JP2024038285A - Sintered compact of silver particle - Google Patents
Sintered compact of silver particle Download PDFInfo
- Publication number
- JP2024038285A JP2024038285A JP2024001136A JP2024001136A JP2024038285A JP 2024038285 A JP2024038285 A JP 2024038285A JP 2024001136 A JP2024001136 A JP 2024001136A JP 2024001136 A JP2024001136 A JP 2024001136A JP 2024038285 A JP2024038285 A JP 2024038285A
- Authority
- JP
- Japan
- Prior art keywords
- silver particles
- sintered body
- silver
- acid
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002245 particle Substances 0.000 title claims abstract description 296
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 238
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 238
- 239000004332 silver Substances 0.000 title claims abstract description 238
- 239000000203 mixture Substances 0.000 description 56
- -1 amine compound Chemical class 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 238000001878 scanning electron micrograph Methods 0.000 description 33
- 239000002904 solvent Substances 0.000 description 32
- 238000005245 sintering Methods 0.000 description 29
- 235000014113 dietary fatty acids Nutrition 0.000 description 27
- 229930195729 fatty acid Natural products 0.000 description 27
- 239000000194 fatty acid Substances 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 26
- 230000001070 adhesive effect Effects 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 23
- 238000005259 measurement Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 239000003495 polar organic solvent Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 9
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004455 differential thermal analysis Methods 0.000 description 8
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000003973 alkyl amines Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 5
- 229960003656 ricinoleic acid Drugs 0.000 description 5
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 5
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940100890 silver compound Drugs 0.000 description 3
- 150000003379 silver compounds Chemical class 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- XBUXARJOYUQNTC-UHFFFAOYSA-N ()-3-Hydroxynonanoic acid Chemical compound CCCCCCC(O)CC(O)=O XBUXARJOYUQNTC-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- JHRQMZPLCYCFPI-UHFFFAOYSA-N 17-hydroxymargaric acid Chemical compound OCCCCCCCCCCCCCCCCC(O)=O JHRQMZPLCYCFPI-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 2
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 2
- CPLYLXYEVLGWFJ-UHFFFAOYSA-N 2-hydroxyarachidic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)C(O)=O CPLYLXYEVLGWFJ-UHFFFAOYSA-N 0.000 description 2
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 2
- JGHSBPIZNUXPLA-UHFFFAOYSA-N 2-hydroxyhexadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)C(O)=O JGHSBPIZNUXPLA-UHFFFAOYSA-N 0.000 description 2
- JYZJYKOZGGEXSX-UHFFFAOYSA-N 2-hydroxymyristic acid Chemical compound CCCCCCCCCCCCC(O)C(O)=O JYZJYKOZGGEXSX-UHFFFAOYSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- JZWLIRVAYJRWLN-UHFFFAOYSA-N 2-hydroxytricosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)C(O)=O JZWLIRVAYJRWLN-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- IBPVZXPSTLXWCG-UHFFFAOYSA-N 22-hydroxydocosanoic acid Chemical compound OCCCCCCCCCCCCCCCCCCCCCC(O)=O IBPVZXPSTLXWCG-UHFFFAOYSA-N 0.000 description 2
- CWSNHZHHWHLJIM-UHFFFAOYSA-N 3-Hydroxytridecanoic acid Chemical compound CCCCCCCCCCC(O)CC(O)=O CWSNHZHHWHLJIM-UHFFFAOYSA-N 0.000 description 2
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- FYSSBMZUBSBFJL-UHFFFAOYSA-N 3-hydroxydecanoic acid Chemical compound CCCCCCCC(O)CC(O)=O FYSSBMZUBSBFJL-UHFFFAOYSA-N 0.000 description 2
- FWZUXWSQLNHYIC-UHFFFAOYSA-N 3-hydroxyheptadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)CC(O)=O FWZUXWSQLNHYIC-UHFFFAOYSA-N 0.000 description 2
- POMQYTSPMKEQNB-UHFFFAOYSA-N 3-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)CC(O)=O POMQYTSPMKEQNB-UHFFFAOYSA-N 0.000 description 2
- NDPLAKGOSZHTPH-UHFFFAOYSA-N 3-hydroxyoctanoic acid Chemical compound CCCCCC(O)CC(O)=O NDPLAKGOSZHTPH-UHFFFAOYSA-N 0.000 description 2
- CBWALJHXHCJYTE-UHFFFAOYSA-N 3-hydroxypalmitic acid Chemical compound CCCCCCCCCCCCCC(O)CC(O)=O CBWALJHXHCJYTE-UHFFFAOYSA-N 0.000 description 2
- FARPMBPKLYEDIL-UHFFFAOYSA-N 3-hydroxyundecanoic acid Chemical compound CCCCCCCCC(O)CC(O)=O FARPMBPKLYEDIL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- KZZKOVLJUKWSKX-UHFFFAOYSA-N cyclobutanamine Chemical compound NC1CCC1 KZZKOVLJUKWSKX-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
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- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
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- 238000003760 magnetic stirring Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- MUCMKTPAZLSKTL-UHFFFAOYSA-N (3RS)-3-hydroxydodecanoic acid Natural products CCCCCCCCCC(O)CC(O)=O MUCMKTPAZLSKTL-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Powder Metallurgy (AREA)
- Die Bonding (AREA)
Abstract
Description
本発明は、銀粒子の焼結体、及び当該焼結体を部材間に備えている電子部品に関する。 The present invention relates to a sintered body of silver particles and an electronic component including the sintered body between members.
ダイボンド剤等を始めとする導電性接着剤は、半導体、ＬＥＤ、パワ－半導体等の電子部品に使われる接合材料である。接合方式として、加圧と加熱による接合、もしくは無加圧で加熱等による焼結によって基材と接合させることが一般に知られている。近年、製造プロセスの簡便さや効率の観点から、無加圧方式の接合材料の開発が進んでいる。 Conductive adhesives such as die bonding agents are bonding materials used for electronic components such as semiconductors, LEDs, and power semiconductors. As a bonding method, it is generally known to bond to a base material by bonding by applying pressure and heating, or by sintering by heating or the like without applying pressure. In recent years, the development of pressureless bonding materials has been progressing from the viewpoint of simplicity and efficiency of the manufacturing process.
無加圧方式の接合材料として、一つはエポキシ樹脂を含む導電性接着剤が挙げられる。この接合材料は、低温処理でエポキシ樹脂を硬化させて使用するものであり、ボイド発生の抑制や基材との接合強度を向上させることができる（特許文献１）。しかしながら、エポキシ樹脂自体が抵抗体となるために、得られる導電性や熱伝導性が低くなる。 One example of a pressureless bonding material is a conductive adhesive containing an epoxy resin. This bonding material is used by curing epoxy resin through low-temperature treatment, and can suppress the generation of voids and improve the bonding strength with the base material (Patent Document 1). However, since the epoxy resin itself becomes a resistor, the resulting electrical conductivity and thermal conductivity are low.
一方、エポキシ樹脂等の熱硬化性樹脂を含まない接合材料として、近年、銀粒子の開発が進んでいる。銀粒子は、低温で短時間の熱処理で容易に焼結する特徴がある。例えば、特許文献２には、銀粒子からなる固形分と溶媒とを混練してなる金属ペ－ストにおいて、前記固形分が、粒径１００～２００ｎｍの銀粒子を粒子数基準で３０％以上含む銀粒子で構成されており、更に、固形分を構成する銀粒子は、保護剤として炭素数の総和が４～８のアミン化合物が結合した金属ペ－ストが開示されている。当該金属ペ－ストによれば、低温域で銀粒子を焼結させることができ、その上で抵抗の低い焼結体や熱伝導性に優れた焼結体を形成可能とされている。 On the other hand, in recent years, silver particles have been developed as a bonding material that does not contain thermosetting resins such as epoxy resins. Silver particles are characterized by being easily sintered by heat treatment at low temperatures and for a short time. For example, Patent Document 2 discloses that in a metal paste made by kneading a solid content consisting of silver particles and a solvent, the solid content contains 30% or more of silver particles with a particle size of 100 to 200 nm based on the number of particles. A metal paste is disclosed in which the silver particles constituting the solid content are bonded with an amine compound having a total of 4 to 8 carbon atoms as a protective agent. According to the metal paste, silver particles can be sintered in a low temperature range, and it is said that it is possible to form a sintered body with low resistance and a sintered body with excellent thermal conductivity.
銀粒子を用いた導電性接着剤の分野において、導電性接着剤を部材（例えば、電子部品に使用される基板、半導体チップなど）に塗布、焼結して得られる焼結体の空隙を少なくする（緻密度を高くする）ために、焼結時に加圧する（圧力は例えば１０～３０ＭＰａ程度）ことが一般的に行われている。導電性接着剤を加圧しながら焼結することで、焼結体の空隙を少なくすることができる。なお、焼結体中に空隙が多い場合、機械的強度（せん断強度）が不十分になったり、焼結体に割れや欠けが生じやすい等、信頼性の点で問題となる。一方で、焼結時の加圧により、導電性接着剤を塗布した部材にダメ－ジを与える、加圧のために特殊な設備が必要となる等の問題点も挙げられる。また、複雑構造を有する半導体チップなどに焼結体を形成する場合には、導電性接着剤を加圧することができないという問題もある。 In the field of conductive adhesives using silver particles, conductive adhesives are applied to components (e.g., substrates used in electronic components, semiconductor chips, etc.) and sintered to reduce voids in the resulting sintered body. In order to increase the density (increase density), it is common practice to apply pressure (for example, about 10 to 30 MPa) during sintering. By sintering the conductive adhesive while pressurizing it, the voids in the sintered body can be reduced. Note that if there are many voids in the sintered body, problems may occur in terms of reliability, such as insufficient mechanical strength (shear strength) or the sintered body to be easily cracked or chipped. On the other hand, there are also problems such as the pressure applied during sintering damages the member coated with the conductive adhesive and the need for special equipment for pressure application. Furthermore, when forming a sintered body on a semiconductor chip or the like having a complicated structure, there is also the problem that the conductive adhesive cannot be pressurized.
そこで、近年、銀粒子の焼結時に加圧を行わなくとも、緻密度の高い焼結体が求められている。 Therefore, in recent years, there has been a demand for a sintered body with high density without applying pressure during sintering of silver particles.
このような状況下、本発明は、銀粒子の焼結体であって、緻密度の高い新規な焼結体を提供することを主な目的とする。さらに、本発明は、当該焼結体を部材間に備えている電子部品を提供することも目的とする。 Under these circumstances, the main object of the present invention is to provide a novel sintered body of silver particles with high density. Furthermore, another object of the present invention is to provide an electronic component that includes the sintered body between members.
本発明者は、上記の課題を解決すべく鋭意検討を行った。その結果、平均粒子径が所定範囲にある相対的に小さい銀粒子と、平均粒子径が所定範囲にある相対的に大きい銀粒子とを用い、大きい銀粒子と小さい銀粒子の平均粒子径を特定の関係に設定した銀粒子を用いて焼結体を製造することにより、緻密度が８５％以上と高く、所定の大きさの空隙を備える新規な焼結体が好適に製造されることを見出した。本発明は、このような知見に基づいて、さらに検討を重ねることにより完成したものである。 The present inventor conducted extensive studies to solve the above problems. As a result, the average particle diameters of the large silver particles and small silver particles were determined using relatively small silver particles whose average particle diameters were within a predetermined range and relatively large silver particles whose average particle diameters were within a predetermined range. It has been discovered that by manufacturing a sintered body using silver particles set in the relationship shown in FIG. Ta. The present invention was completed through further studies based on such knowledge.
即ち、本発明は、下記に掲げる態様の発明を提供する。
項１． 銀粒子の焼結体であって、
前記焼結体は、緻密度が８５％以上であり、
前記焼結体は、空隙の個数平均の大きさが０．５０μｍ以上である、焼結体。
項２． 厚みが２００μｍ以下である、項１に記載の焼結体。
項３． 前記焼結体を平面視した場合の面積が、５０ｍｍ2以下である、項１又は２に記
載の焼結体。
項４． 比抵抗値が３．５μΩ・ｃｍ以下である、項１～３のいずれか１項に記載の焼結体。
項５． せん断強度が７０ＭＰａ以上である、項１～４のいずれか１項に記載の焼結体。項６． 項１～５のいずれか１項に記載の焼結体によって部材間が接合されてなる電子部品。
That is, the present invention provides the inventions of the following aspects.
Item 1. A sintered body of silver particles,
The sintered body has a density of 85% or more,
The sintered body is a sintered body in which the number average size of voids is 0.50 μm or more.
Item 2. Item 2. The sintered body according to item 1, which has a thickness of 200 μm or less.
Item 3. Item 3. The sintered body according to Item 1 or 2, wherein the sintered body has an area of 50 mm 2 or less when viewed in plan.
Item 4. The sintered body according to any one of Items 1 to 3, having a specific resistance value of 3.5 μΩ·cm or less.
Item 5. The sintered body according to any one of items 1 to 4, which has a shear strength of 70 MPa or more. Item 6. An electronic component in which members are joined by the sintered body according to any one of items 1 to 5.
