JP6338419B2 - Metal particle composition, bonding material, and bonding method using the same - Google Patents
Metal particle composition, bonding material, and bonding method using the same Download PDFInfo
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- JP6338419B2 JP6338419B2 JP2014067867A JP2014067867A JP6338419B2 JP 6338419 B2 JP6338419 B2 JP 6338419B2 JP 2014067867 A JP2014067867 A JP 2014067867A JP 2014067867 A JP2014067867 A JP 2014067867A JP 6338419 B2 JP6338419 B2 JP 6338419B2
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- nickel
- weight
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- fine particles
- component
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- 239000000463 material Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 41
- 239000000203 mixture Substances 0.000 title claims description 20
- 239000002923 metal particle Substances 0.000 title claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 227
- 229910052759 nickel Inorganic materials 0.000 claims description 123
- 239000010419 fine particle Substances 0.000 claims description 71
- 239000002245 particle Substances 0.000 claims description 69
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 40
- 229910052718 tin Inorganic materials 0.000 claims description 40
- 239000003960 organic solvent Substances 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 24
- 238000005304 joining Methods 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000007561 laser diffraction method Methods 0.000 claims description 5
- 238000000790 scattering method Methods 0.000 claims description 5
- 239000011135 tin Substances 0.000 description 43
- 238000010438 heat treatment Methods 0.000 description 41
- 229910052751 metal Inorganic materials 0.000 description 32
- 239000002184 metal Substances 0.000 description 31
- 150000003141 primary amines Chemical class 0.000 description 30
- -1 nickel carboxylate Chemical class 0.000 description 28
- 239000002002 slurry Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000005755 formation reaction Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 229910000679 solder Inorganic materials 0.000 description 15
- 229910000765 intermetallic Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 229910001453 nickel ion Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 230000000536 complexating effect Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 11
- 230000009918 complex formation Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 8
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 8
- 229940088601 alpha-terpineol Drugs 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000002815 nickel Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NNRLDGQZIVUQTE-UHFFFAOYSA-N gamma-Terpineol Chemical compound CC(C)=C1CCC(C)(O)CC1 NNRLDGQZIVUQTE-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 2
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- GMWUGZRYXRJLCX-UHFFFAOYSA-N 2-methoxypentan-2-ol Chemical compound CCCC(C)(O)OC GMWUGZRYXRJLCX-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- 241000132023 Bellis perennis Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000005633 Chrysanthemum balsamita Nutrition 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910008599 TiW Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- NAVSKFYJNZQECG-UHFFFAOYSA-N nickel;propanoic acid Chemical compound [Ni].CCC(O)=O NAVSKFYJNZQECG-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Description
本発明は、電子部品の製造に利用可能な金属粒子組成物、接合材及びそれを用いた接合方法に関する。 The present invention relates to a metal particle composition that can be used for manufacturing electronic components, a bonding material, and a bonding method using the same.
金属微粒子は、バルク金属とは異なる物理的・化学的特性を有することから、様々な工業材料に利用されている。近年では、電子機器の小型化や薄型化に伴い、工業用の金属微粒子の粒子径も、数十〜数百ｎｍ程度まで微粒子化が進んでいる。例えば、比較的に安価で、高温での使用が可能なニッケル材料を利用した電子部品の接合材として、ニッケル又はニッケル合金により構成される金属微粒子と、該金属微粒子を被覆する酸素含有皮膜と、を備え、平均粒子径が１００ｎｍ以下である金属ナノ粒子を含むものが提案されている（例えば、特許文献１）。 Metal fine particles have physical and chemical properties different from those of bulk metals, and are therefore used in various industrial materials. In recent years, with the downsizing and thinning of electronic devices, the particle diameter of industrial metal fine particles has been reduced to about several tens to several hundreds of nanometers. For example, as a bonding material for electronic parts using a nickel material that is relatively inexpensive and can be used at high temperatures, metal fine particles composed of nickel or a nickel alloy, and an oxygen-containing film that covers the metal fine particles, And a metal nanoparticle having an average particle diameter of 100 nm or less has been proposed (for example, Patent Document 1).
また、ニッケル粒子をはんだと組み合わせて接合材料に用いた例も提案されている。例えば特許文献２では平均粒径が２０〜３００μｍのニッケル粒子をフォームはんだ中に分散させることにより、半導体素子の基板に対する傾斜を防止し、さらにニッケル粒子表面とはんだ間に金属間化合物を形成することで高接合強度を達成している。 An example in which nickel particles are used as a bonding material in combination with solder has also been proposed. For example, in Patent Document 2, nickel particles having an average particle diameter of 20 to 300 μm are dispersed in foam solder to prevent the inclination of the semiconductor element relative to the substrate, and further, an intermetallic compound is formed between the nickel particle surface and the solder. High joint strength is achieved.
近年、電力変換器用途をはじめとするパワーデバイスのさらなる高効率駆動を実現するため、高温駆動時の信頼性が求められるようになり、半導体実装材料における接合信頼性は重要な課題となっている。しかしながら、特許文献２のようなスズ系はんだによる接合材を用いた場合では、金属間化合物の形成は金属粒子の表面に限られているため、融点以上の温度で駆動する際に、当然ではあるが接合材の再融解が生じる、という問題があった。 In recent years, in order to realize further high-efficiency driving of power devices including power converter applications, reliability during high-temperature driving has been required, and bonding reliability in semiconductor mounting materials has become an important issue. . However, in the case of using a tin-based solder bonding material as in Patent Document 2, since the formation of intermetallic compounds is limited to the surface of the metal particles, it is natural when driving at a temperature above the melting point. However, there was a problem that remelting of the bonding material occurred.
本発明の目的は、はんだの融点以上の温度でも、はんだが再融解せず、高い接合強度を発現する接合層を形成することが可能な接合材および接合方法を提供することである。 An object of the present invention is to provide a bonding material and a bonding method capable of forming a bonding layer that exhibits high bonding strength without remelting the solder even at a temperature equal to or higher than the melting point of the solder.
本発明者は、ナノサイズのニッケル微粒子を用いることにより、溶融したはんだとの間で金属間化合物形成が効率的に生じ、はんだの融点以上の温度であっても高い接合強度が得られることを見出した。 By using nano-sized nickel fine particles, the present inventor efficiently forms an intermetallic compound with molten solder, and a high bonding strength can be obtained even at a temperature higher than the melting point of the solder. I found it.
本発明の金属粒子組成物は、次の成分Ａ及びＢ；
Ａ）レーザー回折／散乱法による平均粒子径が０．５〜２０μｍの範囲内であり、スズ元素を９５重量％以上含有するスズ粒子、
Ｂ）走査型電子顕微鏡観察による平均一次粒子径が３０〜２００ｎｍの範囲内であり、ニッケル元素を９０〜９９．５重量％の範囲内で含有するニッケル微粒子、
からなる金属粒子組成物であって、前記成分Ａ及び成分Ｂの重量比（成分Ａ：成分Ｂ）が５０：５０〜１０：９０の範囲内である。
The metal particle composition of the present invention comprises the following components A and B;
A) a tin particle having an average particle diameter by laser diffraction / scattering method in the range of 0.5 to 20 μm and containing 95% by weight or more of tin element;
B) Nickel fine particles having an average primary particle diameter in a range of 30 to 200 nm by observation with a scanning electron microscope and containing nickel element in a range of 90 to 99.5% by weight,
The weight ratio of the component A and the component B (component A: component B) is in the range of 50:50 to 10:90.
本発明の接合材は、上記金属粒子組成物を含有する接合材であって、前記金属粒子組成物の含有量が７０〜９５重量％の範囲内である。 The joining material of this invention is a joining material containing the said metal particle composition, Comprising: Content of the said metal particle composition exists in the range of 70 to 95 weight%.
本発明の接合材は、さらに、沸点１５０〜２６０℃の範囲内にある有機溶媒を含有していてもよく、前記有機溶媒の含有量が５〜３０重量％の範囲内であってもよい。 The bonding material of the present invention may further contain an organic solvent having a boiling point in the range of 150 to 260 ° C., and the content of the organic solvent may be in the range of 5 to 30% by weight.
本発明の接合方法は、上記接合材を、被接合部材の間に介在させて還元性ガスを含有する還元性ガス雰囲気下で２５０〜５００℃の範囲内の温度で加熱することにより、被接合部材の間に接合層を形成する。 In the joining method of the present invention, the joining material is interposed between the members to be joined and heated at a temperature in the range of 250 to 500 ° C. in a reducing gas atmosphere containing a reducing gas. A bonding layer is formed between the members.
本発明の金属粒子組成物、接合材及び接合方法によれば、２５０℃以上の温度で、ニッケル微粒子とはんだとの間に金属間化合物を効率的に形成することが可能となり、はんだの融点以上の温度でも、はんだが再融解せず、高い接合強度を発現する接合層が得られる。 According to the metal particle composition, the bonding material, and the bonding method of the present invention, it becomes possible to efficiently form an intermetallic compound between the nickel fine particles and the solder at a temperature of 250 ° C. or higher, which is higher than the melting point of the solder. Even at this temperature, the solder does not remelt and a bonding layer that exhibits high bonding strength is obtained.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
［金属粒子組成物］
本発明の実施の形態の金属粒子組成物は、次の成分Ａ及びＢ；
Ａ）レーザー回折／散乱法による平均粒子径が０．５〜２０μｍの範囲内であり、スズ元素を９５重量％以上含有するスズ粒子、
Ｂ）走査型電子顕微鏡観察による平均一次粒子径が３０〜２００ｎｍの範囲内であり、ニッケル元素を９０〜９９．５質量％の範囲内で含有するニッケル微粒子、
からなる金属粒子組成物であって、前記成分Ａ及び成分重量Ｂの重量比（Ａ：Ｂ）が５０：５０〜１０：９０の範囲内である。
[Metal particle composition]
The metal particle composition of the embodiment of the present invention includes the following components A and B;
A) a tin particle having an average particle diameter by laser diffraction / scattering method in the range of 0.5 to 20 μm and containing 95% by weight or more of tin element;
B) Nickel fine particles having an average primary particle diameter in a range of 30 to 200 nm by observation with a scanning electron microscope and containing nickel element in a range of 90 to 99.5% by mass,
A weight ratio (A: B) of the component A and the component weight B is in the range of 50:50 to 10:90.
