JP2004111254A - Metal contained composition for electrical connection of electronic device - Google Patents
Metal contained composition for electrical connection of electronic device Download PDFInfo
- Publication number
- JP2004111254A JP2004111254A JP2002273233A JP2002273233A JP2004111254A JP 2004111254 A JP2004111254 A JP 2004111254A JP 2002273233 A JP2002273233 A JP 2002273233A JP 2002273233 A JP2002273233 A JP 2002273233A JP 2004111254 A JP2004111254 A JP 2004111254A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- particles
- conductive
- powder
- particle size
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 145
- 229910052751 metal Inorganic materials 0.000 title claims description 116
- 239000002184 metal Substances 0.000 title claims description 116
- 239000002245 particle Substances 0.000 claims abstract description 263
- 239000000843 powder Substances 0.000 claims abstract description 227
- 239000002923 metal particle Substances 0.000 claims description 173
- 239000007787 solid Substances 0.000 claims description 93
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 229910052718 tin Inorganic materials 0.000 claims description 23
- 229910052738 indium Inorganic materials 0.000 claims description 19
- 229910052741 iridium Inorganic materials 0.000 claims description 19
- 229910052762 osmium Inorganic materials 0.000 claims description 19
- 229910052702 rhenium Inorganic materials 0.000 claims description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 150000001722 carbon compounds Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 6
- 238000002296 dynamic light scattering Methods 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004693 Polybenzimidazole Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002480 polybenzimidazole Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 abstract description 11
- 239000013528 metallic particle Substances 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 87
- 239000006228 supernatant Substances 0.000 description 55
- 239000000725 suspension Substances 0.000 description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 33
- 239000010949 copper Substances 0.000 description 31
- 239000011882 ultra-fine particle Substances 0.000 description 27
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 23
- 239000011135 tin Substances 0.000 description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 239000012153 distilled water Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000001935 peptisation Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000004576 sand Substances 0.000 description 16