本発明によれば、銀粒子の焼結体であって、緻密度の高い新規な焼結体を提供することができる。具体的には、緻密度が８５％以上と高く、かつ、所定の大きさの空隙を有する新規な焼結体を提供することができる。さらに、本発明によれば、当該焼結体を部材間に備えている電子部品を提供することもできる。 According to the present invention, it is possible to provide a novel sintered body of silver particles with high density. Specifically, it is possible to provide a novel sintered body having a high density of 85% or more and having voids of a predetermined size. Furthermore, according to the present invention, it is also possible to provide an electronic component that includes the sintered body between members.
本発明の焼結体は、銀粒子の焼結体であって、緻密度が８５％以上であり、かつ、空隙の個数平均の大きさが０．５０μｍ以上であることを特徴としている。本発明の焼結体は、緻密度及び空隙の個数平均大きさが所定値以上の新規な焼結体である。後述の通り、このような特定の緻密度及び空隙の個数平均大きさを備える焼結体は、後述する製造方法を採用することによって好適に製造することができる。 The sintered body of the present invention is a sintered body of silver particles, and is characterized in that the density is 85% or more and the number average size of voids is 0.50 μm or more. The sintered body of the present invention is a novel sintered body in which the density and the number average size of voids are greater than predetermined values. As described later, a sintered body having such a specific density and number average size of voids can be suitably manufactured by employing the manufacturing method described below.
以下、本発明の銀粒子の焼結体、及び当該焼結体を部材間に備えている電子部品について詳述する。なお、本明細書において、「～」で結ばれた数値は、「～」の前後の数値を下限値及び上限値として含む数値範囲を意味する。複数の下限値と複数の上限値が別個に記載されている場合、任意の下限値と上限値を選択し、「～」で結ぶことができるものとする。 Hereinafter, the sintered body of silver particles of the present invention and the electronic component including the sintered body between members will be described in detail. In this specification, numerical values connected by "-" mean a numerical range that includes the numerical values before and after "-" as lower and upper limits. If multiple lower limit values and multiple upper limit values are listed separately, it is possible to select any lower limit value and upper limit value and connect them with "~".
１．焼結体
本発明の焼結体は、銀粒子の焼結体であり、具体的には、銀粒子と溶媒を含む組成物（導電性接着剤として使用される。）を焼結することにより得られる。本発明の焼結体の好ましい製造方法については、後述する。
1. Sintered body The sintered body of the present invention is a sintered body of silver particles, and specifically, by sintering a composition containing silver particles and a solvent (used as a conductive adhesive). can get. A preferred method for manufacturing the sintered body of the present invention will be described later.
本発明の焼結体は、緻密度が８５％以上であり、かつ、空隙の個数平均の大きさが０．５０μｍ以上である。本発明の焼結体は、銀粒子の焼結体であるから、焼結体の内部には空隙が存在し、緻密度は１００％未満となる。本発明の焼結体の緻密度は、８７％以上であってもよいし、９０％以上であってもよい。また、空隙の個数平均の大きさは、好ましくは０．５０～１．００μｍ程度、より好ましくは０．５０～０．９５μｍ程度である。本発明の焼結体の緻密度及び空隙の個数平均の大きさの測定方法は、以下の通りである。 The sintered body of the present invention has a compactness of 85% or more and an average size of voids of 0.50 μm or more. Since the sintered body of the present invention is a sintered body of silver particles, voids exist inside the sintered body, and the density is less than 100%. The compactness of the sintered body of the present invention may be 87% or more, or 90% or more. Further, the average size of the voids is preferably about 0.50 to 1.00 μm, more preferably about 0.50 to 0.95 μm. The method for measuring the density and the number average size of voids of the sintered body of the present invention is as follows.
＜緻密度＞
まず、銅板上に無電解銀めっきを０．５μｍ施した基材を準備する。基材の上（銀めっきが形成された表面）に、銀粒子と溶媒の組成物（導電性接着剤：銀粒子９０質量％、テキサノール１０質量％の銀粒子分散液））を塗膜厚みが５０μｍとなるように、均一に塗布する。さらに、塗膜の上に、裏面（導電性接着剤と接する面）に金めっきが施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を積層して積層体を得る。次に、乾燥器（循環式）を用い、得られた積層体を所定の焼結温度（２００℃又は２５０℃）で６０分間の焼結条件で加熱し、基材とシリコンウエハとの間の各導電性接着剤が焼結し、基材とシリコンウエハとが焼結体を介して接合された積層体を作製する。次に、焼結体を、積層体ごとエポキシ樹脂（例えば、ビューラー社製）で樹脂包埋し、２４時間静置して樹脂を硬化させる。次に、樹脂包埋された積層体を精密低速切断機（例えば、ＡＬＬＩＥＤ社製ＴｅｃｈＣｕｔ４）で切断し、（例えば、日立ハイテクノロジーズ社製）イオンミリング（例えば、日立ハイテクノロジーズ社製のＩＭ４０００ＰＬＵＳ）により、断面ミリングを実施する。なお、断面ミリングは、放電電圧１．５ｋＶ、加速電圧６ｋＶにて、アルゴンガス流量０．０７ｃｍ3/ｍｉｎ、±３０°のスイングによってイオンビームを照射して実施する。断面ミリングによって得られた焼結体の断面を走査型電子顕微鏡で観察してＳＥＭ画像を取得する。観察にはＳＥＤモード（二次電子検出器）を用いて、加速電圧２０ｋＶ、２０００倍の視野にて、横幅６０μｍの範囲を観察する。なお、ＳＥＭ画像の縦方向については、銀の焼結層の縦幅１０μｍ以上、２００μｍ以下の範囲とする。これは銀の焼結層が１０μｍ未満であると、接合体としての特性上、機械的強度を損なう恐れがあり、また、２００μｍを超えると、積層体の嵩が高くなることから、焼結時のアウトガスが均一に起こりづらいと想定され、信頼性の観点から不利であるからである。密度の算出は、得られたＳＥＭ画像を二値化ソフト（Ｉｍａｇｅ ｊ）で濃淡を白と黒の二階調に画像変換し、以下の関係式で求める。
緻密度（％）＝焼結銀面積（白色画素数）÷焼結体全面積｛焼結銀面積（白色画素数）＋空孔面積（黒色画素数）｝×１００
<Density>
First, a base material having a copper plate plated with electroless silver to a thickness of 0.5 μm is prepared. A composition of silver particles and a solvent (conductive adhesive: silver particle dispersion containing 90% by mass of silver particles and 10% by mass of Texanol)) is applied onto the base material (the surface on which silver plating is formed) to a coating thickness of Apply uniformly to a thickness of 50 μm. Further, a silicon wafer (size 2 mm x 2 mm) whose back surface (the surface in contact with the conductive adhesive) is gold-plated is laminated on the coating film to obtain a laminate. Next, using a dryer (circulating type), the obtained laminate is heated at a predetermined sintering temperature (200°C or 250°C) for 60 minutes, and the sintering conditions between the base material and the silicon wafer are Each conductive adhesive is sintered to produce a laminate in which the base material and the silicon wafer are bonded via the sintered body. Next, the sintered body and the laminate are embedded in an epoxy resin (for example, manufactured by Buehler), and left to stand for 24 hours to harden the resin. Next, the resin-embedded laminate is cut with a precision low-speed cutting machine (for example, TechCut4 manufactured by ALLIED), and then cut by ion milling (for example, IM4000PLUS manufactured by Hitachi High-Technologies) (for example, manufactured by Hitachi High-Technologies). , carry out cross-sectional milling. Note that the cross-sectional milling is performed by irradiating an ion beam with a swing of ±30° at a discharge voltage of 1.5 kV, an acceleration voltage of 6 kV, and an argon gas flow rate of 0.07 cm 3 /min. A cross section of the sintered body obtained by cross-sectional milling is observed with a scanning electron microscope to obtain an SEM image. For observation, an SED mode (secondary electron detector) is used to observe an area with a width of 60 μm at an acceleration voltage of 20 kV and a field of view magnified 2000 times. In addition, regarding the vertical direction of the SEM image, the vertical width of the silver sintered layer is in the range of 10 μm or more and 200 μm or less. This is because if the silver sintered layer is less than 10 μm, the mechanical strength of the bonded body may be impaired, and if it exceeds 200 μm, the bulk of the laminate will increase. This is because it is assumed that it is difficult for outgassing to occur uniformly, which is disadvantageous from a reliability standpoint. The density is calculated by converting the obtained SEM image into two gradations of white and black using binarization software (Image j), and using the following relational expression.
Density (%) = sintered silver area (number of white pixels) ÷ total area of sintered body {sintered silver area (number of white pixels) + pore area (number of black pixels)} x 100
＜空隙の測定＞
焼結体のＳＥＭ像を前記の＜緻密度＞の測定と同様にして取得した、Ｉｍａｇｅ ｊを用いて２値化されたＳＥＭ画像について、（マウンテック社製）画像解析式粒度分布測定ソフトウェア（Ｍａｃｖｉｅｗ）を用いて画像処理（色差の自動読み取りによって、２値化した画像の空隙部分を粒子として解析）し、焼結体の空隙を球形と仮定し、その空隙の個数平均の大きさを算出する。このとき、焼結体の比表面積は、前記球形の単位体積あたりの表面積から算出することが出来る。なお、空隙部分とは、ボイドやクラックとは異なる、アウトガスや粒子成長により発生した細孔部のことであり、細孔部とは直径が５０ｎｍ以上、かつ１０μｍ以下のもとする。１０μｍ以上の大きさとなる孔はボイドやクラックと呼称し、空隙部分とは除外して換算する。
<Measurement of voids>
The SEM image of the sintered body was obtained in the same manner as the above-mentioned <Density> measurement, and the SEM image was binarized using Image j. ) is used to process the image (by automatically reading the color difference, the voids in the binarized image are analyzed as particles), and the voids in the sintered body are assumed to be spherical, and the average size of the voids is calculated. . At this time, the specific surface area of the sintered body can be calculated from the surface area per unit volume of the spherical shape. Note that the void portion refers to a pore portion generated by outgas or particle growth, which is different from voids or cracks, and a pore portion is defined as having a diameter of 50 nm or more and 10 μm or less. Holes with a size of 10 μm or more are called voids or cracks, and are excluded from voids in the calculation.
本発明の焼結体の空隙の比表面積は、好ましくは０．１５～０．８０μｍ2程度、より好ましくは０．１８～０．７５μｍ2程度である。 The specific surface area of the voids in the sintered body of the present invention is preferably about 0.15 to 0.80 μm 2 , more preferably about 0.18 to 0.75 μm 2 .
また、本発明の焼結体のせん断強度は、好ましくは７０ＭＰａ以上、より好ましくは７２ＭＰａ以上である。なお、当該せん断強度の上限については、例えば２００ＭＰａ以下である。焼結体のせん断強度の測定方法は、以下の通りであり、具体的には実施例に記載の方法で測定される。 Further, the shear strength of the sintered body of the present invention is preferably 70 MPa or more, more preferably 72 MPa or more. Note that the upper limit of the shear strength is, for example, 200 MPa or less. The shear strength of the sintered body is measured as follows, and specifically, it is measured by the method described in Examples.
＜せん断強度＞
前記の＜緻密度＞と同様にして、基材とシリコンウエハとが焼結体を介して接合された積層体を９個作製する。得られた積層体について、それぞれ、室温でボンドテスター（例えば、西進商事製ＳＳ３０－ＷＤ）を用い、０．１２０ｍｍ／ｓの条件で焼結体に負荷をかけ、各積層体のダイシェアテストを実施して破断時の最大荷重を測定する。このようにして得られた最大荷重を接合面積で除することでせん断強度値を得る。なお、測定結果は、せん断強度を測定した９個の金めっきシリコンウエハの平均値である。
<Shear strength>
Nine laminates in which a base material and a silicon wafer are bonded via a sintered body are manufactured in the same manner as in <Denseness> described above. A die shear test was performed on each of the obtained laminates by applying a load to the sintered body at room temperature using a bond tester (for example, SS30-WD manufactured by Seishin Shoji Co., Ltd.) at a rate of 0.120 mm/s. Measure the maximum load at break. The shear strength value is obtained by dividing the maximum load thus obtained by the joint area. Note that the measurement results are the average values of nine gold-plated silicon wafers whose shear strengths were measured.
また、本発明の焼結体の比抵抗値は、好ましくは３．５μΩ・ｃｍ以下、より好ましくは３．２μΩ・ｃｍ以下、さらに好ましくは３．０μΩ・ｃｍ以下である。なお、当該比抵抗値の下限は、例えば２．０μΩ・ｃｍ以上である。焼結体の比抵抗値の測定方法は、以下の通りであり、具体的には実施例に記載の方法で測定される。 Further, the specific resistance value of the sintered body of the present invention is preferably 3.5 μΩ·cm or less, more preferably 3.2 μΩ·cm or less, and still more preferably 3.0 μΩ·cm or less. Note that the lower limit of the specific resistance value is, for example, 2.0 μΩ·cm or more. The method for measuring the specific resistance value of the sintered body is as follows, and specifically, it is measured by the method described in Examples.
＜比抵抗値＞
厚みが５０μｍの焼結体を用意する。次に、焼結体の抵抗値を室温条件で、抵抗計（例えば、ＨＩＯＫＩ ＲＭ３５４８）で測定し、実際の膜厚をマイクロメーターにて計測した値から、比抵抗（体積抵抗）値を求める。なお、この比抵抗値は焼結体の４か所を測定した値の平均値である。
<Specific resistance value>
A sintered body having a thickness of 50 μm is prepared. Next, the resistance value of the sintered body is measured at room temperature using a resistance meter (for example, HIOKI RM3548), and the specific resistance (volume resistance) value is determined from the actual film thickness measured using a micrometer. Note that this specific resistance value is the average value of values measured at four locations on the sintered body.
