상적으로 허용가능하다. 금속 염을 함유하지 않는 실시예 J는 더 높은 다이 전단 강도를 나타내었으며, 이는 금속 염의 첨가가 조성물의 다이 전단 강도를 개선할 수 있음을 표시한다. 결과를 표 5에 기록한다.
Claims (14)
- 하나 이상의 금속 및/또는 하나 이상의 금속 합금을 포함하는 물질의 조성물로서, 여기서 하나 이상의 금속 및/또는 하나 이상의 금속 합금은 고 융점 상 및 저 융점 상에 존재하고, 저 융점 상은 300℃ 미만의 온도에서 용융되고,
여기서 하나 이상의 금속 및/또는 하나 이상의 금속 합금은 Ag를 함유하며, 상기 조성물은
리튬 아세테이트, 리튬 아세틸아세토네이트, 리튬 벤조에이트, 리튬 포스페이트, 팔라듐, 팔라듐 메타크릴레이트, 팔라듐(II) 아세틸아세토네이트 및 주석(II) 2-에틸 헥사노에이트로 이루어진 군으로부터 선택된 소결 보조제를 포함하는 것인, 물질의 조성물. - 제1항에 있어서, 소결 필름의 형태인 물질의 조성물.
- 제1항에 있어서, 그래핀, 탄소 나노튜브 또는 전도성 유기 중합체를 추가로 포함하는 물질의 조성물.
- 제1항에 있어서, 고체 또는 반고체 유기 결합제를 추가로 포함하는 물질의 조성물.
- 제4항에 있어서, 고체 또는 반고체 유기 결합제가 플럭싱(fluxing) 작용성을 갖는 것인 물질의 조성물.
- 제5항에 있어서, 플럭싱 작용성이 히드록실, 카르복실, 무수물, 에스테르, 아민, 아미드, 티올, 티오에스테르 및 포스페이트 에스테르 기로 이루어진 군으로부터 선택되는 기로부터인 물질의 조성물.
- 제4항에 있어서, 결합제가 50℃ 미만의 연화점을 갖는 화합물인 물질의 조성물.
- 제7항에 있어서, 결합제가 아크릴 수지 또는 알킬화 폴리비닐피롤리돈인 물질의 조성물.
- 제7항에 있어서, 결합제가 플럭싱 작용성을 갖는 것인 물질의 조성물.
- 제9항에 있어서, 결합제가 카르복실 산 또는 말레산 무수물로 작용화된 아크릴 수지, 또는 이소부틸렌 및 말레산 무수물의 공중합체, 또는 에폭시드를 이용한 폴리-알킬렌 카르보네이트 공중합체인 물질의 조성물.
- 제4항에 있어서, 결합제가 ≤350℃의 온도에서 열적으로 분해되는 화합물인 물질의 조성물.
- (a) 제1항에 따른 물질의 조성물을 결합제와 함께 또는 결합제 없이 용매에 분산시켜 소결 페이스트를 형성하고;
(b) 소결 페이스트를 기판에 적용하거나, 또는
(c) 소결 페이스트를 발포체 또는 메쉬에 주입하고,
(d) 소결 페이스트를 가열하여 이것을 소결 필름으로 건조시키는 것
을 포함하는, 소결 필름의 제조 방법. - 제12항에 있어서,
(e) 필름을 ≤300℃의 온도 및 ≤15 MPa의 압력에서 압축시키고/거나
(f) 필름을 기판에 적층하는 것
을 추가로 포함하는 제조 방법. - 제2항에 있어서, 캐리어 필름, 금속 호일, 규소 다이, 규소 웨이퍼, 금속 회로 기판 또는 세라믹 지지체인 기판에 적용된 소결 필름의 형태인 물질의 조성물.
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- 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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Also Published As
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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 |
CN105473257B (zh) | 2018-11-13 |
EP3041627A1 (en) | 2016-07-13 |
KR20160051766A (ko) | 2016-05-11 |
EP3041627A4 (en) | 2017-05-03 |
US20160151864A1 (en) | 2016-06-02 |
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