- 235000021355 Stearic acid Nutrition 0.000 description 15
- 238000001723 curing Methods 0.000 description 15
- 238000010586 diagram Methods 0.000 description 15
- 239000010931 gold Substances 0.000 description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 15
- 239000008117 stearic acid Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000011033 desalting Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000000108 ultra-filtration Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000011362 coarse particle Substances 0.000 description 12
- 239000011231 conductive filler Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 description 7
- 239000012279 sodium borohydride Substances 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- 229910002710 Au-Pd Inorganic materials 0.000 description 6
- 241000287462 Phalacrocorax carbo Species 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910001111 Fine metal Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910002708 Au–Cu Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- 229910002696 Ag-Au Inorganic materials 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
- IIQBISCKFGIEED-UHFFFAOYSA-K [OH-].[OH-].[OH-].[Sn].[Sb+3] Chemical compound [OH-].[OH-].[OH-].[Sn].[Sb+3] IIQBISCKFGIEED-UHFFFAOYSA-K 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- KVXKIRARVMGHKF-UHFFFAOYSA-G indium(3+);tin(4+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[In+3].[Sn+4] KVXKIRARVMGHKF-UHFFFAOYSA-G 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- YOLNUNVVUJULQZ-UHFFFAOYSA-J iridium;tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ir] YOLNUNVVUJULQZ-UHFFFAOYSA-J 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000487 osmium oxide Inorganic materials 0.000 description 1
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- UACQLNPCDXDCID-UHFFFAOYSA-K trichloroosmium;trihydrate Chemical compound O.O.O.Cl[Os](Cl)Cl UACQLNPCDXDCID-UHFFFAOYSA-K 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
Images
Landscapes
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は電子デバイスの電気的接続用金属含有組成物に関するものである。
【０００２】
【従来の技術】
従来、銀粉等の導電性粒子および樹脂を含有する金属含有組成物（導電性ペーストと呼ばれることもある）を塗布、印刷または充填し、硬化処理して導電性組成物となし、プリント配線板、電子部品等の電気回路（配線導体）やコンタクトホール充填部材を形成する方法が一般的に知られている。（たとえば、非特許文献１参照。）。
【０００３】
このような金属含有組成物を用いて形成される電気的接続部位では、導電性組成物中で銀粒子等の金属粒子間に物理的接触が生じ、形成された導電パスによって導電性が発現している。このため、導電性を上げるためには導電パスの形成が不可欠であり、導電パスの形成の点から、金属含有組成物中の導電フィラーの比率を上げることや、導電フィラーの形状を扁平状にし、フィラー間の接触をより大きくする試みが知られている（たとえば、特許文献１参照。）。
【０００４】