本発明の焼結体の厚みは、焼結体の用途に応じて適宜設計できるが、例えば２００μｍ以下、好ましくは１５０μｍ以下、より好ましくは１００μｍ以下である。また、焼結体の厚みの下限は、好ましくは１０μｍである。本発明の焼結体を平面視した場合の面積についても、焼結体の用途に応じて適宜設計できるが、好ましくは２５ｍｍ2以下、より好ましくは１６ｍｍ2以下である。当該面積の下限は、例えば１ｍｍ2以上である。 The thickness of the sintered body of the present invention can be appropriately designed depending on the use of the sintered body, but is, for example, 200 μm or less, preferably 150 μm or less, and more preferably 100 μm or less. Further, the lower limit of the thickness of the sintered body is preferably 10 μm. The area of the sintered body of the present invention when viewed in plan can also be appropriately designed depending on the use of the sintered body, but is preferably 25 mm 2 or less, more preferably 16 mm 2 or less. The lower limit of the area is, for example, 1 mm 2 or more.
本発明の焼結体の製造方法は、前記の緻密度及び空隙の個数平均の大きさを満たすものが製造されれば、特に制限されない。本発明の焼結体の好ましい製造方法を以下に説明する。 The method for manufacturing the sintered body of the present invention is not particularly limited as long as the sintered body is manufactured to satisfy the above-mentioned density and number average size of voids. A preferred method for manufacturing the sintered body of the present invention will be described below.
２．焼結体の製造方法
本発明の焼結体は、銀粒子を焼結することにより製造することができる。より具体的には、銀粒子と溶媒を含む組成物を焼結させることにより製造することができる。
2. Method for manufacturing a sintered body The sintered body of the present invention can be manufactured by sintering silver particles. More specifically, it can be manufactured by sintering a composition containing silver particles and a solvent.
銀粒子は、銀を含む粒子であって、本発明の焼結体を好適に製造する観点から、銀粒子は、平均粒子径の異なる銀粒子Ａ及び銀粒子Ｂを含む。銀粒子Ａの平均粒子径は、好ましくは５０～５００ｎｍの範囲である。また、銀粒子Ｂの平均粒子径は、好ましくは０．５～５．５μｍの範囲である。さらに、銀粒子Ｂの平均粒子径は、銀粒子Ａの平均粒子径の５～１１倍の関係を充足することが好ましい。すなわち、例えば銀粒子Ａの平均粒子径が下限値の５０ｎｍである場合、銀粒子Ｂの平均粒子径は、０．５～０．５５μｍの範囲内であることが好ましい。また、例えば銀粒子Ａの平均粒子径が上限値の５００ｎｍである場合、銀粒子Ｂの平均粒子径は、２．５～５．５μｍの範囲内であることが好ましい。 The silver particles are particles containing silver, and from the viewpoint of suitably manufacturing the sintered body of the present invention, the silver particles include silver particles A and silver particles B having different average particle diameters. The average particle diameter of silver particles A is preferably in the range of 50 to 500 nm. Further, the average particle diameter of the silver particles B is preferably in the range of 0.5 to 5.5 μm. Further, it is preferable that the average particle diameter of the silver particles B satisfies a relationship of 5 to 11 times the average particle diameter of the silver particles A. That is, for example, when the average particle diameter of silver particles A is the lower limit of 50 nm, the average particle diameter of silver particles B is preferably within the range of 0.5 to 0.55 μm. Further, for example, when the average particle diameter of silver particles A is the upper limit of 500 nm, the average particle diameter of silver particles B is preferably within the range of 2.5 to 5.5 μm.
本発明の焼結体を好適に製造する観点から、銀粒子Ａの平均粒子径は、好ましくは５０～５００ｎｍの範囲であるが、下限については、好ましくは６０ｎｍ以上が挙げられ、上限については、好ましくは３００ｎｍ以下、より好ましくは２５０ｎｍ以下、さらに好ましくは２００ｎｍ以下が挙げられ、好ましい範囲としては、５０～３００ｎｍ、５０～２５０ｎｍ、５０～２００ｎｍ、６０～３００ｎｍ、６０～２５０ｎｍ、６０～２００ｎｍなどが挙げられる。 From the viewpoint of suitably manufacturing the sintered body of the present invention, the average particle diameter of the silver particles A is preferably in the range of 50 to 500 nm, but the lower limit is preferably 60 nm or more, and the upper limit is: Preferably, the wavelength is 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. Preferred ranges include 50 to 300 nm, 50 to 250 nm, 50 to 200 nm, 60 to 300 nm, 60 to 250 nm, and 60 to 200 nm. Can be mentioned.
また、本発明の焼結体を好適に製造する観点から、銀粒子Ｂの平均粒子径は、好ましくは０．５～５．５μｍの範囲であるが、本発明の効果をより一層好適に奏する観点から、下限については、好ましくは０．６μｍ以上が挙げられ、上限については、好ましくは３．０μｍ以下、より好ましくは２．５μｍ以下、さらに好ましくは２．０μｍ以下が挙げられ、好ましい範囲としては、０．５～３．０μｍ、０．５～２．５μｍ、０．５～２．０μｍ、０．６～３．０μｍ、０．６～２．５μｍ、０．６～２．０μｍが挙げられる。 In addition, from the viewpoint of suitably manufacturing the sintered body of the present invention, the average particle diameter of the silver particles B is preferably in the range of 0.5 to 5.5 μm, but the effect of the present invention is more preferably achieved. From this point of view, the lower limit is preferably 0.6 μm or more, and the upper limit is preferably 3.0 μm or less, more preferably 2.5 μm or less, even more preferably 2.0 μm or less, and the preferred range is is 0.5-3.0μm, 0.5-2.5μm, 0.5-2.0μm, 0.6-3.0μm, 0.6-2.5μm, 0.6-2.0μm. Can be mentioned.
本発明において、銀粒子の平均粒子径は、ＳＥＭ画像について、画像解析ソフト（例えば、Ｍａｃｖｉｅｗ（マウンテック社製））を用いて、無作為に選択した２００個の粒子について測定した体積基準平均粒子径である。なお、観察にはＳＥＤモード（二次電子検出器）を用いて、加速電圧を２０ｋＶ、５０００～３００００倍の観察倍率にて、横幅１～２０μｍの範囲を観察する。なお、ＳＥＭ画像の縦方向については、横幅１～２０μｍの範囲に２００個以上（通常、２００～３００個程度）の銀粒子が含まれる幅とする。また、体積基準平均粒子径は、ＳＥＭ画像に観察される粒子が、その直径を有する球形であると仮定して測定される値である。具体的な測定方法は、実施例に記載のとおりである。 In the present invention, the average particle diameter of the silver particles is the volume-based average particle diameter measured for 200 randomly selected particles using image analysis software (for example, Macview (manufactured by Mountech)) on a SEM image. It is. Note that an SED mode (secondary electron detector) is used for observation, and an accelerating voltage of 20 kV and an observation magnification of 5,000 to 30,000 times are used to observe a width range of 1 to 20 μm. Note that in the vertical direction of the SEM image, the width is such that 200 or more (usually about 200 to 300) silver particles are included in the width range of 1 to 20 μm. Further, the volume-based average particle diameter is a value measured on the assumption that the particles observed in the SEM image are spherical with that diameter. The specific measurement method is as described in Examples.
本発明の焼結体を好適に製造する観点から、銀粒子において、銀粒子Ｂの平均粒子径は、銀粒子Ａの平均粒子径の５～１１倍の関係を充足することが好ましく、８～１１倍の関係を充足することがより好ましく、９～１１倍の関係を充足することがさらに好ましい。 From the viewpoint of suitably manufacturing the sintered body of the present invention, it is preferable that the average particle diameter of silver particles B satisfies a relationship of 5 to 11 times the average particle diameter of silver particles A, and 8 to 11 times the average particle diameter of silver particles A. It is more preferable to satisfy an 11-fold relationship, and even more preferable to satisfy a 9- to 11-fold relationship.
銀粒子において、銀粒子Ａと銀粒子Ｂの質量比（銀粒子Ａ：銀粒子Ｂ）は、好ましくは１：９から９：１の範囲であり、より好ましくは７：３から３：７の範囲であり、さらに好ましくは６：４から４：６の範囲である。なお、銀粒子には、銀粒子Ａ及び銀粒子Ｂが支配的に含まれており、これら合計含有量は、好ましくは８０質量％以上、より好ましくは９０質量％以上、さらに好ましくは９５質量％以上、特に好ましくは９８質量％以上であり、１００質量％であってもよい。 In the silver particles, the mass ratio of silver particles A and silver particles B (silver particles A: silver particles B) is preferably in the range of 1:9 to 9:1, more preferably in the range of 7:3 to 3:7. The ratio is preferably from 6:4 to 4:6. Note that the silver particles predominantly contain silver particles A and silver particles B, and the total content thereof is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass. Above, it is particularly preferably 98% by mass or more, and may be 100% by mass.
銀粒子は、粒子径が５０ｎｍ未満の銀粒子を含んでいてもよい。ただし、本発明の焼結体を好適に製造する観点から、粒子径が５０ｎｍ未満の銀粒子の割合は、例えば銀粒子の個数基準で、３０％以下、好ましくは２０％以下、より好ましくは１０％以下である。同様に、銀粒子は、粒子径が５．５μｍ超の銀粒子を含んでいてもよい。粒子径が５．５μｍ超の銀粒子の割合は、例えば銀粒子の個数基準で、３０％以下、好ましくは２０％以下、より好ましくは１０％以下である。なお、ここでいう粒子径とは体積基準粒子径のことであり、前記粒径の測定手法によって算出されたものである。この該当粒子の個数割合は、画像解析ソフト（Ｍａｃｖｉｅｗ）により、銀粒子２００個中から測定する。 The silver particles may include silver particles having a particle diameter of less than 50 nm. However, from the viewpoint of suitably manufacturing the sintered body of the present invention, the proportion of silver particles with a particle diameter of less than 50 nm is, for example, 30% or less, preferably 20% or less, more preferably 10% or less, based on the number of silver particles. % or less. Similarly, the silver particles may include silver particles having a particle size of more than 5.5 μm. The proportion of silver particles having a particle diameter of more than 5.5 μm is, for example, 30% or less, preferably 20% or less, more preferably 10% or less, based on the number of silver particles. Note that the particle size here refers to a volume-based particle size, and is calculated using the particle size measurement method described above. The number ratio of the corresponding particles is measured from among 200 silver particles using image analysis software (Macview).
また、銀粒子は、熱重量示差熱分析における発熱ピ－クが、１２０～２５０℃の範囲に複数観察されることが好ましい。具体的には、熱重量示差熱分析における発熱ピ－クが、１２０～１５０℃の間に少なくとも１つ（通常は１つ）、１６０～２５０℃の間に少なくとも１つ（通常は１つ又は２つ）観察されることが好ましい。また、銀粒子の乾燥粉末は、熱重量示差熱分析によって３０℃から５００℃まで加熱したときの重量減少率が１．５重量％以下であることが好ましく、０．０５～１．３重量％であることがより好ましい。熱重量示差熱分析の方法は以下の通りである。 Further, it is preferable that the silver particles have a plurality of exothermic peaks observed in the range of 120 to 250° C. in thermogravimetric differential thermal analysis. Specifically, there is at least one (usually one) exothermic peak between 120 and 150°C and at least one (usually one or more) exothermic peak between 160 and 250°C in thermogravimetric differential thermal analysis. 2) It is preferable to be observed. Further, the dry powder of silver particles preferably has a weight loss rate of 1.5% by weight or less, and 0.05 to 1.3% by weight when heated from 30°C to 500°C according to thermogravimetric differential thermal analysis. It is more preferable that The method of thermogravimetric differential thermal analysis is as follows.
＜熱重量示差熱分析（ＴＧ－ＤＴＡ）＞
まず、風乾した銀粒子を用意する。例えば、導電性接着剤から銀粒子を取得して分析する場合には、各導電性接着剤１ｇに対し、メタノ－ル２ｇを加えてよく分散させたのち、銀粒子をろ取、風乾して銀粒子乾燥粉末を得て、分析対象とする。銀粒子の乾燥粉末のＴＧ－ＤＴＡを熱重量示差熱分析装置（例えば、ＨＩＴＡＣＨＩ Ｇ３００ ＡＳＴ－２）で測定する。測定条件は、雰囲気：空気、測定温度：３０～５００℃、昇温速度：１０℃／ｍｉｎとする。得られたＴＧ－ＤＴＡチャ－トから、ＴＧ－ＤＴＡ分析における銀粒子の結合に起因する発熱ピ－クと、熱分析によって３０℃から５００℃まで加熱したときの重量減少率を得る。
<Thermogravimetric differential thermal analysis (TG-DTA)>
First, air-dried silver particles are prepared. For example, when collecting and analyzing silver particles from conductive adhesives, add 2 g of methanol to 1 g of each conductive adhesive and disperse well, then collect the silver particles by filtration and air dry. A dry powder of silver particles is obtained and used for analysis. The TG-DTA of the dry powder of silver particles is measured using a thermogravimetric differential thermal analyzer (eg, HITACHI G300 AST-2). The measurement conditions are: atmosphere: air, measurement temperature: 30 to 500°C, and temperature increase rate: 10°C/min. From the obtained TG-DTA chart, the exothermic peak due to the bonding of silver particles in TG-DTA analysis and the weight loss rate when heated from 30° C. to 500° C. are obtained by thermal analysis.