＜成分Ａ：スズ粒子＞
成分Ａのスズ粒子は、接合前の接合層に適度な厚みを持たせ、骨格を形成する観点から、レーザー回折／散乱法による平均粒子径が０．５〜２０μｍの範囲内とする。平均粒子径が０．５μｍ未満であると、焼結過程で成分Ｂのニッケル微粒子が動きやすくなり、成分Ｂの凝集体が生じやすくなる。一方、平均粒子径が２０μｍを超えると、ニッケル微粒子と効率良く金属間化合物が形成されず、スズの偏在箇所が多くなり、脆弱な接合層となる。
<Component A: Tin particles>
The tin particles of component A have an average particle diameter in the range of 0.5 to 20 μm by laser diffraction / scattering method from the viewpoint of giving an appropriate thickness to the bonding layer before bonding and forming a skeleton. When the average particle size is less than 0.5 μm, the nickel fine particles of component B are likely to move during the sintering process, and the aggregates of component B are liable to occur. On the other hand, when the average particle diameter exceeds 20 μm, the nickel fine particles and the intermetallic compound are not efficiently formed, and the unevenly distributed portions of tin increase, resulting in a fragile bonding layer.
また、スズ粒子は、スズ元素を９５重量％以上含有する。スズ元素の含有率を９５重量％以上とするのは、この含有率が融点２００℃以上の鉛フリーはんだにおいて一般的な値であり、加熱時の溶融挙動を把握しやすいためである。 The tin particles contain 95% by weight or more of tin element. The reason why the content of tin element is 95% by weight or more is that this content is a common value for lead-free solder having a melting point of 200 ° C. or higher, and it is easy to grasp the melting behavior during heating.
成分Ａのスズ粒子は、スズ以外の金属を含有していてもよい。スズ以外の金属としては、例えば、例えば、ニッケル、チタン、コバルト、銅、クロム、マンガン、鉄、ジルコニウム、タングステン、モリブデン、バナジウム等の卑金属、金、銀、白金、パラジウム、イリジウム、オスミウム、ルテニウム、ロジウム、レニウム等の貴金属などの金属元素を挙げることができる。これらは、単独で又は２種以上含有していてもよい。 The tin particles of component A may contain a metal other than tin. Examples of metals other than tin include, for example, base metals such as nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tungsten, molybdenum, vanadium, gold, silver, platinum, palladium, iridium, osmium, ruthenium, Examples of the metal element include noble metals such as rhodium and rhenium. These may be contained alone or in combination of two or more.
成分Ａのスズ粒子は、その製造方法を問わず利用できる。成分Ａのスズ粒子としては、例えば、株式会社日本フィラーメタルズ製（製品名：ＤＳ−１０）、福田金属箔粉工業株式会社製（製品名：Ｓｎ−Ａｔ−６００）などの市販品を好ましく利用できる。 The tin particles of component A can be used regardless of the production method. As the tin particles of component A, for example, commercially available products such as those manufactured by Nippon Filler Metals Co., Ltd. (product name: DS-10) and Fukuda Metal Foil Powder Industry Co., Ltd. (product name: Sn-At-600) are preferably used. it can.
＜成分Ｂ;ニッケル微粒子＞
成分Ｂのニッケル微粒子は、走査型電子顕微鏡観察による平均一次粒子径が３０〜２００ｎｍの範囲内である。ニッケル微粒子の平均一次粒子径が３０ｎｍ未満であると、ニッケル微粒子が凝集しやすくなり、スズ粒子との均一な混合が困難となる。一方、ニッケル微粒子の平均一次粒子径が２００ｎｍを超えると、後述する比較例２のように、スズ粒子との間で効率良く金属間化合物が形成されず、ニッケル微粒子同士の焼結性も低下する。なお、本明細書において、ニッケル微粒子の一次粒子の平均粒子径は、実施例で用いた値を含めて、電界放出形走査電子顕微鏡（Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ−Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：ＦＥ−ＳＥＭ）により試料の写真を撮影して、その中から無作為に２００個を抽出してそれぞれの面積を求め、真球に換算したときの粒子径を個数基準として算出した値である。
<Component B: Nickel fine particles>
The nickel fine particles of component B have an average primary particle diameter in the range of 30 to 200 nm as observed with a scanning electron microscope. When the average primary particle diameter of the nickel fine particles is less than 30 nm, the nickel fine particles are easily aggregated, and uniform mixing with the tin particles becomes difficult. On the other hand, when the average primary particle diameter of the nickel fine particles exceeds 200 nm, an intermetallic compound is not efficiently formed with the tin particles as in Comparative Example 2 described later, and the sinterability between the nickel fine particles also decreases. . In addition, in this specification, the average particle diameter of the primary particles of the nickel fine particles, including the values used in the examples, is a photograph of a sample by a field emission scanning electron microscope (FE-SEM). Is a value calculated based on the number of particles, which is obtained by randomly extracting 200 images from each of the images, obtaining the respective areas, and converting them into true spheres.
成分Ｂのニッケル微粒子は、ニッケル元素を９０〜９９．５重量％の範囲内で含有する。成分Ｂとして、湿式還元法で製造したニッケル微粒子や分散処理を行ったニッケル微粒子を使用する場合は、それらの平均一次粒子径が３０〜２００ｎｍの範囲内であると、表面被覆の炭素や不動態酸素の存在で、ニッケル元素の含有量は上記の値となる。
The nickel fine particle of component B contains nickel element in the range of 90 to 99.5 % by weight. When using nickel fine particles produced by a wet reduction method or nickel fine particles that have been subjected to a dispersion treatment as component B, if the average primary particle diameter is within the range of 30 to 200 nm, the surface coating carbon and the passive state are used. In the presence of oxygen, the content of nickel element is the above value.
成分Ｂのニッケル微粒子は、ニッケル以外の金属を含有していてもよい。ニッケル以外の金属としては、例えば、スズ、チタン、コバルト、銅、クロム、マンガン、鉄、ジルコニウム、タングステン、モリブデン、バナジウム等の卑金属、金、銀、白金、パラジウム、イリジウム、オスミウム、ルテニウム、ロジウム、レニウム等の貴金属などの金属元素を挙げることができる。これらは、単独で又は２種以上含有していてもよい。 The nickel fine particles of component B may contain a metal other than nickel. Examples of metals other than nickel include, for example, base metals such as tin, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tungsten, molybdenum, and vanadium, gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, A metal element such as a noble metal such as rhenium can be given. These may be contained alone or in combination of two or more.
また、成分Ｂとして、湿式還元法で製造したニッケル微粒子や分散処理を行ったニッケル微粒子を使用する場合は、例えば、酸素元素、炭素元素などの非金属元素を含有していてもよい。炭素元素を含有する場合、その含有率は、例えば０．３〜２．５重量％の範囲内、好ましくは０．５〜２．０重量％の範囲内である。炭素元素は、ニッケル微粒子の表面に存在する有機化合物に由来するものであり、ニッケル微粒子の分散性向上に寄与する。従って、炭素元素の含有量が０．３重量％未満では、十分な分散性が得られない場合があり、２．５重量％を超える場合は、焼成後に炭化して残炭となり、接合層の導電性を低下させる可能性がある。また、酸素元素を含有する場合、その含有率は、例えば０．７〜７．５重量％の範囲内、好ましくは１．０〜２．０重量％の範囲内である。酸素元素は、主に水酸化ニッケルの被膜に由来するものであり、水酸化ニッケルの被膜が還元されて存在しなくなると、ニッケル微粒子の焼結が開始される。酸素元素の含有率が７．５重量％を超えると、ニッケル微粒子の凝集が生じやすくなり、ペースト状態を保持できず、粉状になる傾向となる。 Moreover, when using the nickel fine particle manufactured by the wet reduction method or the nickel fine particle which performed the dispersion process as component B, nonmetallic elements, such as an oxygen element and a carbon element, may be contained, for example. When the carbon element is contained, the content thereof is, for example, in the range of 0.3 to 2.5% by weight, preferably in the range of 0.5 to 2.0% by weight. The carbon element is derived from an organic compound present on the surface of the nickel fine particles, and contributes to an improvement in the dispersibility of the nickel fine particles. Therefore, when the carbon element content is less than 0.3% by weight, sufficient dispersibility may not be obtained. When the carbon element content exceeds 2.5% by weight, carbonization is performed after firing to form residual charcoal. There is a possibility of reducing the conductivity. Moreover, when it contains an oxygen element, the content rate is in the range of 0.7 to 7.5 weight%, for example, Preferably it exists in the range of 1.0 to 2.0 weight%. The oxygen element is mainly derived from the nickel hydroxide coating, and when the nickel hydroxide coating is reduced and no longer exists, the sintering of the nickel fine particles is started. When the oxygen element content exceeds 7.5% by weight, the nickel fine particles are likely to aggregate, and the paste state cannot be maintained and tends to be powdery.
成分Ｂのニッケル微粒子は、その製造方法を問わず利用できるが、ニッケル塩及び有機アミンを含む混合物から、湿式還元法によりニッケルイオンを加熱還元して析出させる公知の方法によって得られたものが好ましい（例えば、特許文献１を参照）。ここでは、湿式還元法によるニッケル微粒子の製造方法の一例について説明する。 The nickel fine particles of component B can be used regardless of the production method, but those obtained by a known method in which nickel ions are heated and reduced by a wet reduction method from a mixture containing a nickel salt and an organic amine are preferable. (For example, see Patent Document 1). Here, an example of a method for producing nickel fine particles by a wet reduction method will be described.
湿式還元法によるニッケル微粒子の製造は、次の工程１及び２；
工程１）カルボン酸ニッケル及び１級アミンを含む混合物を、１００℃〜１６５℃の範囲内の温度に加熱して錯化反応液を得る錯化反応液生成工程、
及び、
工程２）該錯化反応液を、マイクロ波照射によって１７０℃以上の温度に加熱して該錯化反応液中のニッケルイオンを還元し、１級アミンで被覆されたニッケル微粒子のスラリーを得るニッケル微粒子スラリー生成工程、
を含むことができる。
The production of nickel fine particles by the wet reduction method includes the following steps 1 and 2;
Step 1) A complexing reaction solution generating step of obtaining a complexing reaction solution by heating a mixture containing nickel carboxylate and a primary amine to a temperature within a range of 100 ° C. to 165 ° C.,
as well as,
Step 2) Nickel to obtain a slurry of nickel fine particles coated with primary amine by heating the complexing reaction liquid to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction liquid Fine particle slurry generation process,
Can be included.