しかしながら、一般に金属含有組成物は粉体である導電性フィラーと樹脂、希釈剤等とによって構成されており、導電フィラー比率を上げすぎると、樹脂、希釈剤量が低下し、金属含有組成物自体が流動性を失ったり粉状となったりするため、塗布、印刷、充填が困難になる。また、扁平状や樹枝形状の導電性フィラーは球形状に比べてタップ密度が低下するため、金属含有組成物における添加濃度は、球形状の導電性フィラーに比べて低下する。更に、回路形成部分が微細になればなるほど金属含有組成物自体に対する流動性の要求は高度になるため、このような欠点は電子デバイスの小型化の動向とともにより顕著になってきている。
【０００５】
一方、金属含有組成物を加熱処理等して得られる導電性組成物よりなる回路やコンタクトホール中の電気的接続部位について、劣化の抑制、すなわち耐久性の向上が望まれている。回路やコンタクトホール中の導電性組成物よりなる電気的接続部位の劣化としては、導電性組成物中の構成材料の熱膨張係数が一様でなく、熱膨張／収縮を繰り返すうちに、電気的接続部位内に微細なクラックが生じ、導電パスが切断されることが知られている。
【０００６】
導電性組成物は導電フィラー同士を樹脂により固め、連結させているものであり、導電フィラー間の物理的接触により導電パスが形成されている。代表的導電性フィラーの材料である銅および銀の熱膨張係数が、それぞれ１７×１０−６℃−１、１９×１０−６℃−１であり、一般に使用されているエポキシ樹脂の熱膨張係数が５０×１０−６〜１００×１０−６℃−１であることを考慮すると、熱膨張／収縮のヒートサイクルに対し、フィラーの物理的接触だけに依存する従来の金属含有組成物では、本質的に耐久性の向上については限界があるといえる。
【０００７】
【特許文献１】
特開平９−９２０２６号公報（段落番号００１６）
【０００８】
【非特許文献１】
「電子材料」，工業調査会，１９９４年１０月号，ｐ．４２−４６
【０００９】
【非特許文献２】
「ジャーナルオブゾルゲルサイエンステクノロジー（Ｊ． Ｓｏｌ−Ｇｅｌ Ｓｃｉｅｎｃｅ Ｔｅｃｈｎｏｌｏｇｙ）」，（オランダ），クルーワーアカデミックパブリッシャーズ（Ｋｌｕｗｅｒ Ａｃａｄｅｍｉｃ Ｐｕｂｌｉｓｈｅｒｓ），２００１年，第２２巻，ｐ．１５１−１６６
【００１０】
【非特許文献３】
津田椎雄，「電気伝導性酸化物」，増補第３版，裳華房，１９８７年７月２５日，ｐ．９−１１
【００１１】
【非特許文献４】
「透明導電膜の技術」，第１版，オーム社発行，１９９０年３月３０日，ｐ．５１
【００１２】
【非特許文献５】
「サーフェスサイエンス（Ｓｕｒｆａｃｅ Ｓｃｉｅｎｃｅ）」，エルスヴィエアサイエンスパブリッシャーズ（Ｅｌｓｅｖｉｅｒ Ｓｃｉｅｎｃｅ Ｐｕｂｌｉｓｈｅｒｓ），１９９２年，第２６０巻，ｐ．１１６−１２８
【００１３】
【発明が解決しようとする課題】
本発明は、流動性が高く、塗布性、印刷性、充填性に優れ、熱処理等のエネルギー付与により、導電性と耐久性とにすぐれた電子デバイスの電気的接続用導電性組成物を与えることができる金属含有組成物を提供することを目的とする。
【００１４】
本発明のさらに他の目的および利点は、以下の説明から明らかになるであろう。
【００１５】
【課題を解決するための手段】
本発明の第１の態様は、平均粒径が２０ｎｍ以下の金属粒子粉（以下、「平均粒径が２０ｎｍ以下の金属粒子粉」を「金属粒子粉Ａ」ともいう）と平均粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子粉（以下、「平均粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子粉」を「金属粒子粉Ｂ」ともいう）と樹脂と、場合によってはさらに平均粒径が２０００ｎｍを超え２０μｍ以下の導電性粒子粉（以下、「平均粒径が２０００ｎｍを超え２０μｍ以下の導電性粒子粉」を「導電性粒子粉Ｃ」ともいう）とを含む、電子デバイスの電気的接続用金属含有組成物である。
【００１６】
本発明の第２の態様は、金属含有組成物中の金属粒子粉Ａの濃度をａ質量％、金属粒子粉Ｂの濃度をｂ質量％、導電性粒子粉Ｃの濃度をｃ質量％とした場合、
ａ：ｂが３：９７〜９０：１０の間にあり、
（ａ＋ｂ）：ｃが１００：０〜６０：４０の間にあり、
５０≦（ａ＋ｂ＋ｃ）≦９５である
上記態様１に記載の金属含有組成物である。
【００１７】
本発明の第３の態様は、金属粒子と樹脂と、場合によっては導電性粒子とを含み、
金属粒子と導電性粒子との総量に対し、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子との量割合が質量比で３：９７〜９０：１０の間にあり、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子とを合計で６０〜１００質量％の割合で含み、２０００ｎｍを超え２０μｍ以下の導電性粒子を４０〜０質量％の割合で含む、
電子デバイスの電気的接続用金属含有組成物である。
【００１８】
本発明の第４の態様は、金属粒子と樹脂と、場合によっては導電性粒子とを含む電子デバイスの電気的接続用金属含有組成物において、
当該金属含有組成物中に存在する固体粒子の動的光散乱による測定法による粒度分布のうち、２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域とにそれぞれピークが存在し、
場合によってはさらに２０００ｎｍを超え２０μｍ以下の粒径領域にピークが存在する
電子デバイスの電気的接続用金属含有組成物である。
【００１９】
本発明の第５の態様は、金属粒子粉Ａと金属粒子粉Ｂとが、それぞれ、Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と当該元素を含む合金粒子との少なくともいずれか一つを含み、
導電性粒子粉Ｃが存在する場合には当該導電性粒子粉Ｃが、
Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と、
当該元素を含む合金粒子と、
Ｉｎ，Ｒｕ，Ｒｅ，Ｏｓ，Ｉｒ，Ｓｎからなる群から選ばれた少なくともいずれか１種の元素を含む導電性酸化物粒子と、