銀粒子に含まれる銀の含有量は、好ましくは９５質量％以上、より好ましくは９８質量％以上である。 The content of silver contained in the silver particles is preferably 95% by mass or more, more preferably 98% by mass or more.
本発明の焼結体を好適に製造する観点から、銀粒子を表面処理することが好ましい。すなわち、銀粒子は、表面処理銀粒子であることが好ましい。 From the viewpoint of suitably manufacturing the sintered body of the present invention, it is preferable to surface-treat the silver particles. That is, the silver particles are preferably surface-treated silver particles.
より具体的には、銀粒子において、銀粒子Ａの表面には、アミン化合物が付着していることが好ましい。また、銀粒子Ｂの表面にもアミン化合物が付着していてもよい。アミン化合物は、銀粒子の表面に付着し、保護層を形成することができる。銀粒子においては、平均粒子径を前記特定範囲に設定するように、アミン化合物を付着させることが好ましい。 More specifically, in the silver particles, it is preferable that an amine compound is attached to the surface of the silver particles A. Further, an amine compound may also be attached to the surface of the silver particles B. The amine compound can adhere to the surface of silver particles and form a protective layer. It is preferable to attach an amine compound to the silver particles so that the average particle diameter is set within the above-mentioned specific range.
アミン化合物としては、特に制限されないが、本発明の効果をより一層好適に奏する観点から、アルキルアミンが好ましい。アルキルアミンとしては、特に制限されないが、好ましくはアルキル基の炭素数が３以上１８以下のアルキルアミン、より好ましくはアルキル基の炭素数が４以上１２以下のアルキルアミンが挙げられる。 The amine compound is not particularly limited, but is preferably an alkylamine from the viewpoint of more favorably achieving the effects of the present invention. The alkylamine is not particularly limited, but preferably includes an alkylamine whose alkyl group has 3 or more carbon atoms and 18 or less, more preferably an alkylamine whose alkyl group has 4 or more carbon atoms and 12 or less.
アルキルアミンの好ましい具体例としては、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、１，２－ジメチルプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｓｅｃ－ブチルアミン、ｔｅｒｔ－ブチルアミン、イソアミルアミン、ｔｅｒｔ－アミルアミン、３－ペンチルアミン、ｎ－アミルアミン、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、ｎ－オクチルアミン、２－オクチルアミン、２－エチルヘキシルアミン、ｎ－ノニルアミン、ｎ－アミノデカン、ｎ－アミノウンデカン、ｎ－ドデシルアミン、ｎ－トリデシルアミン、２－トリデシルアミン、ｎ－テトラデシルアミン、ｎ－ペンタデシルアミン、ｎ－ヘキサデシルアミン、ｎ－ヘプタデシルアミン、ｎ－オクタデシルアミン、ｎ－オレイルアミン、Ｎ－エチル－１，３－ジアミノプロパン、Ｎ，Ｎ－ジイソプロピルエチルアミン、Ｎ，Ｎ－ジメチルアミノプロパン、Ｎ，Ｎ－ジブチルアミノプロパン、Ｎ，Ｎ－ジメチル－１，３－ジアミノプロパン、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパン、Ｎ，Ｎ－ジイソブチル－１，３－ジアミノプロパン、Ｎ－ラウリルジアミノプロパン等を例示することができる。さらに、２級アミンであるジブチルアミンや環状アルキルアミンであるシクロプロピルアミン、シクロブチルアミン、シクロプロピルアミン、シクロヘキシルアミン、シクロヘプチルアミン、シクロオクチルアミン等も例示することができる。これらの中でも、本発明の効果をより一層好適に奏する観点から、ｎ－プロピルアミン、イソプロピルアミン、シクロプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｓｅｃ－ブチルアミン、ｔｅｒｔ－ブチルアミン、シクロブチルアミン、ｎ－アミルアミン、ｎ－ヘキシルアミン、シクロヘキシルアミン、ｎ－オクチルアミン、２－エチルヘキシルアミン、ｎ－ドデシルアミン、ｎ－オレイルアミン、Ｎ，Ｎ－ジメチル－１，３－ジアミノプロパン、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパンが好ましく、ｎ－ブチルアミン、ｎ－ヘキシルアミン、シクロヘキシルアミン、ｎ－オクチルアミン、ｎ－ドデシルアミン、Ｎ，Ｎ－ジメチル－１，３－ジアミノプロパン、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパンがより好ましい。アミン化合物は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Preferred specific examples of the alkylamine include ethylamine, n-propylamine, isopropylamine, 1,2-dimethylpropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, isoamylamine, tert-amylamine, -Pentylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-octylamine, 2-ethylhexylamine, n-nonylamine, n-aminodecane, n-aminoundecane, n-dodecylamine , n-tridecylamine, 2-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-oleylamine, N-ethyl- 1,3-diaminopropane, N,N-diisopropylethylamine, N,N-dimethylaminopropane, N,N-dibutylaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1 , 3-diaminopropane, N,N-diisobutyl-1,3-diaminopropane, N-lauryldiaminopropane and the like. Further examples include dibutylamine, which is a secondary amine, and cyclopropylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, and cyclooctylamine, which are cyclic alkylamines. Among these, n-propylamine, isopropylamine, cyclopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclobutylamine, n-amylamine are preferred from the viewpoint of achieving the effects of the present invention even more favorably. , n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-oleylamine, N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3 -Diaminopropane is preferred, and n-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, n-dodecylamine, N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3 -Diaminopropane is more preferred. One type of amine compound may be used alone, or two or more types may be used in combination.
銀粒子のアミン化合物の付着量としては、特に制限されないが、銀粒子の質量を１００質量％として、好ましくは１．５質量％以下、より好ましくは１．３質量％以下であり、下限については、好ましくは０．０５質量％以上である。同様に、銀粒子Ａ、Ｂのアミン化合物の付着量についても、それぞれ銀粒子Ａ、Ｂの質量を１００質量％として、好ましくは１．５質量％以下、より好ましくは１．３質量％以下であり、下限については、好ましくは０．０５質量％以上である。銀粒子に付着しているアミン化合物の含有量は、熱重量示差熱分析により測定することができる。 The amount of the amine compound attached to the silver particles is not particularly limited, but is preferably 1.5% by mass or less, more preferably 1.3% by mass or less, based on the mass of the silver particles as 100% by mass, and the lower limit is , preferably 0.05% by mass or more. Similarly, the amount of the amine compound attached to silver particles A and B is preferably 1.5% by mass or less, more preferably 1.3% by mass or less, based on the mass of silver particles A and B as 100% by mass. The lower limit is preferably 0.05% by mass or more. The content of the amine compound attached to the silver particles can be measured by thermogravimetric differential thermal analysis.
また、銀粒子の表面には、脂肪酸、ヒドロキシ脂肪酸などが付着していてもよい。脂肪酸としては、特に制限されないが、好ましくはアルキル基の炭素数が３以上１８以下の脂肪酸、より好ましくはアルキル基の炭素数が４以上１８以下の脂肪酸が挙げられる。脂肪酸の好ましい具体例としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、２－エチルヘキサン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノ－ル酸、α－リノレン酸等が挙げられる。また、脂肪酸の具体例としては、シクロヘキサンカルボン酸のような環状アルキルカルボン酸等も挙げられる。また、ヒドロキシ脂肪酸としては、炭素数３～２４で、かつ水酸基を１個以上（例えば、１個）有する化合物を使用できる。また、ヒドロキシ脂肪酸として、例えば、２－ヒドロキシデカン酸、２－ヒドロキシドデカン酸、２－ヒドロキシテトラデカン酸、２－ヒドロキシヘキサデカン酸、２－ヒドロキシオクタデカン酸、２－ヒドロキシエイコサン酸、２－ヒドロキシドコサン酸、２－ヒドロキシトリコサン酸、２－ヒドロキシテトラコサン酸、３－ヒドロキシヘキサン酸、３－ヒドロキシオクタン酸、３－ヒドロキシノナン酸、３－ヒドロキシデカン酸、３－ヒドロキシウンデカン酸、３－ヒドロキシドデカン酸、３－ヒドロキシトリデカン酸、３－ヒドロキシテトラデカン酸、３－ヒドロキシヘキサデカン酸、３－ヒドロキシヘプタデカン酸、３－ヒドロキシオクタデカン酸、ω－ヒドロキシ－２－デセン酸、ω－ヒドロキシペンタデカン酸、ω－ヒドロキシヘプタデカン酸、ω－ヒドロキシエイコサン酸、ω－ヒドロキシドコサン酸、６－ヒドロキシオクタデカン酸、リシノ－ル酸、１２－ヒドロキシステアリン酸、［Ｒ－（Ｅ）］－１２－ヒドロキシ－９－オクタデセン酸等が挙げられる。中でも、炭素数４～１８で、かつω位以外（特に、１２位）に１個の水酸基を有するヒドロキシ脂肪酸が好ましく、リシノ－ル酸、１２－ヒドロキシステアリン酸がより好ましい。脂肪酸及びヒドロキシ脂肪酸は、それぞれ、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Furthermore, fatty acids, hydroxy fatty acids, etc. may be attached to the surface of the silver particles. The fatty acid is not particularly limited, but preferably includes a fatty acid whose alkyl group has 3 or more carbon atoms and 18 or less carbon atoms, and more preferably a fatty acid whose alkyl group has 4 or more carbon atoms and 18 or less carbon atoms. Preferred specific examples of fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid. Examples include oleic acid, α-linolenic acid, and the like. Further, specific examples of fatty acids include cyclic alkyl carboxylic acids such as cyclohexane carboxylic acid. Further, as the hydroxy fatty acid, a compound having 3 to 24 carbon atoms and one or more (for example, one) hydroxyl group can be used. In addition, examples of hydroxy fatty acids include 2-hydroxydecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyeicosanoic acid, and 2-hydroxydocosane. Acid, 2-hydroxytricosanoic acid, 2-hydroxytetracosanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecane Acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxyhexadecanoic acid, 3-hydroxyheptadecanoic acid, 3-hydroxyoctadecanoic acid, ω-hydroxy-2-decenoic acid, ω-hydroxypentadecanoic acid, ω -Hydroxyheptadecanoic acid, ω-hydroxyeicosanoic acid, ω-hydroxydocosanoic acid, 6-hydroxyoctadecanoic acid, ricinoleic acid, 12-hydroxystearic acid, [R-(E)]-12-hydroxy-9 -Octadecenoic acid, etc. Among these, hydroxy fatty acids having 4 to 18 carbon atoms and one hydroxyl group other than the ω-position (particularly the 12-position) are preferred, and ricinoleic acid and 12-hydroxystearic acid are more preferred. Each of the fatty acids and hydroxy fatty acids may be used singly or in combination of two or more.
銀粒子において、脂肪酸やヒドロキシ脂肪酸の付着量についても、アミン化合物と同様、適宜調整する。具体的な脂肪酸やヒドロキシ脂肪酸の付着量は、特に制限されないが、銀粒子の質量を１００質量％として、好ましくは１．５質量％以下、より好ましくは１．３質量％以下であり、下限については、好ましくは０．０１質量％以上である。同様に、銀粒子Ａ、Ｂの脂肪酸やヒドロキシ脂肪酸の付着量についても、それぞれ銀粒子Ａ、Ｂの質量を１００質量％として、好ましくは１．５質量％以下、より好ましくは１．３質量％以下であり、下限については、好ましくは０．０１質量％以上である。銀粒子に付着している脂肪酸、ヒドロキシ脂肪酸の含有量は示差熱分析により測定することができる。 In the silver particles, the amount of fatty acid or hydroxy fatty acid attached is also adjusted as appropriate, similarly to the amine compound. The amount of attached fatty acids and hydroxy fatty acids is not particularly limited, but is preferably 1.5% by mass or less, more preferably 1.3% by mass or less, based on the mass of silver particles as 100% by mass, and the lower limit is is preferably 0.01% by mass or more. Similarly, the amount of fatty acids and hydroxy fatty acids attached to silver particles A and B is preferably 1.5% by mass or less, more preferably 1.3% by mass, assuming the mass of silver particles A and B as 100% by mass. The lower limit is preferably 0.01% by mass or more. The content of fatty acids and hydroxy fatty acids attached to silver particles can be measured by differential thermal analysis.
なお、アミン化合物、脂肪酸、ヒドロキシ脂肪酸は、併用してもよいし、また、これらとは異なる他の化合物が銀粒子の表面に付着していてもよい。銀粒子の表面には、アミン化合物が付着していることが特に好ましい。 Note that the amine compound, fatty acid, and hydroxy fatty acid may be used in combination, or other compounds different from these may be attached to the surface of the silver particles. It is particularly preferable that an amine compound is attached to the surface of the silver particles.
銀粒子の製造方法
銀粒子の製造方法の一例を以下に示す。
Method for producing silver particles An example of a method for producing silver particles is shown below.