工程１）錯化反応液生成工程：
（カルボン酸ニッケル）
カルボン酸ニッケル（カルボン酸のニッケル塩）は、カルボン酸の種類を限定するものではなく、例えば、カルボキシル基が１つのモノカルボン酸であってもよく、また、カルボキシル基が２つ以上のカルボン酸であってもよい。また、非環式カルボン酸であってもよく、環式カルボン酸であってもよい。このようなカルボン酸ニッケルとして、非環式モノカルボン酸ニッケルを好適に用いることができ、非環式モノカルボン酸ニッケルのなかでも、ギ酸ニッケル、酢酸ニッケル、プロピオン酸ニッケル、シュウ酸ニッケル、安息香酸ニッケル等を用いることがより好ましい。これらの非環式モノカルボン酸ニッケルを用いることによって、例えば、得られるニッケル微粒子は、その形状のばらつきが抑制され、均一な形状として形成されやすくなる。カルボン酸ニッケルは、無水物であってもよく、また水和物であってもよい。
Step 1) Complexation reaction solution generation step:
(Nickel carboxylate)
The nickel carboxylate (nickel salt of carboxylic acid) is not limited to the type of carboxylic acid. For example, the carboxyl group may be a monocarboxylic acid having one carboxyl group, or a carboxylic acid having two or more carboxyl groups. It may be. Moreover, acyclic carboxylic acid may be sufficient and cyclic carboxylic acid may be sufficient. As such nickel carboxylate, nickel acyclic monocarboxylate can be preferably used, and among nickel acyclic monocarboxylate, nickel formate, nickel acetate, nickel propionate, nickel oxalate, benzoic acid It is more preferable to use nickel or the like. By using these nickel acyclic monocarboxylates, for example, the resulting nickel fine particles are less likely to have a variation in shape and are easily formed as a uniform shape. The nickel carboxylate may be an anhydride or a hydrate.
（１級アミン）
１級アミンは、ニッケルイオンとの錯体を形成することができ、ニッケル錯体（又はニッケルイオン）に対する還元能を効果的に発揮する。一方、２級アミンは立体障害が大きいため、ニッケル錯体の良好な形成を阻害するおそれがあり、３級アミンはニッケルイオンの還元能を有しないため、いずれも単独では使用できないが、１級アミンを使用する上で、生成するニッケル微粒子の形状に支障を与えない範囲でこれらを併用することは差し支えない。１級アミンは、ニッケルイオンとの錯体を形成できるものであれば、特に限定するものではなく、常温で固体又は液体のものが使用できる。ここで、常温とは、２０℃±１５℃をいう。常温で液体の１級アミンは、ニッケル錯体を形成する際の有機溶媒としても機能する。なお、常温で固体の１級アミンであっても、１００℃以上の加熱によって液体であるか、又は有機溶媒を用いて溶解するものであれば、特に問題はない。
(Primary amine)
The primary amine can form a complex with nickel ions, and effectively exhibits a reducing ability for nickel complexes (or nickel ions). On the other hand, secondary amines have great steric hindrance and may hinder the good formation of nickel complexes. Since tertiary amines do not have the ability to reduce nickel ions, none can be used alone. When these are used, these may be used in combination as long as the shape of the nickel fine particles to be produced is not hindered. The primary amine is not particularly limited as long as it can form a complex with nickel ions, and can be a solid or liquid at room temperature. Here, room temperature means 20 ° C. ± 15 ° C. The primary amine that is liquid at room temperature also functions as an organic solvent for forming the nickel complex. In addition, even if it is a primary amine solid at normal temperature, there is no particular problem as long as it is liquid by heating at 100 ° C. or higher, or can be dissolved using an organic solvent.
１級アミンは、芳香族１級アミンであってもよいが、反応液におけるニッケル錯体形成の容易性の観点からは脂肪族１級アミンが好適である。脂肪族１級アミンは、例えばその炭素鎖の長さを調整することによって生成するニッケル微粒子の粒径を制御することができ、特に平均一次粒子径が３０ｎｍ〜２００ｎｍの範囲内にあるニッケル微粒子を製造する場合において有利である。ニッケル微粒子の粒径を制御する観点から、脂肪族１級アミンは、その炭素数が６〜２０程度のものから選択して用いることが好適である。炭素数が多いほど得られるニッケル微粒子の粒径が小さくなる。このようなアミンとして、例えばオクチルアミン、トリオクチルアミン、ジオクチルアミン、ヘキサデシルアミン、ドデシルアミン、テトラデシルアミン、ステアリルアミン、オレイルアミン、ミリスチルアミン、ラウリルアミン等を挙げることができる。例えばオレイルアミンは、ニッケル微粒子生成過程に於ける温度条件下において液体状態として存在するため均一溶液で反応を効率的に進行できる。 The primary amine may be an aromatic primary amine, but an aliphatic primary amine is preferred from the viewpoint of easy nickel complex formation in the reaction solution. The aliphatic primary amine can control the particle diameter of the nickel fine particles produced by adjusting the length of the carbon chain, for example, especially the nickel fine particles having an average primary particle diameter in the range of 30 nm to 200 nm. This is advantageous when manufacturing. From the viewpoint of controlling the particle diameter of the nickel fine particles, the aliphatic primary amine is preferably selected from those having about 6 to 20 carbon atoms. The larger the carbon number, the smaller the particle size of the nickel fine particles obtained. Examples of such amines include octylamine, trioctylamine, dioctylamine, hexadecylamine, dodecylamine, tetradecylamine, stearylamine, oleylamine, myristylamine, and laurylamine. For example, oleylamine exists in a liquid state under the temperature conditions in the nickel fine particle production process, and therefore the reaction can proceed efficiently in a homogeneous solution.
１級アミンは、ニッケル微粒子の生成時に表面修飾剤として機能するため、１級アミンの除去後においても二次凝集を抑制できる。また、１級アミンは、還元反応後の生成したニッケル微粒子の固体成分と溶剤または未反応の１級アミン等を分離する洗浄工程における処理操作の容易性の観点からは室温で液体のものが好ましい。更に、１級アミンは、ニッケル錯体を還元してニッケル微粒子を得るときの反応制御の容易性の観点からは還元温度より沸点が高いものが好ましい。すなわち、脂肪族１級アミンにおいては沸点が１８０℃以上のものが好ましく、２００℃以上のものがより好ましく、また、炭素数が９以上のものが好ましい。ここで、例えば炭素数が９である脂肪族アミンのＣ９Ｈ２１Ｎ(ノニルアミン)の沸点は２０１℃である。１級アミンの量は、ニッケル１ｍｏｌに対して２ｍｏｌ以上用いることが好ましく、２．２ｍｏｌ以上用いることがより好ましく、４ｍｏｌ以上用いることが望ましい。１級アミンの量が２ｍｏｌ未満では、得られるニッケル微粒子の粒子径の制御が困難となり、粒子径がばらつきやすくなる。また、１級アミンの量の上限は特にはないが、例えば生産性の観点からは２０ｍｏｌ以下とすることが好ましい。 Since the primary amine functions as a surface modifier during the production of the nickel fine particles, secondary aggregation can be suppressed even after removal of the primary amine. The primary amine is preferably liquid at room temperature from the viewpoint of ease of processing operation in the washing step of separating the solid component of the nickel fine particles produced after the reduction reaction and the solvent or unreacted primary amine. . Further, the primary amine is preferably one having a boiling point higher than the reduction temperature from the viewpoint of ease of reaction control when the nickel complex is reduced to obtain nickel fine particles. That is, the aliphatic primary amine preferably has a boiling point of 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably has 9 or more carbon atoms. Here, for example, the boiling point of C 9 H 21 N (nonylamine) of an aliphatic amine having 9 carbon atoms is 201 ° C. The amount of primary amine is preferably 2 mol or more, more preferably 2.2 mol or more, and more preferably 4 mol or more with respect to 1 mol of nickel. When the amount of primary amine is less than 2 mol, it is difficult to control the particle diameter of the obtained nickel fine particles, and the particle diameter tends to vary. The upper limit of the amount of primary amine is not particularly limited, but is preferably 20 mol or less from the viewpoint of productivity, for example.
（有機溶媒）
工程１では、均一溶液での反応をより効率的に進行させるために、１級アミンとは別の有機溶媒を新たに添加してもよい。有機溶媒を用いる場合、有機溶媒をカルボン酸ニッケル及び１級アミンと同時に混合してもよいが、カルボン酸ニッケル及び１級アミンを先ず混合し錯形成した後に有機溶媒を加えると、１級アミンが効率的にニッケル原子に配位するので、より好ましい。使用できる有機溶媒としては、１級アミンとニッケルイオンとの錯形成を阻害しないものであれば、特に限定するものではなく、例えば炭素数４〜３０のエーテル系有機溶媒、炭素数７〜３０の飽和又は不飽和の炭化水素系有機溶媒、炭素数８〜１８のアルコール系有機溶媒等を使用することができる。また、マイクロ波照射による加熱条件下でも使用を可能とする観点から、使用する有機溶媒は、沸点が１７０℃以上のものを選択することが好ましく、より好ましくは２００〜３００℃の範囲内にあるものを選択することがよい。このような有機溶媒の具体例としては、例えばテトラエチレングリコール、ｎ−オクチルエーテル等が挙げられる。
(Organic solvent)
In step 1, an organic solvent different from the primary amine may be newly added in order to allow the reaction in the homogeneous solution to proceed more efficiently. When an organic solvent is used, the organic solvent may be mixed simultaneously with the nickel carboxylate and the primary amine. However, when the organic solvent is added after first mixing the nickel carboxylate and the primary amine to form a complex, It is more preferable because it efficiently coordinates to a nickel atom. The organic solvent that can be used is not particularly limited as long as it does not inhibit the complex formation between the primary amine and the nickel ion. For example, the organic solvent having 4 to 30 carbon atoms, 7 to 30 carbon atoms, and the like. A saturated or unsaturated hydrocarbon organic solvent, an alcohol organic solvent having 8 to 18 carbon atoms, or the like can be used. Moreover, from the viewpoint of enabling use even under heating conditions by microwave irradiation, it is preferable to select an organic solvent having a boiling point of 170 ° C. or higher, more preferably in the range of 200 to 300 ° C. It is better to choose one. Specific examples of such an organic solvent include tetraethylene glycol and n-octyl ether.