まず、銀粒子を製造するための組成物（銀粒子調製用組成物）を用意する。具体的には、銀粒子の原料となる銀化合物と、必要に応じて、銀粒子の表面に付着させるアミン化合物などや、溶媒を準備する。本発明の効果をより一層好適に奏する観点から、好ましい銀化合物としては、硝酸銀、シュウ酸銀等が挙げられ、特にシュウ酸銀が好ましい。なお、溶媒としては、後述の組成物に配合される溶媒として例示したものと同じものが例示される。次に、これらの各成分を混合して銀粒子調製用組成物を得る。当該組成物における各成分の割合は、適宜調整する。例えば、組成物中のシュウ酸銀の含有量は、組成物の全量に対して、２０～７０質量％程度とすることが好ましい。また、銀粒子の表面にアミン化合物を付着させる場合であれば、アミン化合物の含有量としては、組成物の全量に対して、５質量％～５５質量％程度とすることが好ましい。また、銀粒子の表面に脂肪酸を付着させる場合であれば、脂肪酸の含有量としては、組成物の全量に対して、０．１質量％～２０質量％程度とすることが好ましい。銀粒子の表面にヒドロキシ脂肪酸を付着させる場合であれば、ヒドロキシ脂肪酸の含有量としては、組成物の全量に対して、０．１質量％～１５質量％程度とすることが好ましい。 First, a composition for producing silver particles (silver particle preparation composition) is prepared. Specifically, a silver compound serving as a raw material for silver particles, and if necessary, an amine compound to be attached to the surface of the silver particles and a solvent are prepared. From the viewpoint of achieving the effects of the present invention even more favorably, preferred silver compounds include silver nitrate, silver oxalate, and the like, with silver oxalate being particularly preferred. In addition, as a solvent, the same thing as what was illustrated as a solvent mix|blended with the below-mentioned composition is illustrated. Next, these components are mixed to obtain a composition for preparing silver particles. The proportion of each component in the composition is adjusted as appropriate. For example, the content of silver oxalate in the composition is preferably about 20 to 70% by mass based on the total amount of the composition. Further, when an amine compound is attached to the surface of the silver particles, the content of the amine compound is preferably about 5% by mass to 55% by mass based on the total amount of the composition. Further, when fatty acids are attached to the surface of silver particles, the content of fatty acids is preferably about 0.1% by mass to 20% by mass based on the total amount of the composition. When hydroxy fatty acids are attached to the surface of silver particles, the content of hydroxy fatty acids is preferably about 0.1% by mass to 15% by mass based on the total amount of the composition.
なお、アミン化合物などの含有量が前記範囲外となるように調整した銀粒子調製用組成物を用いて、一旦、銀粒子を合成し、後述する方法によって、アミン化合物などの種類や付着量を前記物性となるように調整（アミン化合物を置換）することも可能である。 Note that silver particles are first synthesized using a composition for preparing silver particles whose content of amine compounds is adjusted to be outside the above range, and then the type and amount of amine compounds are determined by the method described below. It is also possible to adjust (substitute an amine compound) so as to have the above-mentioned physical properties.
また、各成分の混合手段も特に制限されず、例えば、メカニカルスタ－ラ－、マグネティックスタ－ラ－、ボルテックスミキサ－、遊星ミル、ボ－ルミル、三本ロ－ル、ラインミキサ－、プラネタリ－ミキサ－、ディゾルバ－等の汎用の装置で混合できる。混合時の溶解熱、摩擦熱等の影響で組成物の温度が上昇し、銀粒子の熱分解反応が開始することを回避するために、組成物の温度を、例えば６０℃以下、特に４０℃以下に抑えながら混合することが好ましい。 Furthermore, the means for mixing each component is not particularly limited, and examples include a mechanical stirrer, magnetic stirrer, vortex mixer, planetary mill, ball mill, three-roll mill, line mixer, and planetary mixer. Can be mixed with general-purpose equipment such as mixers and dissolvers. In order to avoid that the temperature of the composition increases due to the effects of heat of dissolution, frictional heat, etc. during mixing and starts a thermal decomposition reaction of the silver particles, the temperature of the composition is set to, for example, 60°C or lower, particularly 40°C. It is preferable to mix while keeping the amount below.
次に、銀粒子調製用組成物を、反応容器内で反応、通常は加熱による反応に供することにより、銀化合物の熱分解反応が起こり、銀粒子が生成する。反応に当たっては、予め加熱しておいた反応容器内に組成物を導入してもよく、組成物を反応容器内に導入した後に加熱してもよい。 Next, the composition for preparing silver particles is subjected to a reaction, usually a reaction by heating, in a reaction container, whereby a thermal decomposition reaction of the silver compound occurs and silver particles are generated. In the reaction, the composition may be introduced into a reaction vessel that has been heated in advance, or the composition may be heated after being introduced into the reaction vessel.
反応温度は、熱分解反応が進行し、銀粒子が生成する温度であればよく、例えば５０～２５０℃程度が挙げられる。また、反応時間は、所望する平均粒子径の大きさや、それに応じた組成物の組成に合せて、適宜選択すればよい。反応時間としては、例えば１分間～１００時間が挙げられる。 The reaction temperature may be any temperature at which the thermal decomposition reaction proceeds and silver particles are produced, and examples thereof include about 50 to 250°C. Further, the reaction time may be appropriately selected depending on the desired average particle diameter and the composition of the composition accordingly. The reaction time is, for example, 1 minute to 100 hours.
熱分解反応により生成した銀粒子は、未反応原料を含む混合物として得られるため、銀粒子を精製することが好ましい。精製方法としては、固液分離方法、銀粒子と有機溶媒等の未反応原料との比重差を利用した沈殿方法等が挙げられる。固液分離方法としては、フィルタ－濾過、遠心分離、サイクロン式、又はデカンタ等の方法が挙げられる。精製時の取り扱いを容易にするために、アセトン、メタノ－ル等の低沸点溶媒で銀粒子を含有する混合物を希釈して、その粘度を調整してもよい。 Since the silver particles produced by the thermal decomposition reaction are obtained as a mixture containing unreacted raw materials, it is preferable to refine the silver particles. Examples of purification methods include solid-liquid separation methods and precipitation methods that utilize the difference in specific gravity between silver particles and unreacted raw materials such as organic solvents. Examples of the solid-liquid separation method include methods such as filter filtration, centrifugation, cyclone method, and decanter method. To facilitate handling during purification, the mixture containing silver particles may be diluted with a low boiling point solvent such as acetone or methanol to adjust its viscosity.
銀粒子製造用組成物の組成や反応条件を調整することにより、得られる銀粒子の平均粒子径を調整することができる。 By adjusting the composition and reaction conditions of the composition for producing silver particles, the average particle diameter of the resulting silver particles can be adjusted.
銀粒子表面のアミン化合物を置換・調整する方法
前記の方法で、一旦合成された銀粒子（表面にアミン化合物が付着）を用意し、これを溶媒中に分散させる。溶媒としては、後述の組成物に配合される溶媒として例示したものと同じものが例示される。次に、他のアミン化合物を銀粒子の質量に対して、０．１～５倍量の範囲で添加し、室温～８０℃で、１分～２４時間撹拌を行う工程に付することで、銀粒子の表面に付着しているアミン化合物の種類を置換したり、付着量を調整することができる。アミン化合物を置換した銀粒子は、前記の固液分離法などによって回収することができる。
Method for substituting and adjusting amine compounds on the surface of silver particles Silver particles (with an amine compound attached to the surface) that have been synthesized by the method described above are prepared and dispersed in a solvent. Examples of the solvent include the same solvents as those exemplified as solvents to be added to the composition described below. Next, by adding another amine compound in an amount of 0.1 to 5 times the mass of the silver particles and stirring at room temperature to 80°C for 1 minute to 24 hours, The type of amine compound attached to the surface of the silver particles can be replaced or the amount attached can be adjusted. Silver particles substituted with an amine compound can be recovered by the solid-liquid separation method described above.
本発明の焼結体を製造するにあたり、銀粒子と溶媒の組成物を用いることにより、銀粒子の流動性が高まり、銀粒子を所望の場所に配置しやすくなる。 When producing the sintered body of the present invention, the use of a composition of silver particles and a solvent increases the fluidity of the silver particles, making it easier to arrange the silver particles at desired locations.
溶媒としては、銀粒子を分散できるものであれば、特に制限されないが、極性有機溶媒を含むことが好ましい。極性有機溶媒としては、アセトン、アセチルアセトン、メチルエチルケトン等のケトン類；ジエチルエ－テル、ジプロピルエ－テル、ジブチルエ－テル、テトラヒドロフラン、１，４－ジオキサン等のエ－テル類；１，２－プロパンジオ－ル、１，２－ブタンジオ－ル、１，３－ブタンジオ－ル、１，４－ブタンジオ－ル、２，３－ブタンジオ－ル、１，２－ヘキサンジオ－ル、１，６－ヘキサンジオ－ル、１，２－ペンタンジオ－ル、１，５－ペンタンジオ－ル、２－メチル－２，４－ペンタンジオ－ル、３－メチル－１，５－ペンタンジオ－ル、１，２－オクタンジオ－ル、１，８－オクタンジオ－ル、２－エチル－１，３－ヘキサンジオ－ル等のジオ－ル類；グリセロ－ル；炭素数１～５の直鎖又は分岐鎖のアルコ－ル、シクロヘキサノ－ル、３－メトキシ－３－メチル－１－ブタノ－ル、３－メトキシ－１－ブタノ－ル等のアルコ－ル類；酢酸エチル、酢酸ブチル、酪酸エチル、蟻酸エチル、テキサノール等の脂肪酸エステル類；ポリエチレングリコ－ル、トリエチレングリコ－ルモノメチルエ－テル、テトラエチレングリコ－ルモノメチルエ－テル、エチレングリコ－ルモノエチルエ－テル、ジエチレングリコ－ルモノエチルエ－テル、ジエチレングリコ－ルジメチルエ－テル、トリエチレングリコ－ルジメチルエ－テル、テトラエチレングリコ－ルジメチルエ－テル、３－メトキシブチルアセテ－ト、エチレングリコ－ルモノブチルエ－テル、エチレングリコ－ルモノブチルエ－テルアセテ－ト、エチレングリコ－ルモノヘキシルエ－テル、エチレングリコ－ルモノオクチルエ－テル、エチレングリコ－ルモノ－２－エチルヘキシルエ－テル、エチレングリコ－ルモノベンジルエ－テル、ジエチレングリコ－ルモノメチルエ－テル、ジエチレングリコ－ルモノメチルエ－テルアセテ－ト、ジエチレングリコ－ルモノエチルエ－テル、ジエチレングリコ－ルモノエチルエ－テルアセテ－ト、ジエチレングリコ－ルモノブチルエ－テル、ジエチレングリコ－ルモノブチルエ－テルアセテ－ト、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノ－２－エチルヘキシルエーテル、ポリプロピレングリコ－ル、プロピレングリコ－ルモノプロピルエ－テル、プロピレングリコ－ルモノブチルエ－テル、ジプロピレングリコ－ルモノメチルエ－テル、ジプロピレングリコ－ルモノエチルエ－テル、ジプロピレングリコ－ルモノプロピルエ－テル、ジプロピレングリコ－ルモノブチルエ－テル、トリプロピレングリコ－ルモノメチルエ－テル、トリプロピレングリコ－ルモノエチルエ－テル、トリプロピレングリコ－ルモノプロピルエ－テル、トリプロピレングリコ－ルモノブチルエ－テル等のグリコ－ル又はグリコ－ルエ－テル類；Ｎ，Ｎ－ジメチルホルムアミド；ジメチルスルホキシド；テルピネオ－ル等のテルペン類；アセトニトリル；γ－ブチロラクトン；２－ピロリドン；Ｎ－メチルピロリドン；Ｎ－（２－アミノエチル）ピペラジン等が挙げられる。これらの中でも、本発明の効果をより一層好適に奏する観点から、炭素数３～５の直鎖又は分岐鎖のアルコ－ル、３－メトキシ－３－メチル－１－ブタノ－ル、３－メトキシ－１－ブタノ－ル、ジエチレングリコ－ルモノブチルエ－テル、ジエチレングリコ－ルモノブチルエ－テルアセテ－ト、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノ－２－エチルヘキシルエーテル、テルピネオ－ル、テキサノールが好ましい。 The solvent is not particularly limited as long as it can disperse silver particles, but preferably includes a polar organic solvent. Examples of polar organic solvents include ketones such as acetone, acetylacetone, and methyl ethyl ketone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, and 1,4-dioxane; and 1,2-propanediol. , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,6-hexanediol, 1 , 2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8 -Diols such as octanediol and 2-ethyl-1,3-hexanediol; glycerol; linear or branched alcohols having 1 to 5 carbon atoms, cyclohexanol, 3- Alcohols such as methoxy-3-methyl-1-butanol and 3-methoxy-1-butanol; Fatty acid esters such as ethyl acetate, butyl acetate, ethyl butyrate, ethyl formate, and texanol; polyethylene glycol triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether -ter, 3-methoxybutyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether, ethylene glycol monooctyl ether, ethylene glycol mono- 2-ethylhexyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, polypropylene glycol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether Glycols or glycol ethers such as ester, tripropylene glycol monobutyl ether; N,N-dimethylformamide; dimethyl sulfoxide; terpenes such as terpineol; acetonitrile; γ-butyrolactone; 2-pyrrolidone; Examples include N-methylpyrrolidone; N-(2-aminoethyl)piperazine and the like. Among these, from the viewpoint of achieving the effects of the present invention even more favorably, linear or branched alcohols having 3 to 5 carbon atoms, 3-methoxy-3-methyl-1-butanol, 3-methoxy Preferred are -1-butanol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, terpineol, and texanol.
溶媒は、極性有機溶媒に加えて、さらに非極性又は疎水性溶媒を含んでいてもよい。非極性有機溶媒としては、ヘキサン、ヘプタン、オクタン、ノナン、デカン、２－エチルヘキサン、シクロヘキサン等の直鎖、分枝、又は環状の飽和炭化水素；炭素数６以上の直鎖又は分岐鎖のアルコ－ル等のアルコ－ル類；ベンゼン、トルエン、ベンゾニトリル等の芳香族化合物；ジクロロメタン、クロロホルム、ジクロロエタン等のハロゲン化炭化水素類；メチル－ｎ－アミルケトン；メチルエチルケトンオキシム；トリアセチン等が挙げられる。これらの中でも、飽和炭化水素及び炭素数６以上の直鎖又は分岐鎖のアルコ－ル類が好ましく、ヘキサン、オクタン、デカン、オクタノ－ル、デカノ－ル、ドデカノ－ルがより好ましい。溶媒は、１種を単独で、又は２種以上を混合して使用できる。 In addition to the polar organic solvent, the solvent may further include a nonpolar or hydrophobic solvent. Examples of non-polar organic solvents include linear, branched, or cyclic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, 2-ethylhexane, and cyclohexane; linear or branched alcohols having 6 or more carbon atoms; Examples include alcohols such as alcohol; aromatic compounds such as benzene, toluene, and benzonitrile; halogenated hydrocarbons such as dichloromethane, chloroform, and dichloroethane; methyl-n-amyl ketone; methyl ethyl ketone oxime; and triacetin. Among these, saturated hydrocarbons and linear or branched alcohols having 6 or more carbon atoms are preferred, and hexane, octane, decane, octanol, decanol, and dodecanol are more preferred. One type of solvent can be used alone or two or more types can be used in combination.
極性有機溶媒と非極性有機溶媒との双方を含む場合、極性有機溶媒の比率は、溶媒の全量に対して、５容量％以上が好ましく、１０容量％以上がより好ましく、１５容量％以上がさらにより好ましい。また、６０容量％以下とすることができ、５５容量％以下とすることもでき、５０容量％以下とすることもできる。溶媒は極性有機溶媒のみからなるものとすることもできる。銀粒子と溶媒を含む組成物は、このように極性有機溶媒を多く含む場合にも、銀粒子の分散性が良い。 When both a polar organic solvent and a non-polar organic solvent are included, the ratio of the polar organic solvent is preferably 5% by volume or more, more preferably 10% by volume or more, and further preferably 15% by volume or more, based on the total amount of the solvent. More preferred. Moreover, it can be set to 60 volume% or less, it can also be set to 55 volume% or less, and it can also be set to 50 volume% or less. The solvent can also consist solely of polar organic solvents. The composition containing silver particles and a solvent has good dispersibility of the silver particles even when it contains a large amount of polar organic solvent.
銀粒子と溶媒を含む組成物において、溶媒の割合としては、特に制限されないが、２０質量％以下が好ましく、５質量％～１５質量％程度がより好ましい。 In a composition containing silver particles and a solvent, the proportion of the solvent is not particularly limited, but is preferably 20% by mass or less, and more preferably about 5% by mass to 15% by mass.
銀粒子と溶媒を含む組成物に含まれる銀粒子の含有量は、好ましくは８０質量％以上、より好ましくは８５質量％以上である。 The content of silver particles contained in the composition containing silver particles and a solvent is preferably 80% by mass or more, more preferably 85% by mass or more.
銀粒子と溶媒を含む組成物は、銀粒子と溶媒を混合する工程を備える方法により製造することができる。 A composition containing silver particles and a solvent can be manufactured by a method including a step of mixing silver particles and a solvent.
また、銀粒子を含む組成物においては、前述の銀粒子の製造方法において、溶媒中に生成された銀粒子を、溶媒と共に当該組成物としてもよい。 Moreover, in the composition containing silver particles, the silver particles produced in the solvent in the above-mentioned method for producing silver particles may be used together with the solvent in the composition.
本発明の焼結体の製造方法においては、銀粒子の表面に付着している成分（アミン化合物など）や溶媒は、焼結の際の高熱により、ほとんどが離脱しており、本発明の焼結体は、実質的に銀により構成されている。 In the method for producing a sintered body of the present invention, most of the components (amine compounds, etc.) and solvents attached to the surface of the silver particles are removed due to the high heat during sintering, and the sintered body of the present invention The body consists essentially of silver.
焼結温度としては、特に制限されないが、低温において好適に焼結させつつ、得られる焼結体のせん断強度及び緻密度を高める観点から、例えば２５０℃以下、好ましくは１５０℃～２５０℃程度、より好ましくは２００℃～２５０℃程度が挙げられる。同様の観点から、焼結時間としては、好ましくは０．４時間～２．０時間程度、より好ましくは０．５時間～１．２時間程度が挙げられる。本発明の焼結体の製造方法において、銀粒子が、平均粒子径が５０～５００ｎｍの範囲である銀粒子Ａと、平均粒子径が０．５～５．５μｍの範囲である銀粒子Ｂとを含み、銀粒子Ｂの平均粒子径は、銀粒子Ａの平均粒子径の５～１１倍の関係を充足する特徴を備えていることにより、銀粒子の焼結の際に加圧しなくとも、２５０℃以下の低温において好適に焼結され、前記所定の緻密度及び空隙を有する本発明の焼結体が好適に形成される。よって、銀粒子の焼結の際に加圧する必要は無い。即ち、本発明の焼結体は、銀粒子の焼結時に無加圧が求められる用途に好適に用いることができる。なお、本発明の焼結体の製造時に加圧してもよく、加圧する場合の圧力は例えば１０～３０ＭＰａ程度である。焼結は、大気、不活性ガス（窒素ガス、アルゴンガス）等の雰囲気下で行うことができる。焼結手段としては、特に制限されず、オ－ブン、熱風式乾燥炉、赤外線乾燥炉、レ－ザ－照射、フラッシュランプ照射、マイクロウェ－ブ等が挙げられる。 The sintering temperature is not particularly limited, but from the viewpoint of increasing the shear strength and compactness of the obtained sintered body while suitably sintering at a low temperature, for example, 250°C or less, preferably about 150°C to 250°C, More preferably, the temperature is about 200°C to 250°C. From the same viewpoint, the sintering time is preferably about 0.4 hours to 2.0 hours, more preferably about 0.5 hours to 1.2 hours. In the method for producing a sintered body of the present invention, the silver particles are silver particles A having an average particle size in the range of 50 to 500 nm, and silver particles B having an average particle size in the range of 0.5 to 5.5 μm. The average particle diameter of silver particles B satisfies the relationship of 5 to 11 times the average particle diameter of silver particles A, so that the silver particles can be sintered without applying pressure. The sintered body of the present invention is preferably sintered at a low temperature of 250° C. or lower, and has the predetermined density and voids. Therefore, there is no need to apply pressure when sintering the silver particles. That is, the sintered body of the present invention can be suitably used in applications where no pressure is required during sintering of silver particles. Note that pressure may be applied during production of the sintered body of the present invention, and the pressure when pressurized is, for example, about 10 to 30 MPa. Sintering can be performed in an atmosphere such as the air or an inert gas (nitrogen gas, argon gas). Sintering means are not particularly limited, and include ovens, hot air drying ovens, infrared drying ovens, laser irradiation, flash lamp irradiation, microwaves, and the like.
３．電子部品
本発明の電子部品は、本発明の焼結体により部材間が接着された部分を備えている。すなわち、本発明の電子部品は、前述の銀粒子を、電子部品の部材間（例えば、回路に含まれる部材間）に配置し、銀粒子を焼結させて、部材間を接着することで好適に製造することができる。
3. Electronic Component The electronic component of the present invention includes a portion in which members are bonded together using the sintered body of the present invention. That is, the electronic component of the present invention can be produced by arranging the silver particles described above between members of the electronic component (for example, between members included in a circuit), sintering the silver particles, and bonding the members. can be manufactured.
前述の通り、本発明の焼結体は、緻密度が高いことから、これを備える電子部品においても、焼結体の緻密度が高い。また、本発明の電子部品の比抵抗値についても低いものとすることができる。 As described above, since the sintered body of the present invention has a high density, the sintered body also has a high density in an electronic component including the same. Moreover, the specific resistance value of the electronic component of the present invention can also be made low.
以下の実施例において本発明をより具体的に説明するが、本発明はこれらに限定されない。 The present invention will be explained in more detail in the following examples, but the present invention is not limited thereto.
実施例及び比較例において使用した各成分の詳細は、以下の通りである。
・シュウ酸銀（（ＣＯＯＡｇ）2）は、特許第５５７４７６１号公報に記載の方法で合成した。
・Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパン（富士フイルム和光純薬株式会社製）
・ｎ－ヘキシルアミン（炭素数６、富士フイルム和光純薬株式会社製）
・リシノ－ル酸（東京化成工業株式会社製）
・１－ブタノ－ル（富士フイルム和光純薬株式会社製）
・メタノ－ル（富士フイルム和光純薬株式会社製）
・エチレングリコ－ル（富士フイルム和光純薬株式会社製）
・テキサノール（富士フイルム和光純薬株式会社製）
Details of each component used in Examples and Comparative Examples are as follows.
- Silver oxalate ((COOAg) 2 ) was synthesized by the method described in Japanese Patent No. 5574761.
・N,N-diethyl-1,3-diaminopropane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・n-hexylamine (6 carbon atoms, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Ricinoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
・1-Butanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Ethylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Texanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
＜銀粒子Ａの合成＞
（１）銀粒子Ａ１（平均粒子径６８ｎｍ）
磁気撹拌子を入れた５０ｍＬガラス製遠沈管に、リシノ－ル酸（２．３４ｇ）、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパン（２０３ｇ）、及び１－ブタノ－ル（３７５ｇ）を投入し、１分間程度攪拌したのち、シュウ酸銀（２５０ｇ）を投入し、約１０分間攪拌することで、銀粒子Ａ１調製用組成物を得た。その後、アルミブロックを備えたホットスタ－ラ－（小池精密機器製作所製ＨＨＥ－１９Ｇ－Ｕ）上に、これらのガラス製遠沈管を立てて設置し、４０℃で３０分間攪拌し、さらに、９０℃で３０分間攪拌した。放冷後、磁気撹拌子を取り出し、各組成物にメタノ－ル１５ｇを添加してボルテックスミキサ－で攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノ－ル１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、銀粒子を回収した。
<Synthesis of silver particles A>
(1) Silver particles A1 (average particle diameter 68 nm)
Ricinoleic acid (2.34 g), N,N-diethyl-1,3-diaminopropane (203 g), and 1-butanol (375 g) were placed in a 50 mL glass centrifuge tube containing a magnetic stir bar. After stirring for about 1 minute, silver oxalate (250 g) was added and stirred for about 10 minutes to obtain a composition for preparing silver particles A1. Thereafter, these glass centrifuge tubes were placed upright on a hot stirrer (HHE-19G-U manufactured by Koike Precision Instruments Co., Ltd.) equipped with an aluminum block, stirred at 40°C for 30 minutes, and further stirred at 90°C. The mixture was stirred for 30 minutes. After cooling, the magnetic stirrer was taken out, 15 g of methanol was added to each composition, and the mixture was stirred with a vortex mixer. A centrifugation operation was performed for 1 minute, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifugation, and removing the supernatant were repeated twice to collect silver particles.
次に、得られた銀粒子の分散液（メタノ－ル溶液）を用いて、ｎ－ヘキシルアミンを銀粒子の質量の３倍量を添加し、室温で４時間撹拌した。撹拌後、磁気撹拌子を取り出し、各組成物にメタノ－ル１５ｇを添加してボルテックスミキサ－で攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノ－ル１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、銀粒子の表面に付着しているＮ，Ｎ－ジエチル－１，３－ジアミノプロパンをｎ－ヘキシルアミンに置換した銀粒子Ａ１（平均粒子径６８ｎｍ）を回収した。 Next, using the obtained silver particle dispersion (methanol solution), n-hexylamine was added in an amount three times the mass of the silver particles, and the mixture was stirred at room temperature for 4 hours. After stirring, take out the magnetic stirring bar, add 15 g of methanol to each composition, stir with a vortex mixer, and then centrifuge (CF7D2 manufactured by Hitachi Koki) at 3000 rpm (approximately 1600 x G) for 1 minute. A centrifugation operation was performed, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifugation, and removing the supernatant were repeated twice to replace N,N-diethyl-1,3-diaminopropane attached to the surface of the silver particles with n-hexylamine. Silver particles A1 (average particle diameter 68 nm) were recovered.