錯形成反応は室温に於いても進行することができるが、十分且つ、より効率の良い錯形成反応を行うために、１００℃〜１６５℃の範囲内の温度に加熱して反応を行う。この加熱は、カルボン酸ニッケルとして、例えばギ酸ニッケル２水和物や酢酸ニッケル４水和物のようなカルボン酸ニッケルの水和物を用いた場合に特に有利である。加熱温度は、好ましくは１００℃を超える温度とし、より好ましくは１０５℃以上の温度とすることで、カルボン酸ニッケルに配位した配位水と１級アミンとの配位子置換反応が効率よく行われ、この錯体配位子としての水分子を解離させることができ、さらにその水を系外に出すことができるので効率よく錯体を形成させることができる。例えば、ギ酸ニッケル２水和物は、室温では２個の配位水と２座配位子である２個のギ酸イオンが存在した錯体構造をとっているため、この２つの配位水と１級アミンの配位子置換により効率よく錯形成させるには、１００℃より高い温度で加熱することでこの錯体配位子としての水分子を解離させることが好ましい。また、カルボン酸ニッケルと１級アミンとの錯形成反応における熱処理は、後に続くニッケル錯体（又はニッケルイオン）のマイクロ波照射による加熱還元の過程と確実に分離し、前記の錯形成反応を完結させるという観点から、上記の上限温度以下とし、好ましくは１６０℃以下、より好ましくは１５０℃以下とすることがよい。 Although the complex formation reaction can proceed even at room temperature, in order to perform a sufficient and more efficient complex formation reaction, the reaction is carried out by heating to a temperature in the range of 100 ° C. to 165 ° C. This heating is particularly advantageous when nickel carboxylate hydrate such as nickel formate dihydrate or nickel acetate tetrahydrate is used as nickel carboxylate. The heating temperature is preferably a temperature exceeding 100 ° C., more preferably a temperature of 105 ° C. or more, so that the ligand substitution reaction between the coordinating water coordinated with nickel carboxylate and the primary amine is efficient. The water molecule as the complex ligand can be dissociated, and the water can be discharged out of the system, so that the complex can be formed efficiently. For example, nickel formate dihydrate has a complex structure in which two coordination waters and two formate ions as bidentate ligands exist at room temperature. In order to efficiently form a complex by substituting a ligand for a primary amine, it is preferable to dissociate the water molecule as the complex ligand by heating at a temperature higher than 100 ° C. In addition, the heat treatment in the complex formation reaction between nickel carboxylate and primary amine is surely separated from the subsequent heat reduction process by microwave irradiation of the nickel complex (or nickel ion) to complete the complex formation reaction. In view of the above, the temperature is set to the upper limit temperature or lower, preferably 160 ° C. or lower, more preferably 150 ° C. or lower.
加熱時間は、加熱温度や、各原料の含有量に応じて適宜決定することができるが、錯形成反応を完結させるという観点から、１０分以上とすることが好ましい。加熱時間の上限は特にないが、長時間熱処理することはエネルギー消費及び工程時間を節約する観点から無駄である。なお、この加熱の方法は、特に制限されず、例えばオイルバスなどの熱媒体による加熱であっても、マイクロ波照射による加熱であってもよい。 The heating time can be appropriately determined according to the heating temperature and the content of each raw material, but is preferably 10 minutes or more from the viewpoint of completing the complex formation reaction. There is no upper limit on the heating time, but heat treatment for a long time is useless from the viewpoint of saving energy consumption and process time. The heating method is not particularly limited, and may be heating by a heat medium such as an oil bath or heating by microwave irradiation.
カルボン酸ニッケルと１級アミンとの錯形成反応は、カルボン酸ニッケルと１級アミンとを有機溶媒中で混合して得られる溶液を加熱したときに、溶液の色の変化によって確認することができる。また、この錯形成反応は、例えば紫外・可視吸収スペクトル測定装置を用いて、３００ｎｍ〜７５０ｎｍの波長領域において観測される吸収スペクトルの吸収極大の波長を測定し、原料の極大吸収波長（例えばギ酸ニッケル２水和物ではその極大吸収波長は７１０ｎｍであり、酢酸ニッケル４水和物ではその極大吸収波長は７１０ｎｍである。）に対する錯化反応液のシフト（極大吸収波長が６００ｎｍにシフト）を観測することによって確認することができる。 The complex formation reaction between nickel carboxylate and primary amine can be confirmed by a change in the color of the solution when a solution obtained by mixing nickel carboxylate and primary amine in an organic solvent is heated. . In addition, this complex formation reaction is carried out by measuring the absorption maximum wavelength of the absorption spectrum observed in the wavelength region of 300 nm to 750 nm using, for example, an ultraviolet / visible absorption spectrum measuring apparatus, and measuring the maximum absorption wavelength of the raw material (for example, nickel formate). In dihydrate, the maximum absorption wavelength is 710 nm, and in nickel acetate tetrahydrate, the maximum absorption wavelength is 710 nm.) The shift of the complexing reaction solution (the maximum absorption wavelength shifts to 600 nm) is observed. Can be confirmed.
カルボン酸ニッケルと１級アミンとの錯形成が行われた後、得られる反応液を、次に説明するように、マイクロ波照射によって加熱することにより、ニッケル錯体のニッケルイオンが還元され、ニッケルイオンに配位しているカルボン酸イオンが同時に分解し、最終的に酸化数が０価のニッケルを含有するニッケル微粒子が生成する。一般にカルボン酸ニッケルは水を溶媒とする以外の条件では難溶性であり、マイクロ波照射による加熱還元反応の前段階として、カルボン酸ニッケルを含む溶液は均一反応溶液とする必要がある。これに対して、本実施の形態で使用される１級アミンは、使用温度条件で液体であり、かつそれがニッケルイオンに配位することで液化し、均一反応溶液を形成すると考えられる。 After the complex formation between nickel carboxylate and primary amine is performed, the resulting reaction solution is heated by microwave irradiation to reduce the nickel ions of the nickel complex as described below. At the same time, the carboxylate ions coordinated in the nuclei are decomposed, and finally nickel fine particles containing nickel having an oxidation number of 0 are generated. In general, nickel carboxylate is hardly soluble under conditions other than using water as a solvent, and a solution containing nickel carboxylate needs to be a homogeneous reaction solution as a pre-stage of the heat reduction reaction by microwave irradiation. On the other hand, the primary amine used in the present embodiment is liquid under the operating temperature conditions, and is considered to be liquefied by coordination with nickel ions to form a homogeneous reaction solution.
工程２）ニッケル微粒子スラリー生成工程：
本工程では、カルボン酸ニッケルと１級アミンとの錯形成反応によって得られた錯化反応液を、マイクロ波照射によって１７０℃以上の温度に加熱し、錯化反応液中のニッケルイオンを還元して１級アミンで被覆されたニッケル微粒子スラリーを得る。マイクロ波照射によって加熱する温度は、得られるニッケル微粒子の形状のばらつきを抑制するという観点から、好ましくは１８０℃以上、より好ましくは２００℃以上とすることがよい。加熱温度の上限は特にないが、処理を能率的に行う観点からは例えば２７０℃以下とすることが好適である。なお、マイクロ波の使用波長は、特に限定するものではなく、例えば２．４５ＧＨｚである。なお、加熱温度は、例えばカルボン酸ニッケルの種類やニッケル微粒子の核発生を促進させる添加剤の使用などによって、適宜調整することができる。
Step 2) Nickel fine particle slurry generation step:
In this step, the complexing reaction solution obtained by the complexation reaction between nickel carboxylate and primary amine is heated to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction solution. To obtain a nickel fine particle slurry coated with a primary amine. The temperature for heating by microwave irradiation is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of suppressing variation in the shape of the obtained nickel fine particles. The upper limit of the heating temperature is not particularly limited, but is preferably set to 270 ° C. or less, for example, from the viewpoint of efficiently performing the treatment. In addition, the use wavelength of a microwave is not specifically limited, For example, it is 2.45 GHz. The heating temperature can be appropriately adjusted depending on, for example, the type of nickel carboxylate and the use of an additive that promotes the nucleation of nickel fine particles.
本工程では、マイクロ波が反応液内に浸透するため、均一加熱が行われ、かつ、エネルギーを媒体に直接与えることができるため、急速加熱を行うことができる。これにより、反応液全体を所望の温度に均一にすることができ、ニッケル錯体（又はニッケルイオン）の還元、核生成、核成長各々の過程を溶液全体において同時に生じさせ、結果として粒径分布の狭い単分散な粒子を短時間で容易に製造することができる。 In this step, since microwaves penetrate into the reaction solution, uniform heating is performed, and energy can be directly applied to the medium, so that rapid heating can be performed. As a result, the entire reaction solution can be made uniform at a desired temperature, and the processes of reduction, nucleation, and nucleation of the nickel complex (or nickel ions) can occur simultaneously in the entire solution. Narrow monodisperse particles can be easily produced in a short time.
均一な粒径を有するニッケル微粒子を生成させるには、工程１の錯化反応液生成工程（ニッケル錯体の生成が行われる工程）でニッケル錯体を均一にかつ十分に生成させることと、本工程２のニッケル微粒子スラリー生成工程で、ニッケル錯体（又はニッケルイオン）の還元により生成するニッケル(０価)の核の同時発生・成長を行う必要がある。すなわち、錯化反応液生成工程の加熱温度を上記の特定の範囲内で調整し、ニッケル微粒子スラリー生成工程におけるマイクロ波による加熱温度よりも確実に低くしておくことで、粒径・形状の整った粒子が生成し易い。例えば、錯化反応液生成工程で加熱温度が高すぎるとニッケル錯体の生成とニッケル(０価)への還元反応が同時に進行し異種の金属種が発生することで、ニッケル微粒子スラリー生成工程での粒子形状の整った粒子の生成が困難となるおそれがある。また、ニッケル微粒子スラリー生成工程の加熱温度が低すぎるとニッケル(０価)への還元反応速度が遅くなり核の発生が少なくなるため粒子が大きくなるだけでなく、ニッケル微粒子の収率の点からも好ましくはない。 In order to generate nickel fine particles having a uniform particle size, the nickel complex is uniformly and sufficiently generated in the complexing reaction liquid generating step (step in which the nickel complex is generated) in step 1; In the nickel fine particle slurry generation step, it is necessary to simultaneously generate and grow nickel (zero-valent) nuclei generated by reduction of the nickel complex (or nickel ions). In other words, by adjusting the heating temperature in the complexing reaction liquid production step within the above specific range and ensuring that it is lower than the microwave heating temperature in the nickel fine particle slurry production step, the particle size and shape are adjusted. Particles are easily generated. For example, if the heating temperature is too high in the complexing reaction liquid generation process, the formation of nickel complex and the reduction reaction to nickel (zero valence) proceed simultaneously, and different metal species are generated. There is a possibility that it is difficult to generate particles having a uniform particle shape. In addition, if the heating temperature of the nickel fine particle slurry generation process is too low, the reduction reaction rate to nickel (zero valence) is slowed and the generation of nuclei is reduced, so that not only the particles are enlarged, but also in terms of the yield of nickel fine particles. Is also not preferred.