（２）銀粒子Ａ２（平均粒子径１８１ｎｍ）
磁気撹拌子を入れた５０ｍＬガラス製遠沈管に、リシノ－ル酸（６．２５ｇ）、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパン（２０３ｇ）、及び１－ブタノ－ル（１８７．５ｇ）を投入し、１分間程度攪拌したのち、シュウ酸銀（２５０ｇ）を投入し、約１０分間攪拌することで、銀粒子Ａ１調製用組成物を得た。その後、アルミブロックを備えたホットスタ－ラ－（小池精密機器製作所製ＨＨＥ－１９Ｇ－Ｕ）上に、これらのガラス製遠沈管を立てて設置し、４０℃で３０分間攪拌し、さらに、９０℃で３０分間攪拌した。放冷後、磁気撹拌子を取り出し、各組成物にメタノ－ル１５ｇを添加してボルテックスミキサ－で攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノ－ル１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、銀粒子を回収した。
(2) Silver particles A2 (average particle diameter 181 nm)
Ricinoleic acid (6.25 g), N,N-diethyl-1,3-diaminopropane (203 g), and 1-butanol (187.5 g) were placed in a 50 mL glass centrifuge tube containing a magnetic stir bar. was added and stirred for about 1 minute, then silver oxalate (250 g) was added and stirred for about 10 minutes to obtain a composition for preparing silver particles A1. Thereafter, these glass centrifuge tubes were placed upright on a hot stirrer (HHE-19G-U manufactured by Koike Precision Instruments Co., Ltd.) equipped with an aluminum block, stirred at 40°C for 30 minutes, and further stirred at 90°C. The mixture was stirred for 30 minutes. After cooling, the magnetic stirrer was taken out, 15 g of methanol was added to each composition, and the mixture was stirred with a vortex mixer. A centrifugation operation was performed for 1 minute, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifugation, and removing the supernatant were repeated twice to collect silver particles.
次に、得られた銀粒子の分散液（メタノ－ル溶液）を用いて、ｎ－ヘキシルアミンを銀粒子の質量の３倍量を添加し、室温で４時間撹拌した。撹拌後、磁気撹拌子を取り出し、各組成物にメタノ－ル１５ｇを添加してボルテックスミキサ－で攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノ－ル１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパンをｎ－ヘキシルアミンに置換した銀粒子Ａ２（平均粒子径１８１ｎｍ）を回収した。 Next, using the obtained silver particle dispersion (methanol solution), n-hexylamine was added in an amount three times the mass of the silver particles, and the mixture was stirred at room temperature for 4 hours. After stirring, take out the magnetic stirring bar, add 15 g of methanol to each composition, stir with a vortex mixer, and then centrifuge (CF7D2 manufactured by Hitachi Koki) at 3000 rpm (approximately 1600 x G) for 1 minute. A centrifugation operation was performed, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifugation, and removing the supernatant were repeated twice to obtain silver particles A2 (average particle size 181 nm) in which N,N-diethyl-1,3-diaminopropane was replaced with n-hexylamine. ) were collected.
＜銀粒子Ｂ＞
・銀粒子Ｂ１（平均粒子径０．６５μｍ）として、ＤＯＷＡエレクトロニクス株式会社製の製品名ＡＧ２－１Ｃを用いた。
・銀粒子Ｂ２（平均粒子径１．８８μｍ）として、ＤＯＷＡエレクトロニクス株式会社製の製品名ＡＧ３－１Ｆを用いた。
・銀粒子Ｂ３（平均粒子径２．２１μｍ）として、ＤＯＷＡエレクトロニクス株式会社製の製品名ＡＧ４－８Ｆを用いた。
<Silver particles B>
- As silver particles B1 (average particle diameter 0.65 μm), product name AG2-1C manufactured by DOWA Electronics Co., Ltd. was used.
- As silver particles B2 (average particle diameter 1.88 μm), product name AG3-1F manufactured by DOWA Electronics Co., Ltd. was used.
- As silver particles B3 (average particle diameter 2.21 μm), product name AG4-8F manufactured by DOWA Electronics Co., Ltd. was used.
銀粒子Ａ１，Ａ２，Ｂ１，Ｂ２，Ｂ３について、それぞれ、走査型電子顕微鏡による観察（ＳＥＭ画像の取得）、平均粒子径（体積基準平均粒子径）の測定、粒度分布の測定、ＴＧ－ＤＴＡの測定を以下の条件にて行った。 Regarding silver particles A1, A2, B1, B2, and B3, observation using a scanning electron microscope (obtaining SEM images), measurement of average particle diameter (volume-based average particle diameter), measurement of particle size distribution, and measurement of TG-DTA were performed. Measurements were conducted under the following conditions.
＜電子顕微鏡による観察＞
銀粒子Ａ１，Ａ２，Ｂ１，Ｂ２，Ｂ３について、それぞれ、走査型電子顕微鏡（ＳＥＭ（日本電子製ＪＳＭ－ＩＴ５００ＨＲ））を用いて、ＳＥＭ画像を取得した。それぞれ、図１に銀粒子Ａ１のＳＥＭ画像、図２に銀粒子Ａ２のＳＥＭ画像、図３に銀粒子Ｂ１のＳＥＭ画像、図４に銀粒子Ｂ２のＳＥＭ画像、及び図５に銀粒子Ｂ３のＳＥＭ画像を示す。
<Observation using an electron microscope>
SEM images were obtained for each of silver particles A1, A2, B1, B2, and B3 using a scanning electron microscope (SEM (JSM-IT500HR manufactured by JEOL Ltd.)). FIG. 1 shows a SEM image of silver particle A1, FIG. 2 shows a SEM image of silver particle A2, FIG. 3 shows a SEM image of silver particle B1, FIG. 4 shows a SEM image of silver particle B2, and FIG. 5 shows a SEM image of silver particle B3. A SEM image is shown.
＜平均粒子径（体積基準平均粒子径）及び粒度分布（Ｄ１０～Ｄ１００）の測定＞
前記＜電子顕微鏡による観察＞で取得した各ＳＥＭ画像（横幅１～２０μｍ）について、画像解析ソフト（マックビュ－（マウンテック社製））を用いて、無作為に選択した２００個の粒子の体積基準平均粒子径及び粒度分布を測定した。ＳＥＭ画像の縦方向については、横幅１～２０μｍの範囲を観察する。なお、ＳＥＭ画像の縦方向については、横幅１～２０μｍの範囲に２００個以上（通常、２００～３００個程度）の銀粒子が含まれる幅とする。なお、体積基準平均粒子径は、ＳＥＭ画像に観察される粒子が、その直径を有する球形であると仮定して測定される値である。結果を表１及び表２に示す。
<Measurement of average particle diameter (volume-based average particle diameter) and particle size distribution (D10 to D100)>
For each SEM image (width 1 to 20 μm) obtained in the above <observation using an electron microscope>, the volume-based average of 200 randomly selected particles was calculated using image analysis software (Macview (manufactured by Mountec)). Particle size and particle size distribution were measured. Regarding the vertical direction of the SEM image, a horizontal width range of 1 to 20 μm is observed. Note that in the vertical direction of the SEM image, the width is such that 200 or more (usually about 200 to 300) silver particles are included in the width range of 1 to 20 μm. Note that the volume-based average particle diameter is a value measured on the assumption that the particles observed in the SEM image are spherical with that diameter. The results are shown in Tables 1 and 2.
＜熱重量示差熱分析（ＴＧ－ＤＴＡの測定）＞
銀粒子Ａ１，Ａ２各々についてのＴＧ－ＤＴＡを用いて測定した。具体的には、まず、後述の＜導電性接着剤の製造＞と同様にして、銀粒子Ａ１及び銀粒子Ａ２に対して、それぞれ、溶媒（テキサノ－ル）を混合して、濃度が９０質量％の各銀粒子分散液を調製した。次に、各銀粒子分散液１ｇに対し、メタノ－ル２ｇを加えてよく分散させたのち、銀粒子をろ取、風乾して銀粒子乾燥粉末を得た。得られた銀粒子乾燥粉末のＴＧ－ＤＴＡを、ＨＩＴＡＣＨＩ Ｇ３００ ＡＳＴ－２で測定した。測定条件は、雰囲気：空気、測定温度：３０～５００℃、昇温速度：１０℃／ｍｉｎとした。得られたＴＧ－ＤＴＡチャ－トから、熱分析によって３０℃から５００℃まで加熱したときの重量減少率を得た。結果を表３に示す。
<Thermogravimetric differential thermal analysis (TG-DTA measurement)>
Measurements were made using TG-DTA for each of silver particles A1 and A2. Specifically, first, in the same manner as in <Manufacture of conductive adhesive> described below, a solvent (Texanol) is mixed with silver particles A1 and silver particles A2, respectively, so that the concentration is 90% by mass. % of each silver particle dispersion was prepared. Next, 2 g of methanol was added to 1 g of each silver particle dispersion and the particles were well dispersed, and then the silver particles were collected by filtration and air-dried to obtain a dry silver particle powder. TG-DTA of the obtained dry silver particle powder was measured using HITACHI G300 AST-2. The measurement conditions were: atmosphere: air, measurement temperature: 30 to 500°C, and temperature increase rate: 10°C/min. From the obtained TG-DTA chart, the weight loss rate when heated from 30°C to 500°C was determined by thermal analysis. The results are shown in Table 3.
また、銀粒子Ａ１及び銀粒子Ａ２に対して、それぞれ、溶媒（テキサノ－ル）を混合して、濃度が９０質量％の各銀粒子分散液を調製した。各銀粒子分散液をＴＧ－ＤＴＡ分析における主な発熱ピ－クの測定に用いて、ＨＩＴＡＣＨＩ Ｇ３００ ＡＳＴ－２で測定した。測定条件は、雰囲気：空気、測定温度：３０～５００℃、昇温速度：１０℃／ｍｉｎとした。得られたＴＧ－ＤＴＡチャ－トを図６に示す。図６の各銀粒子の発熱ピークの温度を表３に表す。 Furthermore, silver particle dispersions having a concentration of 90% by mass were prepared by mixing a solvent (Texanol) with each of silver particles A1 and silver particles A2. Each silver particle dispersion was used to measure the main exothermic peak in TG-DTA analysis using HITACHI G300 AST-2. The measurement conditions were: atmosphere: air, measurement temperature: 30 to 500°C, and temperature increase rate: 10°C/min. The obtained TG-DTA chart is shown in FIG. Table 3 shows the temperature of the exothermic peak of each silver particle in FIG.
＜導電性接着剤の製造＞
表４に示される組成となるようにして、銀粒子Ａ、銀粒子Ｂ及び溶媒（テキサノ－ル）を混合して導電性接着剤を調製した。具体的には、はじめに、銀粒子Ａ１、銀粒子Ａ２、銀粒子Ｂ１、銀粒子Ｂ２、及び銀粒子Ｂ３のそれぞれについて、１０質量％相当のテキサノ－ルを添加して、濃度が９０質量％の各銀粒子分散液（それぞれ、銀粒子分散液Ａ１、銀粒子分散液Ａ２、銀粒子分散液Ｂ１、銀粒子分散液Ｂ２、及び銀粒子分散液Ｂ３）を調製した。混合には、クラボウ社製のマゼルスタ－を用い、２回撹拌優先モ－ドにて混合を行った。次に、表４に示される組成となるようにして、各銀粒子分散液及びテキサノ－ルを混合して、実施組成１－２，比較組成１－４の組成を備える各導電性接着剤を得た。
<Manufacture of conductive adhesive>
A conductive adhesive was prepared by mixing silver particles A, silver particles B, and a solvent (Texanol) so as to have the composition shown in Table 4. Specifically, first, texanol equivalent to 10% by mass was added to each of silver particles A1, silver particles A2, silver particles B1, silver particles B2, and silver particles B3, so that the concentration was 90% by mass. Each silver particle dispersion liquid (silver particle dispersion liquid A1, silver particle dispersion liquid A2, silver particle dispersion liquid B1, silver particle dispersion liquid B2, and silver particle dispersion liquid B3, respectively) was prepared. For mixing, a Mazel Star manufactured by Kurabo Industries, Ltd. was used, and the mixing was performed in the twice-stirring priority mode. Next, each silver particle dispersion liquid and Texanol were mixed so that the compositions shown in Table 4 were obtained, and each conductive adhesive having the composition of Example Composition 1-2 and Comparative Composition 1-4 was prepared. Obtained.
表４の銀粒子Ａ、銀粒子Ｂ、及び溶媒について記載された数値の単位は質量部である。なお、実施組成１－２及び比較組成１－４の導電性接着剤には、粒子の個数を１００％としたとき、粒径が５０ｎｍ未満の粒子が１０％以下含まれていた。５０ｎｍ未満の粒子の測定には、前記＜電子顕微鏡による観察＞で取得した各ＳＥＭ画像（横幅１～２０μｍ）について、画像解析ソフト（マックビュ－（マウンテック社製））を用いて、無作為に選択した２００個の粒子の体積粒子径を測定し、そこに含まれる個数割合を計算した。ＳＥＭ画像の縦方向については、横幅１～２０μｍの範囲に２００個以上の銀粒子が含まれる幅（１～２０μｍの範囲）とした。 The units of numerical values described for silver particles A, silver particles B, and solvent in Table 4 are parts by mass. Note that the conductive adhesives of the practical composition 1-2 and the comparative composition 1-4 contained 10% or less of particles with a particle size of less than 50 nm, when the number of particles was 100%. To measure particles smaller than 50 nm, each SEM image (width 1 to 20 μm) obtained in the above <observation using an electron microscope> was randomly selected using image analysis software (Macview (manufactured by Mountec)). The volume particle diameters of the 200 particles were measured, and the proportion of the particles contained therein was calculated. Regarding the vertical direction of the SEM image, the width was such that 200 or more silver particles were included in the width range of 1 to 20 μm (range of 1 to 20 μm).