マイクロ波照射によって加熱して得られるニッケル微粒子スラリーを、例えば、静置分離し、上澄み液を取り除いた後、適当な溶媒を用いて洗浄し、乾燥することで、ニッケル微粒子が得られる。ニッケル微粒子スラリー生成工程においては、必要に応じ、前述した有機溶媒を加えてもよい。なお、前記したように、錯形成反応に使用する１級アミンを有機溶媒としてそのまま用いることが好ましい。 The nickel fine particle slurry obtained by heating by microwave irradiation is, for example, left and separated, and after removing the supernatant liquid, washed with an appropriate solvent and dried to obtain nickel fine particles. In the nickel fine particle slurry production step, the organic solvent described above may be added as necessary. As described above, the primary amine used for the complex formation reaction is preferably used as it is as the organic solvent.
以上のようにして、平均一次粒子径が３０〜２００ｎｍの範囲内のニッケル微粒子を調製することができる。ニッケル以外の原料金属微粒子についても、上記方法に準じて製造できる。 As described above, nickel fine particles having an average primary particle diameter in the range of 30 to 200 nm can be prepared. Raw metal fine particles other than nickel can also be produced according to the above method.
＜配合比＞
金属粒子組成物は、成分Ａ及び成分Ｂの重量比（成分Ａ：成分Ｂ）が５０：５０〜１０：９０の範囲内である。上記範囲よりもスズ粒子の割合が高くなると、金属化合物を形成していないスズ成分が再溶融するので、高温での接合層としての適用が困難となる。一方、上記範囲よりもスズ粒子の割合が低くなると、ニッケル微粒子どうしの焼結が支配的となり、無加圧による接合が困難となり、その結果として後述する比較例１に示したように接合層としての強度不足が生じる。
<Combination ratio>
In the metal particle composition, the weight ratio of component A and component B (component A: component B) is in the range of 50:50 to 10:90. When the ratio of the tin particles is higher than the above range, the tin component not forming the metal compound is remelted, so that application as a bonding layer at a high temperature becomes difficult. On the other hand, when the proportion of tin particles is lower than the above range, the sintering of the nickel fine particles becomes dominant, and it becomes difficult to perform bonding without pressure, and as a result, as shown in Comparative Example 1 described later, as a bonding layer Insufficient strength occurs.
［接合材］
本実施の形態の接合材は、上記金属粒子組成物を含有する。本実施の形態の接合材は、さらに、沸点１５０〜２６０℃の範囲内にある有機溶媒を含有することができる。接合材は、高沸点の有機溶媒を添加後、濃縮し、ペーストの形態とすることが好ましい。使用する有機溶媒の沸点が１５０℃未満であると、長期安定性に欠く傾向があり、２６０℃を超えると、焼成時に揮発せずに、接合層中に残炭が生じ、粒子同士の焼結や金属間化合物の形成を阻害する傾向がある。
[Bonding material]
The bonding material of the present embodiment contains the metal particle composition. The bonding material of the present embodiment can further contain an organic solvent having a boiling point in the range of 150 to 260 ° C. The joining material is preferably concentrated after adding a high-boiling organic solvent to form a paste. If the boiling point of the organic solvent used is less than 150 ° C., long-term stability tends to be lacking. If it exceeds 260 ° C., residual carbon is generated in the joining layer without volatilization during firing, and particles are sintered. And tends to inhibit the formation of intermetallic compounds.
接合材における金属粒子組成物の含有量は、例えば７０〜９５重量％の範囲内であり、８５〜９４重量％の範囲内が好ましい。金属粒子組成物の含有量が７０重量％未満であると、接合層の厚みが薄くなる場合があり、例えば塗布などを複数回繰り返す必要が生じてムラの原因となり、また十分な接合強度が得られない場合がある。一方、金属粒子組成物の含有量が９５重量％を超えると、ペーストとしての流動性が失われ、塗布が困難になるなど使用性が低下する場合がある。 The content of the metal particle composition in the bonding material is, for example, in the range of 70 to 95% by weight, and preferably in the range of 85 to 94% by weight. If the content of the metal particle composition is less than 70% by weight, the thickness of the bonding layer may be reduced, for example, it may be necessary to repeat coating several times, resulting in unevenness, and sufficient bonding strength is obtained. It may not be possible. On the other hand, when the content of the metal particle composition exceeds 95% by weight, the fluidity as a paste is lost, and the usability may be lowered, such as difficulty in coating.
沸点が１５０〜２６０℃の範囲内にある溶媒として、例えば、アルコール系、芳香族系、炭化水素系、エステル系、ケトン系、エーテル系の溶媒が使用できる。アルコール系溶媒の例としては、１−ヘプタノール、１−オクタノール、２−オクタノール、２−エチル−１−ヘキサノール、１−ノナノール、３，５，５−トリメチル−１−ヘキサノール、１−デカノールなどの炭素数７以上の脂肪族アルコール類、エチレングリコール、ジエチレングリコール、プロピレングリコール、トリメチレングリコール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、テトラメチレングリコール、メチルトリグリコール等の多価アルコール類、α−テルピネオール、β−テルピネオール、γ−テルピネオール等のテルピネオール類、さらにエチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、メチルメトキシブタノール、ジエチレングリコール、ジプロピレングリコール、２−フェノキシエタノール、１−フェノキシ−２−プロパノール等のエーテル基を有するアルコール類を挙げることができる。 As the solvent having a boiling point in the range of 150 to 260 ° C., for example, alcohol-based, aromatic-based, hydrocarbon-based, ester-based, ketone-based, and ether-based solvents can be used. Examples of alcohol solvents include carbons such as 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5,5-trimethyl-1-hexanol, and 1-decanol. 7 or more aliphatic alcohols, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, methyltriglycol, etc. Terpineols such as α-terpineol, β-terpineol, γ-terpineol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, methyl methoxybutanol, diethylene glycol, di- B propylene glycol, 2-phenoxyethanol, can be mentioned alcohols having an ether group such as 1-phenoxy-2-propanol.
本実施の形態の接合材における有機溶媒の含有量は、例えば、５〜３０重量％の範囲内であり、６〜１５重量％の範囲内が好ましい。接合材における有機溶媒の含有量が５重量％未満であると、流動性が低下して接合材としての使用性が低下する場合がある。一方、有機溶媒の含有量が３０重量％を超えると、例えば塗布などを複数回繰り返す必要が生じてムラの原因となり、また十分な接合強度が得られない場合がある。 The content of the organic solvent in the bonding material of the present embodiment is, for example, in the range of 5 to 30% by weight, and preferably in the range of 6 to 15% by weight. When the content of the organic solvent in the bonding material is less than 5% by weight, the fluidity may be lowered and the usability as the bonding material may be lowered. On the other hand, when the content of the organic solvent exceeds 30% by weight, for example, it becomes necessary to repeat coating several times, which may cause unevenness, and sufficient bonding strength may not be obtained.
本実施の形態の接合材は、ニッケル−スズの金属間化合物の形成およびニッケル粒子間の焼結を阻害しない範囲で、上記成分以外に、各種添加剤を加えてもよい。添加剤としては、例えば、粘度調整剤、チキソ材、バインダー樹脂等を挙げることができる。 In the bonding material of the present embodiment, various additives may be added in addition to the above components as long as the formation of the nickel-tin intermetallic compound and the sintering between the nickel particles are not inhibited. Examples of the additive include a viscosity modifier, a thixo material, and a binder resin.
［接合方法］
本実施の形態の接合方法は、上記接合材を、被接合部材の間に介在させて還元性ガスを含有する還元性ガス雰囲気下で２５０〜５００℃の範囲内、好ましくは３００〜３５０℃の範囲内の温度で加熱することにより、被接合部材の間に接合層を形成する。スズとニッケルは、２３０℃程度で金属間化合物を形成する。従って、還元性ガス雰囲気下で加熱を行うことにより、ニッケル微粒子表面の不動態層を除去し、スズとの金属化合物の形成を進行させ、ニッケル微粒子間の焼結も進行させることができる。また、スズ系はんだを融解させるための加熱温度は２３０℃程度でよいが、ニッケル微粒子の表面が露出した状態になってから初めて焼結が進行すると考えられることから、ニッケル微粒子の表面に存在する有機物を揮発又は分解させるために、加熱温度を２５０℃以上とすることが好ましい。一方、加熱温度が５００℃を超えると、被接合部材としての半導体デバイスなどにダメージを与える場合がある。
[Joint method]
In the joining method of the present embodiment, the joining material is interposed between the members to be joined, and the reducing gas is contained in a reducing gas atmosphere containing a reducing gas. By heating at a temperature within the range, a bonding layer is formed between the members to be bonded. Tin and nickel form an intermetallic compound at about 230 ° C. Therefore, by heating in a reducing gas atmosphere, the passive layer on the surface of the nickel fine particles can be removed, the formation of the metal compound with tin can be advanced, and the sintering between the nickel fine particles can also be advanced. Further, the heating temperature for melting the tin-based solder may be about 230 ° C., but since the sintering is considered to proceed only after the surface of the nickel fine particles is exposed, it exists on the surface of the nickel fine particles. In order to volatilize or decompose organic substances, the heating temperature is preferably 250 ° C. or higher. On the other hand, if the heating temperature exceeds 500 ° C., the semiconductor device or the like as the bonded member may be damaged.
本実施の形態の接合方法は、例えば、ペースト状の接合材を一対の被接合部品の片方又は両方の被接合面に塗布する工程（塗布工程）、被接合面どうしを貼り合せ、例えば温度２５０〜５００℃の範囲内、好ましくは３００〜３５０℃の範囲内で加熱することにより、接合材を焼結させる工程（焼成工程）、並びに、焼結した接合材を冷却することにより固化し、金属接合層を形成する工程（固化工程）、を含むことができる。 In the bonding method of the present embodiment, for example, a process of applying a paste-like bonding material to one or both bonded surfaces of a pair of bonded components (application process), the bonded surfaces are bonded together, for example, a temperature of 250 By heating within a range of ˜500 ° C., preferably within a range of 300 ° C. to 350 ° C., a step of sintering the bonding material (firing step), and solidifying by cooling the sintered bonding material, a metal A step of forming a bonding layer (solidification step).
接合材を塗布する塗布工程では、例えばスプレー塗布、インクジェット塗布、印刷等の方法を採用できる。接合材は、目的に応じて、例えばパターン状、アイランド状、メッシュ状、格子状、ストライプ状など任意の形状に塗布することができる。塗布工程では、塗布膜の厚みが５０〜２００μｍの範囲内となるように、接合材を塗布することが好ましい。このような厚みで塗布をすることで、接合部分の欠陥を少なくできるため、電気抵抗の上昇や接合強度の低下を防止できる。 In the coating process for coating the bonding material, for example, methods such as spray coating, inkjet coating, and printing can be employed. The bonding material can be applied in an arbitrary shape such as a pattern shape, an island shape, a mesh shape, a lattice shape, or a stripe shape according to the purpose. In the coating step, it is preferable to apply the bonding material so that the thickness of the coating film is in the range of 50 to 200 μm. By applying with such a thickness, defects in the joint portion can be reduced, so that an increase in electrical resistance and a decrease in joint strength can be prevented.
また、焼成工程は、例えばＨ２などの還元性ガスが存在する雰囲気で行うことが好ましい。また、減圧することで、ボイド発生を抑制する効果が得られる。例えば大気圧の９５％以下の圧力でその効果が確認できる。また、接合面を貼り合わせる際には、必要に応じて加圧することができる。 The firing step is preferably, for example, carried out in an atmosphere of reducing gas such as H 2 is present. Moreover, the effect which suppresses void generation | occurrence | production is acquired by decompressing. For example, the effect can be confirmed at a pressure of 95% or less of the atmospheric pressure. Moreover, when bonding a joint surface, it can be pressurized as needed.
焼成工程及び固化工程では、スズとニッケルが金属間化合物を形成するとともに、ニッケル微粒子どうしが焼結し、均一で強固な接着力を持つ金属接合層を形成することができる。また、金属接合層を形成することによって金属接合層の導電性が確保される。 In the firing step and the solidification step, tin and nickel form an intermetallic compound, and the nickel fine particles are sintered to form a metal bonding layer having a uniform and strong adhesive force. Moreover, the conductivity of the metal bonding layer is ensured by forming the metal bonding layer.
金属微粒子が焼結して形成される接合部分（金属接合層）の厚みは、例えば４０〜１００μｍの範囲内が好ましい。接合部分の厚みがこれよりも薄い場合は、接合部分の欠陥が多くなり、電気抵抗の上昇や、強度の低下を引き起こす原因となる。 The thickness of the joining portion (metal joining layer) formed by sintering the metal fine particles is preferably in the range of 40 to 100 μm, for example. When the thickness of the joint portion is thinner than this, defects in the joint portion increase, which causes an increase in electrical resistance and a decrease in strength.
本実施の形態の接合方法は、例えば、Ｓｉ、ＳｉＣの半導体材料の接合や、電子部品の製造過程で利用できる。ここで、電子部品としては、主に半導体装置、エネルギー変換モジュール部品などを例示できる。電子部品が半導体装置である場合、例えば、半導体素子の裏面と基板との間、半導体電極と基板電極との間、半導体電極と半導体電極との間、パワーデバイス若しくはパワーモジュールと放熱部材との間などの接合に適用できる。 The bonding method of the present embodiment can be used, for example, in the bonding of Si or SiC semiconductor materials or in the manufacturing process of electronic components. Here, examples of the electronic component mainly include a semiconductor device and an energy conversion module component. When the electronic component is a semiconductor device, for example, between the back surface of the semiconductor element and the substrate, between the semiconductor electrode and the substrate electrode, between the semiconductor electrode and the semiconductor electrode, between the power device or the power module and the heat dissipation member. It can be applied to joining.
電子部品を接合させる際は、接合強度を高めるため、予め被接合面の片方又は両方に、例えば、Ａｕ，Ｃｕ，Ｐｄ，Ｎｉ，Ａｇ，Ｃｒ，Ｔｉあるいはそれらの合金などの材質の接触金属層を設けておくことが好ましい。また、被接合面の材質が、ＳｉＣもしくはＳｉあるいはそれらの表面の酸化膜である場合は、例えばＴｉ，ＴｉＷ，ＴｉＮ，Ｃｒ，Ｎｉ、Ｐｄ，Ｖあるいはそれらの合金などの材質の接触金属層を設けておくことが好ましい。接触金属層の膜厚は、それぞれ、例えば５０ｎｍ以上２μｍ以下の範囲内であることが好ましい。接触金属層の厚みが５０ｎｍ未満では、欠陥が生じやすく、２μｍ超では蒸着工程が長くなり、生産効率が低下することがある。 When bonding electronic components, in order to increase the bonding strength, for example, a contact metal layer made of a material such as Au, Cu, Pd, Ni, Ag, Cr, Ti or an alloy thereof is previously formed on one or both of the surfaces to be bonded. Is preferably provided. When the material of the surface to be joined is SiC or Si or an oxide film on the surface thereof, a contact metal layer made of a material such as Ti, TiW, TiN, Cr, Ni, Pd, V or an alloy thereof is used. It is preferable to provide it. The thickness of each contact metal layer is preferably in the range of, for example, 50 nm or more and 2 μm or less. If the thickness of the contact metal layer is less than 50 nm, defects are likely to occur, and if it exceeds 2 μm, the vapor deposition process becomes long, and the production efficiency may be reduced.
また、本実施の形態の接合方法は、金属材料などの接合にも利用できる。特に蝋材や溶接による接合で、熱影響部における母材の劣化がみられる場合に低温で接合することが好適である。また、本実施の形態の接合方法は、例えば、焼き入れ鋼、ステンレス鋼、加工硬化により強化された金属材料、熱酸化や熱ひずみにより劣化する無機材料や金属材料の接合にも適している。被接合体は管、板、継手、ロッド、ワイヤ、ボルトなどがあげられるが、これらに限定されるものではない。 Further, the bonding method of the present embodiment can also be used for bonding metal materials and the like. In particular, when the base material deteriorates in the heat-affected zone in joining by wax material or welding, it is preferable to join at a low temperature. The joining method of the present embodiment is also suitable for joining, for example, hardened steel, stainless steel, metal materials strengthened by work hardening, inorganic materials and metal materials that deteriorate due to thermal oxidation and thermal strain. Examples of the joined body include, but are not limited to, a pipe, a plate, a joint, a rod, a wire, and a bolt.
以下に実施例を示し、本発明の特徴をより具体的に説明する。ただし、本発明は、実施例によって制約されるものではない。なお、以下の実施例において、特にことわりのない限り各種測定、評価は下記によるものである。 The features of the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.
［平均粒子径の測定］
成分Ａ（スズ粒子）および比較例２で使用されるニッケル粒子の平均粒子径はレーザー回折／散乱法にて求めた。成分Ｂ（ニッケル微粒子）の平均粒子径の測定は、電界放出形走査電子顕微鏡（Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ−Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：ＦＥ−ＳＥＭ）により試料の写真を撮影して、その中から無作為に２００個を抽出してそれぞれの面積を求め、真球に換算したときの粒子径を個数基準として一次粒子の平均粒子径を算出した。また、ＣＶ値（変動係数）は、（標準偏差）÷（平均粒子径）によって算出した。なお、ＣＶ値が小さいほど、粒子径がより均一であることを示す。
[Measurement of average particle size]
The average particle diameter of the nickel particles used in Component A (tin particles) and Comparative Example 2 was determined by a laser diffraction / scattering method. The average particle diameter of component B (nickel fine particles) was measured by taking a picture of a sample with a field emission scanning electron microscope (FE-SEM), and randomly 200 samples were taken. The respective areas were extracted and the average particle diameter of primary particles was calculated based on the number of particles when converted to a true sphere. The CV value (coefficient of variation) was calculated by (standard deviation) / (average particle diameter). In addition, it shows that a particle diameter is so uniform that a CV value is small.
［焼成方法］
焼結性試験用サンプルの焼成は、小型イナートガスオーブン（光洋サーモシステム社製、商品名；ＫＬＯ−３０ＮＨ）を使用し、昇温速度５℃/分で、常温から３５０℃まで昇温した後、３５０℃で１時間保持した。次いで、４００分間かけて５０℃まで降温した後、常温まで放置した。
[Baking method]
The sample for sinterability test was fired using a small inert gas oven (manufactured by Koyo Thermo Systems Co., Ltd., trade name: KLO-30NH) at a heating rate of 5 ° C./min. It was held at 350 ° C. for 1 hour. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then left to room temperature.
[金属間化合物の定性分析]
熱分析）成分Ａ（スズ粒子）中のＳｎの加熱溶融と、成分Ｂとの金属間化合物生成によって再溶融が生じないことを、示差熱熱重量同時測定装置（Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｙ−Ｄｉｆｆｅｒｅｎｔｉａｌ Ｔｈｅｒｍａｌ Ａｎａｌｙｓｉｓ：ＴＧ−ＤＴＡ、株式会社日立ハイテクサイエンス製、商品名；ＴＧ／ＤＴＡ７２２０）を用いて確認した。測定は以下の条件を連続して実施した。
昇温１）
昇温条件 ：３０℃から３２５℃まで５℃／分の速度で昇温後１０分保持
ガスフロー ：窒素／水素＝９７／３体積比 混合ガス ２００ｍｌ／分
降温）
降温条件 ：３２５℃から１００℃以下まで１５℃／分の速度で降温後１０分保持
ガスフロー ：窒素／水素＝９７／３体積比 混合ガス ２００ｍｌ／分
昇温２）
昇温条件 ：３０℃から３００℃まで５℃／分の速度で昇温後１０分保持
ガスフロー ：窒素 ２００ｍｌ／分
[Qualitative analysis of intermetallic compounds]
Thermal analysis) The fact that remelting does not occur due to heat melting of Sn in component A (tin particles) and formation of an intermetallic compound with component B (Thermogravimetric-Differential Thermal Analysis: TG-) DTA, manufactured by Hitachi High-Tech Science Co., Ltd., trade name: TG / DTA7220). The measurement was performed continuously under the following conditions.
Temperature rise 1)
Temperature rising condition: Maintained for 10 minutes after heating at a rate of 5 ° C / min from 30 ° C to 325 ° C
Gas flow: Nitrogen / hydrogen = 97/3 volume ratio Mixed gas 200 ml / min.