＜焼結体（焼結温度２００℃）の製造＞
まず、銅板上に無電解銀めっきを０．５μｍ施した基材を準備した。基材の上（銀めっきが形成された表面）に導電性接着剤（銀粒子９０質量％、テキサノール１０質量％の銀粒子分散液）を塗膜厚みが５０μｍとなるように、均一に塗布した。さらに、塗膜の上に、裏面（導電性接着剤と接する面）に金めっきが施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を積層して積層体を得た。次に、乾燥器（循環式）を用い、得られた積層体を所定の焼結温度（２００℃又は２５０℃）で６０分間の焼結条件で加熱し、基材とシリコンウエハとの間の各導電性接着剤が焼結し、基材とシリコンウエハとが焼結体を介して接合された９個の積層体を得た。
<Manufacture of sintered body (sintering temperature 200°C)>
First, a base material having a copper plate plated with electroless silver plating to a thickness of 0.5 μm was prepared. A conductive adhesive (a silver particle dispersion containing 90% by mass of silver particles and 10% by mass of Texanol) was uniformly applied onto the base material (the surface on which silver plating was formed) so that the coating thickness was 50 μm. . Further, a silicon wafer (size 2 mm x 2 mm) whose back surface (the surface in contact with the conductive adhesive) was plated with gold was laminated on the coating film to obtain a laminate. Next, using a dryer (circulating type), the obtained laminate is heated at a predetermined sintering temperature (200°C or 250°C) for 60 minutes, and the sintering conditions between the base material and the silicon wafer are Each conductive adhesive was sintered to obtain nine laminates in which the base material and the silicon wafer were bonded via the sintered bodies.
また、参考のため、前記の＜導電性接着剤の製造＞で調製した銀粒子分散液Ａ１、銀粒子分散液Ａ２、銀粒子分散液Ｂ１、銀粒子分散液Ｂ２（それぞれ、銀粒子Ａ１、銀粒子Ａ２、銀粒子Ｂ１、及び銀粒子Ｂ２について、１０質量％相当のテキサノ－ルを添加し、濃度を９０質量％とした各銀粒子分散液）を、導電性接着剤（表５に示すように、それぞれ、比較例５～８）として同様に焼結体を製造した。 For reference, silver particle dispersion A1, silver particle dispersion A2, silver particle dispersion B1, and silver particle dispersion B2 (silver particle dispersion A1, silver particle dispersion B2, respectively) prepared in <Production of conductive adhesive> are also shown below. For particles A2, silver particles B1, and silver particles B2, a conductive adhesive (as shown in Table 5) was added to each silver particle dispersion solution containing 10% by mass of Texanol to give a concentration of 90% by mass. Then, sintered bodies were produced in the same manner as Comparative Examples 5 to 8).
実施組成１－２，比較組成１－８の導電性接着剤から得られた各焼結体の各種物性を以下の測定条件で測定した。 Various physical properties of each sintered body obtained from the conductive adhesives of the practical composition 1-2 and the comparative composition 1-8 were measured under the following measurement conditions.
＜焼結体の緻密度＞
各焼結体を、前記の積層体ごとエポキシ樹脂（ビュ－ラ－社製）で樹脂包埋し、２４時間静置して樹脂を硬化させた。次に、樹脂包埋された焼結体を（ＡＬＬＩＥＤ社製）精密低速切断機ＴｅｃｈＣｕｔ４で切断し、（日立ハイテクノロジーズ社製）イオンミリング（ＩＭ４０００ＰＬＵＳ）により、３時間断面ミリングを実施した。なお、断面ミリングは、放電電圧１．５ｋＶ、加速電圧６ｋＶにて、アルゴンガス流量０．０７ｃｍ3/ｍｉｎ、±３０°のスイングによってイオンビームを照射して実施した。断面ミリングによって得られた焼結体の断面を（日本電子製）走査型電子顕微鏡ＪＳＭ－ＩＴ５００ＨＲで観察してＳＥＭ画像を取得した。なお、観察にはＳＥＤモード（二次電子検出器）を用いて、加速電圧２０ｋＶ、２０００倍の視野にて、横幅６０μｍの範囲を観察した。なお、ＳＥＭ画像の縦方向については、銀の焼結層の縦幅１０μｍ以上、２００μｍ以下の範囲とした。緻密度の算出は、得られたＳＥＭ画像を２値化ソフト「ｉｍａｇｅ Ｊ」で濃淡を白と黒の二階調に画像変換し、以下の関係式で求めた。緻密度の測定結果を表５に示す。
緻密度（％）＝焼結銀面積（白色画素数）÷焼結体全面積｛焼結銀面積（白色画素数）＋空孔面積（黒色画素数）｝×１００
<Density of sintered body>
Each sintered body was embedded in an epoxy resin (manufactured by Buehler) together with the above-mentioned laminate, and left to stand for 24 hours to harden the resin. Next, the resin-embedded sintered body was cut using a precision low-speed cutting machine TechCut4 (manufactured by ALLIED), and cross-sectional milling was performed for 3 hours using ion milling (IM4000PLUS) (manufactured by Hitachi High-Technologies). Note that the cross-sectional milling was performed by irradiating the ion beam with a swing of ±30° at a discharge voltage of 1.5 kV and an acceleration voltage of 6 kV, with an argon gas flow rate of 0.07 cm 3 /min. The cross section of the sintered body obtained by cross-sectional milling was observed using a scanning electron microscope JSM-IT500HR (manufactured by JEOL Ltd.) to obtain an SEM image. For observation, an SED mode (secondary electron detector) was used to observe an area with a width of 60 μm at an accelerating voltage of 20 kV and a field of view magnified 2000 times. In addition, regarding the vertical direction of the SEM image, the vertical width of the silver sintered layer was set in a range of 10 μm or more and 200 μm or less. The density was calculated by converting the obtained SEM image into two gradations of white and black using binarization software "image J" and using the following relational expression. Table 5 shows the measurement results of compactness.
Density (%) = sintered silver area (number of white pixels) ÷ total area of sintered body {sintered silver area (number of white pixels) + pore area (number of black pixels)} x 100
＜焼結体の機械的強度（せん断強度）＞
得られた積層体について、室温でボンドテスター（西進商事製ＳＳ３０－ＷＤ）を用い、０．１２０ｍｍ／ｓの条件で焼結体に負荷をかけ、各積層体のダイシェアテストを実施して破断時の最大荷重を測定した。このようにして得られた最大荷重を接合面積で除することでせん断強度値を得た。なお、測定結果は、せん断強度を測定した９個の金めっきシリコンウエハの平均値である。せん断強度の測定結果を表５に示す。
<Mechanical strength of sintered body (shear strength)>
The resulting laminate was subjected to a die shear test by applying a load to the sintered body at room temperature using a bond tester (SS30-WD manufactured by Seishin Shoji Co., Ltd.) at a rate of 0.120 mm/s to determine whether the laminate would break. The maximum load at the time was measured. The shear strength value was obtained by dividing the maximum load thus obtained by the joint area. Note that the measurement results are the average values of nine gold-plated silicon wafers whose shear strengths were measured. Table 5 shows the measurement results of shear strength.
＜焼結体の比抵抗値＞
導電性接着剤（銀粒子９０質量％、テキサノール１０質量％の銀粒子分散液）をポリイミドフィルム上に２ｍｍ×６０ｍｍ×塗膜厚みが５０μｍとなるように、均一に塗布し、所定温度（２００℃又は２５０℃）で６０分間焼成し、焼結体を得た。次に、焼結体の抵抗値を室温条件で、抵抗計（ＨＩＯＫＩ ＲＭ３５４８）を用いて二端子測定法で測定し、実際の膜厚をマイクロメーターにて計測した値から、比抵抗（体積抵抗）値を求めた。なお、この比抵抗値は焼結体の４か所を測定した値の平均値である。比抵抗値の測定結果を表５に示す。
<Specific resistance value of sintered body>
A conductive adhesive (silver particle dispersion containing 90% by mass of silver particles and 10% by mass of Texanol) was uniformly applied onto a polyimide film in a size of 2 mm x 60 mm x coating thickness of 50 μm, and heated at a predetermined temperature (200°C). or 250° C.) for 60 minutes to obtain a sintered body. Next, the resistance value of the sintered body was measured at room temperature using a two-terminal measurement method using a resistance meter (HIOKI RM3548), and the specific resistance (volume resistance) was determined from the actual film thickness measured using a micrometer. ) value was calculated. Note that this specific resistance value is an average value of values measured at four locations on the sintered body. Table 5 shows the measurement results of specific resistance values.
＜焼結体（焼結温度２００℃）の空隙＞
前記＜電子顕微鏡による観察＞で取得した、「Ｉｍａｇｅ ｊ」を用いて２値化された各ＳＥＭ画像について、（マウンテック社製）画像解析式粒度分布測定ソフトウェア（Ｍａｃｖｉｅｗ）を用いて画像処理（色差の自動読み取りによって、２値化した画像の空隙部分を粒子として解析）し、焼結体の空隙の個数平均の大きさ及び比表面積を算出した。結果を表６に示す。なお、ここでいう個数平均の大きさは、空隙を球体と仮定して画像解析ソフトウェア（Ｍａｃｖｉｅｗ）にて解析したものであり、比表面積値は前記球体の単位体積あたりの表面積を計算により求めたものである。
<Voids in sintered body (sintering temperature 200°C)>
For each SEM image obtained in the above <observation using an electron microscope> and binarized using "Image j", image processing (color difference The voids in the binarized image were analyzed as particles by automatic reading of the sintered body, and the average size and specific surface area of the voids in the sintered body were calculated. The results are shown in Table 6. Note that the number average size here was analyzed using image analysis software (Macview) assuming that the void was a sphere, and the specific surface area value was determined by calculating the surface area per unit volume of the sphere. It is something.
＜焼結体（焼結温度２５０℃）の製造＞
次に、焼結温度２００℃で焼結体を製造した場合に、緻密度が８５％以上であり、かつ、空隙の個数平均の大きさが０．５０μｍ以上を満たした実施組成１，２の各導電性接着剤について、焼結温度をさらに高温の２５０℃としたこと以外は、前記の＜焼結体（焼結温度２００℃）の製造＞と同様にして、焼結体を得た。さらに、得られた焼結体について、せん断強度、緻密度、及び比抵抗値を、前記の＜焼結体の機械的強度（せん断強度）＞、＜焼結体の緻密度＞、及び＜焼結体の比抵抗値＞と同様にして測定した。結果を表７に示す。
<Production of sintered body (sintering temperature 250°C)>
Next, when a sintered body is produced at a sintering temperature of 200°C, the practical compositions 1 and 2 have a compactness of 85% or more and an average size of voids of 0.50 μm or more. For each conductive adhesive, a sintered body was obtained in the same manner as in <Manufacture of sintered body (sintering temperature: 200°C)>, except that the sintering temperature was set to a higher temperature of 250°C. Furthermore, the shear strength, compactness, and specific resistance values of the obtained sintered compact were determined from the above <mechanical strength (shear strength) of the sintered compact>, <density of the sintered compact>, and <sintered compact The specific resistance value of the solid body was measured in the same manner as above. The results are shown in Table 7.
＜焼結体（焼結温度２５０℃）の空隙＞
前記＜電子顕微鏡による観察＞と同様にして、＜焼結体（焼結温度２５０℃）の製造＞で得た各焼結体のＳＥＭ像を取得し、各ＳＥＭ画像について、（マウンテック社製）画像解析式粒度分布測定ソフトウェア（Ｍａｃｖｉｅｗ）を用いて画像処理（色差の自動読み取りによって、２値化した画像の空隙部分を粒子として解析）し、焼結体の空隙の個数平均の大きさ及び比表面積を算出した。結果を表８に示す。なお、ここでいう個数平均の大きさは、空隙を球体と仮定して画像解析ソフトウェア（Ｍａｃｖｉｅｗ）にて解析したものであり、比表面積値は前記球体の単位体積あたりの表面積を計算により求めたものである。
<Voids in sintered body (sintering temperature 250°C)>
In the same manner as the above <Observation using an electron microscope>, SEM images of each sintered body obtained in <Manufacture of sintered body (sintering temperature 250°C)> were obtained, and for each SEM image, (manufactured by Mountech) Image processing is performed using image analysis type particle size distribution measurement software (Macview) (by automatically reading color differences, the voids in the binarized image are analyzed as particles), and the average number size and ratio of voids in the sintered body are determined. The surface area was calculated. The results are shown in Table 8. Note that the number average size here was analyzed using image analysis software (Macview) assuming that the void was a sphere, and the specific surface area value was determined by calculating the surface area per unit volume of the sphere. It is something.
Claims (6)
前記焼結体は、緻密度が８５％以上であり、
前記焼結体は、空隙の個数平均の大きさが０．５０μｍ以上である、焼結体。 A sintered body of silver particles,
The sintered body has a density of 85% or more,
The sintered body is a sintered body in which the number average size of voids is 0.50 μm or more.
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