Temperature drop condition: Holds for 10 minutes after temperature drop from 325 ° C to below 100 ° C at a rate of 15 ° C / min
Gas flow: Nitrogen / hydrogen = 97/3 volume ratio Mixed gas 200ml / min temperature rise 2)
Temperature rising condition: Maintained for 10 minutes after heating at a rate of 5 ° C / min from 30 ° C to 300 ° C
Gas flow: Nitrogen 200ml / min
［せん断強度（シェア強度）の評価］
ステンレス製マスク（マスク幅；２．０ｍｍ×長さ；２．０ｍｍ×厚さ；０．１ｍｍ）を用いて、試料を金めっき銅基板（幅；１０ｍｍ×長さ；１０ｍｍ×厚さ；１．０ｍｍ）上に塗布して塗布膜を形成した後、その塗布膜の上に、シリコンダイ（幅；２．０ｍｍ×長さ；２．０ｍｍ×厚さ；０．４０ｍｍ）を搭載し、焼成を行った。得られた接合サンプル（接合層の厚さ；５０μｍ程度）を接合強度試験機（デイジ・ジャパン社製、商品名；ボンドテスター４０００）により、せん断強度を測定した。測定は常温または加熱ステージで銅基板を２６０℃に加熱しながら実施した。ダイ側面からボンドテスターツールを、基板からの高さ５０μｍ、ツール速度１００μｍ／秒で押圧し、接合部がせん断破壊したときの荷重をせん断強度（シェア強度）とした。なお、金めっき銅基板は、Ｃｕ基板（厚さ；１．０ｍｍ）の表面に、Ｎｉ／Ａｕをそれぞれ４μｍ／４０〜５０ｎｍの厚みでめっきしたものであり、シリコンダイは、Ｓｉ基板（厚さ；０．４０ｍｍ）の接合面に、Ａｕを１５〜２０ｎｍの厚みで蒸着したものである。
[Evaluation of shear strength (shear strength)]
Using a stainless steel mask (mask width; 2.0 mm × length; 2.0 mm × thickness; 0.1 mm), the sample was gold-plated copper substrate (width; 10 mm × length; 10 mm × thickness; 0 mm) is applied to form a coating film, and then a silicon die (width: 2.0 mm × length; 2.0 mm × thickness: 0.40 mm) is mounted on the coating film and firing is performed. went. The shear strength of the obtained joined sample (joint layer thickness; about 50 μm) was measured with a joint strength tester (manufactured by Daisy Japan, trade name: Bond Tester 4000). The measurement was performed while heating the copper substrate to 260 ° C. at room temperature or a heating stage. A bond tester tool was pressed from the side of the die at a height of 50 μm from the substrate and a tool speed of 100 μm / second, and the load when the joint was sheared was determined as shear strength (shear strength). The gold-plated copper substrate is obtained by plating Ni / Au with a thickness of 4 μm / 40 to 50 nm on the surface of a Cu substrate (thickness: 1.0 mm), and the silicon die is a Si substrate (thickness). ; 0.40 mm), and Au is deposited in a thickness of 15 to 20 nm on the joint surface.
［接合サンプルの断面ＳＥＭ観察］
上記せん断強度評価と同様に作製した接合サンプルを、エポキシ樹脂により包埋後、断面加工を施し、電界放出形走査電子顕微鏡（ＦＥ−ＳＥＭ）にて観察した。
[Cross-sectional SEM observation of bonded sample]
A bonded sample prepared in the same manner as in the above-described shear strength evaluation was embedded with an epoxy resin, subjected to cross-section processing, and observed with a field emission scanning electron microscope (FE-SEM).
（合成例１）
６４２重量部のオレイルアミンに１００．１重量部の酢酸ニッケル四水和物を加え、窒素フロー下、１５０℃で２０分加熱することによって酢酸ニッケルを溶解させて錯化反応液を得た。次いで、その錯化反応液に、４９２重量部のオレイルアミンを加え、マイクロ波を用いて２５０℃で５分加熱することによって、ニッケル微粒子スラリーを得た。
(Synthesis Example 1)
To 642 parts by weight of oleylamine, 100.1 parts by weight of nickel acetate tetrahydrate was added and heated at 150 ° C. for 20 minutes under a nitrogen flow to dissolve nickel acetate to obtain a complexing reaction solution. Next, 492 parts by weight of oleylamine was added to the complexing reaction solution, and the mixture was heated at 250 ° C. for 5 minutes using a microwave to obtain a nickel fine particle slurry.
ニッケル微粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンとメタノールを用いて洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してニッケル微粒子（平均一次粒子径；９２ｎｍ、ＣＶ値；０．１９）を得た。 The nickel fine particle slurry was allowed to stand and separated, the supernatant was removed, washed with toluene and methanol, and then dried in a vacuum dryer maintained at 60 ° C. for 6 hours to obtain nickel fine particles (average primary particle size; 92 nm CV value; 0.19) was obtained.
＜スラリー溶液の調製＞
合成例１で得られたニッケル微粒子を１００重量部分取し、これに２０重量部のオクタン酸を加え、１５分間撹拌した後、トルエンで洗浄し、スラリー溶液１（固形分濃度６８．１重量％）を調製した。
<Preparation of slurry solution>
100 parts by weight of the nickel fine particles obtained in Synthesis Example 1 were taken, 20 parts by weight of octanoic acid was added thereto, and the mixture was stirred for 15 minutes and then washed with toluene to obtain slurry solution 1 (solid content concentration 68.1% by weight). ) Was prepared.
（実施例１）
＜ペースト１の調製＞
スラリー溶液１の１５２重量部を分取し、これに１０．３重量部のＳｎ粒子（重量比Ｓｎ／Ａｇ／Ｃｕ＝９６．５／２．９／０．５１、製品名ＤＳ−１０ 株式会社日本フィラーメタルズ製 平均粒径１２．８μｍ）、１２．４重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、４．６重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．０６重量部のバインダー樹脂（製品名エスレックＳＶ−０５ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、１３０．９重量部のペースト１（固形分濃度８７．０ｗｔ％）を調製した。
Example 1
<Preparation of paste 1>
152 parts by weight of the slurry solution 1 was collected, and 10.3 parts by weight of Sn particles (weight ratio Sn / Ag / Cu = 96.5 / 2.9 / 0.51, product name DS-10 Co., Ltd.) Nippon Filler Metals average particle size 12.8 μm), 12.4 parts by weight of α-terpineol (Wako Pure Chemical Industries, Ltd., boiling point; 220 ° C.), 4.6 parts by weight of tetradecane (Wako Pure Chemical Industries, Ltd.) (Boiling point: 254 ° C.), 0.06 part by weight of binder resin (product name: S-LEC SV-05 manufactured by Sekisui Chemical Co., Ltd.) is mixed, and concentrated at 60 ° C. and 100 hPa using an evaporator, and 130.9 parts by weight of paste 1 (solid content concentration 87.0 wt%) was prepared.
実施例１のペースト１を用いて、上記方法にて接合サンプルを作製し、測定したせん断強度は、０．１ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A joining sample was prepared by the above method using the paste 1 of Example 1, and the measured shear strength was 0.1 kgf / mm 2 . The results are shown in Table 1.
（実施例２）
＜ペースト２の調製＞
スラリー溶液１の１０４重量部を分取し、これに１８．０重量部のはんだ粒子（重量比Ｓｎ／Ａｇ／Ｃｕ＝９６．５／２．９／０．５１、製品名ＤＳ−１０ 株式会社日本フィラーメタルズ製 平均粒径１２．８μｍ）、７．２重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、２．７重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．０５重量部のバインダー樹脂（製品名エスレックＳＶ−０５ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、９８．８重量部のペースト２（固形分濃度８９．９重量％）を調製した。
(Example 2)
<Preparation of paste 2>
104 parts by weight of the slurry solution 1 was collected, and 18.0 parts by weight of solder particles (weight ratio Sn / Ag / Cu = 96.5 / 2.9 / 0.51, product name DS-10 Co., Ltd.) Nippon Filler Metals average particle size 12.8 μm), 7.2 parts by weight of α-terpineol (manufactured by Wako Pure Chemical Industries, Ltd., boiling point; 220 ° C.), 2.7 parts by weight of tetradecane (manufactured by Wako Pure Chemical Industries, Ltd.) (Boiling point 254 ° C.), 0.05 parts by weight of binder resin (product name: S-LEC SV-05, manufactured by Sekisui Chemical Co., Ltd.), concentrated at 60 ° C. and 100 hPa with an evaporator, and 98.8 parts by weight of paste 2 (solid content concentration 89.9% by weight) was prepared.
実施例２のペースト２を用いて、上記方法にて接合サンプルを作製し、測定したせん断強度は、１．１ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A joining sample was prepared by the above method using the paste 2 of Example 2, and the measured shear strength was 1.1 kgf / mm 2 . The results are shown in Table 1.
（実施例３）
＜ペースト３の調製＞
スラリー溶液１の１２１重量部を分取し、これに２０．６重量部のはんだ粒子（重量比Ｓｎ／Ａｇ／Ｃｕ＝９６．５／２．９／０．５１、製品名ＤＳ−１０ 株式会社日本フィラーメタルズ製 平均粒径１２．８μｍ）、６．７重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、１．４重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．４８重量部のバインダー樹脂（製品名エスレックＢＨ−Ａ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、９５．３重量部のペースト３（固形分濃度９１．０重量％）を調製した。
(Example 3)
<Preparation of paste 3>
121 parts by weight of the slurry solution 1 was collected, and 20.6 parts by weight of solder particles (weight ratio Sn / Ag / Cu = 96.5 / 2.9 / 0.51, product name DS-10 Co., Ltd.) Nippon Filler Metals average particle size 12.8 μm), 6.7 parts by weight of α-terpineol (Wako Pure Chemical Industries, Ltd., boiling point; 220 ° C.), 1.4 parts by weight of tetradecane (Wako Pure Chemical Industries, Ltd.) (Boiling point: 254 ° C.), 0.48 parts by weight of binder resin (product name: S-REC BH-A manufactured by Sekisui Chemical Co., Ltd.), concentrated at 60 ° C. and 100 hPa with an evaporator, and 95.3 parts by weight of paste 3 (solid content concentration 91.0% by weight) was prepared.
実施例３のペースト３を用いて、上記方法にて接合サンプルを作製し、測定したせん断強度は、３．０ｋｇｆ／ｍｍ２であった。また、２６０℃加熱ステージを用いて測定したせん断強度は２．９ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A joining sample was prepared by the above method using the paste 3 of Example 3, and the measured shear strength was 3.0 kgf / mm 2 . The shear strength measured using a 260 ° C. heating stage was 2.9 kgf / mm 2 . The results are shown in Table 1.
（実施例４）
＜ペースト４の調製＞
スラリー溶液１の１３３重量部を分取し、これに２２．８重量部のスズ粒子（製品名Ｓｎ−Ａｔ−６００ 福田金属箔粉工業株式会社製 平均粒径７．３μｍ）、８．３重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、１．８重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．６重量部のバインダー樹脂（製品名エスレックＢＨ−Ａ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、１２４重量部のペースト４（固形分濃度９１．４重量％）を調製した。
Example 4
<Preparation of paste 4>
133 parts by weight of the slurry solution 1 was collected, and 22.8 parts by weight of tin particles (product name: Sn-At-600, Fukuda Metal Foil Powder Co., Ltd. average particle size: 7.3 μm), 8.3 parts by weight. Part of α-terpineol (Wako Pure Chemical Industries, Ltd., boiling point; 220 ° C.), 1.8 parts by weight of tetradecane (Wako Pure Chemical Industries, Ltd., boiling point: 254 ° C.), 0.6 parts by weight of binder resin (product name) ESREC BH-A manufactured by Sekisui Chemical Co., Ltd.) was mixed and concentrated with an evaporator at 60 ° C. and 100 hPa to prepare 124 parts by weight of paste 4 (solid content concentration 91.4 wt%).
実施例４のペースト４を用いて、上記方法にて接合サンプルを作製し、測定したせん断強度は、３．３ｋｇｆ／ｍｍ２であった。また、２６０℃加熱ステージを用いて測定したせん断強度は３．７ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A joining sample was prepared by the above method using the paste 4 of Example 4, and the measured shear strength was 3.3 kgf / mm 2 . The shear strength measured using a 260 ° C. heating stage was 3.7 kgf / mm 2 . The results are shown in Table 1.
実施例４のペースト４を上記方法にてＴＧ−ＤＴＡを測定した。その結果を図１に示す。図１より、昇温１における２３０℃の吸熱ピークから、スズ粒子の溶融が確認できる。さらに、昇温２において発熱ピーク、吸熱ピークが検出されないことから、スズは昇温１の段階にてニッケルとの金属間化合物が生成したと推定できる。 TG-DTA of the paste 4 of Example 4 was measured by the above method. The result is shown in FIG. From FIG. 1, melting of the tin particles can be confirmed from the endothermic peak at 230 ° C. at the temperature rise 1. Further, since no exothermic peak or endothermic peak is detected at the temperature rise 2, it can be estimated that tin produced an intermetallic compound with nickel at the stage of the temperature rise 1.
ペースト４を用いて、上記方法にて断面ＳＥＭ観察を実施した。その結果を図２に示す。図２より、良好な接合層の形成が確認される。 Using paste 4, cross-sectional SEM observation was carried out by the above method. The result is shown in FIG. FIG. 2 confirms the formation of a good bonding layer.
（実施例５）
＜ペースト５の調製＞
スラリー溶液１の１２６重量部を分取し、これに５７．３重量部のスズ粒子（製品名Ｓｎ−Ａｔ−６００ 福田金属箔粉工業株式会社製 平均粒径７．３μｍ）、９．８重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、２．１重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．８重量部のバインダー樹脂（製品名エスレックＢＨ−Ａ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、１５５重量部のペースト５（固形分濃度９１．８重量％）を調製した。
(Example 5)
<Preparation of paste 5>
126 parts by weight of the slurry solution 1 was collected, and 57.3 parts by weight of tin particles (product name: Sn-At-600, Fukuda Metal Foil Powder Co., Ltd. average particle size: 7.3 μm), 9.8% by weight Part of α-terpineol (Wako Pure Chemical Industries, Ltd., boiling point: 220 ° C.), 2.1 parts by weight of tetradecane (Wako Pure Chemical Industries, Ltd., boiling point: 254 ° C.), 0.8 parts by weight of binder resin (product name) ESREC BH-A manufactured by Sekisui Chemical Co., Ltd.) was mixed and concentrated at 60 ° C. and 100 hPa using an evaporator to prepare 155 parts by weight of paste 5 (solid content concentration 91.8% by weight).
実施例５のペースト５を上記方法にて接合サンプルを作製し、測定したせん断強度は、２．９ｋｇｆ／ｍｍ２であった。また、２６０℃加熱ステージを用いて測定したせん断強度は４．２ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A joining sample of the paste 5 of Example 5 was prepared by the above method, and the measured shear strength was 2.9 kgf / mm 2 . The shear strength measured using a 260 ° C. heating stage was 4.2 kgf / mm 2 . The results are shown in Table 1.
実施例５のペースト５を上記方法にてＴＧ−ＤＴＡを測定した。その結果を図３に示す。図３より、昇温１における２３０℃の吸熱ピークから、スズ粒子の溶融が確認できる。さらに、昇温２において発熱ピーク、吸熱ピークが検出されないことから、スズは昇温１の段階にてニッケルとの金属間化合物が生成したと推定できる。 TG-DTA was measured for the paste 5 of Example 5 by the above method. The result is shown in FIG. From FIG. 3, the melting of the tin particles can be confirmed from the endothermic peak at 230.degree. Further, since no exothermic peak or endothermic peak is detected at the temperature rise 2, it can be estimated that tin produced an intermetallic compound with nickel at the stage of the temperature rise 1.
（比較例１）
＜ペースト６の調製＞
スラリー溶液１の１６６重量部を分取し、これに、２０．７重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、７．６重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．７重量部のバインダー樹脂（製品名エスレックＢＨ−Ａ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、１４２重量部のペースト６（固形分濃度８０．０重量％）を調製した。
(Comparative Example 1)
<Preparation of paste 6>
166 parts by weight of the slurry solution 1 was collected, and 20.7 parts by weight of α-terpineol (boiling point; 220 ° C., manufactured by Wako Pure Chemical Industries, Ltd.) and 7.6 parts by weight of tetradecane (Wako Pure Chemical Industries, Ltd.). Co., Ltd., boiling point 254 ° C.), 0.7 part by weight of a binder resin (product name: S-REC BH-A manufactured by Sekisui Chemical Co., Ltd.) is mixed and concentrated at 60 ° C. and 100 hPa using an evaporator. Paste 6 (solid content concentration 80.0% by weight) was prepared.
比較例１のペースト６を上記方法にて接合サンプルを作製し、測定したせん断強度は、０ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A joining sample of the paste 6 of Comparative Example 1 was prepared by the above method, and the measured shear strength was 0 kgf / mm 2 . The results are shown in Table 1.
（比較例２）
＜ペースト７の調製＞
ニッケル粉（関東化学工業株式会社製 平均粒径３．２μｍ）の７９．２重量部を分取し、これに１９．７重量部のスズ粒子（製品名Ｓｎ−Ａｔ−６００ 福田金属箔粉工業株式会社製 平均粒径７．３μｍ）、９．３重量部のα−テルピネオール（和光純薬工業株式会社製 沸点；２２０℃）、２．０重量部のテトラデカン（和光純薬工業株式会社製 沸点２５４℃）、０．６重量部のバインダー樹脂（製品名エスレックＢＨ−Ａ 積水化学工業株式会社製）を混合し、エバポレータにて６０℃、１００ｈＰａで濃縮を行い、１１１重量部のペースト７（固形分濃度８９．１重量％）を調製した。
(Comparative Example 2)
<Preparation of paste 7>
79.2 parts by weight of nickel powder (average particle size 3.2 μm manufactured by Kanto Chemical Co., Ltd.) was collected, and 19.7 parts by weight of tin particles (product name: Sn-At-600 Fukuda Metal Foil Powder Industry) Co., Ltd. average particle size 7.3 μm), 9.3 parts by weight of α-terpineol (Wako Pure Chemical Industries, Ltd., boiling point; 220 ° C.), 2.0 parts by weight of tetradecane (Wako Pure Chemical Industries, Ltd., boiling point) 254 ° C.) and 0.6 parts by weight of a binder resin (product name: S-REC BH-A manufactured by Sekisui Chemical Co., Ltd.), concentrated at 60 ° C. and 100 hPa with an evaporator, and 111 parts by weight of paste 7 (solid A partial concentration of 89.1% by weight) was prepared.
比較例２のペースト７を上記方法にて接合サンプルを作製し、測定したせん断強度は、０ｋｇｆ／ｍｍ２であった。結果を表１に示す。 A bonding sample was prepared from the paste 7 of Comparative Example 2 by the above method, and the measured shear strength was 0 kgf / mm 2 . The results are shown in Table 1.
（参考例１）
スズ粒子（製品名Ｓｎ−Ａｔ−６００ 福田金属箔粉工業株式会社製 平均粒径７．３μｍ）のＴＧ−ＤＴＡ測定を下記条件で行った。その結果を図４に示す。図４より、昇温２における再融解のピークの発生を確認した。
昇温１）
昇温条件 ：３０℃から３００℃まで５℃／分の速度で昇温
ガスフロー ：窒素／水素＝９７／３体積比 混合ガス ２００ｍｌ／分
降温）
降温条件 ：３００℃から１００℃以下まで１５℃／分の速度で降温後１０分保持
ガスフロー ：窒素／水素＝９７／３体積比 混合ガス ２００ｍｌ／分
昇温２）
昇温条件 ：３０℃から３００℃まで５℃／分の速度で昇温
ガスフロー ：大気 ２００ｍｌ／分
(Reference Example 1)
TG-DTA measurement of tin particles (product name Sn-At-600, Fukuda Metal Foil Powder Co., Ltd. average particle size 7.3 μm) was performed under the following conditions. The result is shown in FIG. From FIG. 4, the occurrence of a remelting peak at a temperature rise of 2 was confirmed.
Temperature rise 1)
Temperature rising condition: Temperature rising from 30 ° C to 300 ° C at a rate of 5 ° C / min
Gas flow: Nitrogen / hydrogen = 97/3 volume ratio Mixed gas 200 ml / min.
Temperature drop condition: Hold for 10 minutes after temperature drop from 300 ° C to below 100 ° C at a rate of 15 ° C / min
Gas flow: Nitrogen / hydrogen = 97/3 volume ratio Mixed gas 200ml / min temperature rise 2)
Temperature rising condition: Temperature rising from 30 ° C to 300 ° C at a rate of 5 ° C / min
Gas flow: Atmosphere 200ml / min
以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはない。 As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment.
Claims (4)
Ａ）レーザー回折／散乱法による平均粒子径が０．５〜２０μｍの範囲内であり、スズ元素を９５重量％以上含有するスズ粒子、
Ｂ）走査型電子顕微鏡観察による平均一次粒子径が３０〜２００ｎｍの範囲内であり、ニッケル元素を９０〜９９．５重量％の範囲内で含有するニッケル微粒子、
からなる金属粒子組成物であって、前記成分Ａ及び成分Ｂの重量比（成分Ａ：成分Ｂ）が２０：８０〜４０：６０の範囲内である金属粒子組成物。 The following components A and B;
A) a tin particle having an average particle diameter by laser diffraction / scattering method in the range of 0.5 to 20 μm and containing 95% by weight or more of tin element;
B) Nickel fine particles having an average primary particle diameter in a range of 30 to 200 nm by observation with a scanning electron microscope and containing nickel element in a range of 90 to 99.5% by weight,
A metal particle composition comprising a weight ratio of the component A and the component B (component A: component B) in the range of 20:80 to 40:60 .
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