グラファイト、グラファイト構造を有するカーボン化合物およびカーボンナノチューブからなる群から選ばれた少なくともいずれか１種の導電性カーボン化合物と
の少なくともいずれか一つを含む、上記態様１または２に記載の金属含有組成物である。
【００２０】
本発明の第６の態様は、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子とが、それぞれ、Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と当該元素を含む合金粒子との少なくともいずれか一つを含み、
２０００ｎｍを超え２０μｍ以下の導電性粒子が存在する場合には当該導電性粒子が、
Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と、
当該元素を含む合金粒子と、
Ｉｎ，Ｒｕ，Ｒｅ，Ｏｓ，Ｉｒ，Ｓｎからなる群から選ばれた少なくともいずれか１種の元素を含む導電性酸化物粒子と、
グラファイト、グラファイト構造を有するカーボン化合物およびカーボンナノチューブからなる群から選ばれた少なくともいずれか１種の導電性カーボン化合物と
の少なくともいずれか一つを含む、上記態様３または４に記載の金属含有組成物である。
【００２１】
本発明の第７の態様は、樹脂が、エポキシ系硬化性樹脂、フェノール系硬化性樹脂、メラミン系硬化性樹脂、シリコーン系硬化性樹脂、アクリル樹脂、ポリエチレン、ポリスチレン、ポリプロピレン、ポリ塩化ビニル、ポリイミド、ポリアミドおよびポリベンゾイミダゾールからなる群から選ばれた少なくとも１種の樹脂を含む、上記態様１〜６のいずれかに記載の金属含有組成物である。
【００２２】
【発明の実施の形態】
以下に、本発明の実施の形態を図、表、実施例等を使用して説明する。なお、これらの図、表、実施例等および説明は本発明を例示するものであり、本発明の範囲を制限するものではない。本発明の趣旨に合致する限り他の実施の形態も本発明の範疇に属し得ることは言うまでもない。
【００２３】
本発明に係る電子デバイスの電気的接続用金属含有組成物は、金属粒子粉Ａと金属粒子粉Ｂと樹脂とを含むペースト状の組成物である。
【００２４】
本発明に係る金属含有組成物は、適度な粘性を有するペーストとすることができ、５０μｍ以下の直径の微細なビアホールなどにも十分充填が可能になり、塗布、印刷等により、線幅が２０μｍ以下の微細な回路配線も良好に形成可能になる。金属含有組成物の粘度としては、たとえば、取り扱い性、塗布性、印刷性、充填性の良好な１０〜２０００ｄＰａ・ｓのペーストを容易に作製することができる。
【００２５】
本発明に係る金属含有組成物は、ビアホールへの充填、配線パターンの形成後、エネルギーを付与し、硬化性樹脂を硬化させ、熱可塑性樹脂であればそれを軟化または溶融させて導電性組成物とするが、その際粒径が２０ｎｍ以下の金属粒子に表面融解が生じる。なお、このレベルの微細粒子では、粒度分布がシャープであるため、実際には、金属粒子粉Ａに表面融解が生じると考えても不都合はない。
【００２６】
なお、以下においては、金属含有組成物に含まれる樹脂として、主に、硬化性樹脂または硬化性樹脂と熱可塑性樹脂との組み合わせについて説明したが、本発明に係る金属含有組成物に含まれる樹脂としては、熱可塑性樹脂のみの場合もあり得る。このように熱可塑性樹脂のみを使用する場合には、本発明の趣旨に反しない範囲で、たとえば「硬化」は「固化」に、「硬化組成物」は「固化組成物」に読み替えることになる。
【００２７】
この時、その融解部分の近傍に金属粒子粉Ｂがあると、エネルギーが付与された場合、金属粒子間の連結が加速度的に生じ、金属粒子粉Ｂを巻き込みながら金属結合体が自己成長を始める。この自己成長機構は、金属粒子粉Ａの金属粒子の表面エネルギーが安定な状態になった段階で終了する。
【００２８】
金属粒子の表面融解は粒子表面元素の異常格子振動によって起こり、平均粒径が小さく、表面原子比率が高ければ高いほど表面溶融温度が低下する。表面原子比率（粒子全体の原子のうちで粒子表面に存在する原子の比率）については、計算上、直径１０ｎｍの粒子で２０％、直径２０ｎｍの粒子で１０％、直径７０ｎｍの粒子で３％以下となる。この影響で、銀の場合、バルク体の融点は９６１℃であるが、直径１０ｎｍの粒子の場合１６０℃前後で表面溶融が観測される。（たとえば、非特許文献２参照。）。
【００２９】
このとき、金属含有組成物中に金属粒子粉Ｂがなく、金属粒子粉Ａと樹脂とのみで金属含有組成物を調製した場合には、その中に存在する金属粒子が微細なため、粒子間の連結が不充分となることが多い。また、粒子間の金属結合を起こりやすくするため、金属粒子粉Ａと溶媒とで流動性の高いペースト状の金属含有組成物を調製した場合には、粒子間の連結は改良されるものの、溶媒の沸点以上まで加熱する必要があり、工程コストが高くなり、かつ、他電子部品の品質低下を招く恐れが大きい。このような挙動は、たとえば微細Ａｇ粒子で容易に観察することができる。
【００３０】
更に、金属粒子粉Ａと平均粒径が２０００ｎｍを超える大きな金属粒子粉と樹脂とのみでペースト状の金属含有組成物を調製した場合には、金属粒子粉Ａの表面溶融が生じた後に、平均粒径が２０００ｎｍを超える大きさの金属粒子粉を巻き込みながらの自己成長が生じにくい。これは、微細な金属粒子の表面溶融が、表面に存在する原子の異常格子振動に依存しているためであり、微細金属粒子に表面溶融が生じた後、平均粒径が２０００ｎｍを超える大きさの大粒子粉に結合し、表面原子比率が著しく低下し、溶融現象が停止するからである。
【００３１】
本発明に係る金属含有組成物では、微細金属粒子近傍に金属粒子粉Ｂの粒子を配することにより、微細金属粒子が表面溶融した後、金属粒子粉Ｂに結合した段階でもその結合体自体が未だ十分に大きくないため、表面エネルギー的に安定になっておらず、更にその近傍に存在する粒子を巻き込みながら自己成長を続けることができると考えられる。
【００３２】
自己成長のメカニズムは必ずしも明らかではないが、粒子サイズによるナノオーダー粒子の表面融解の効果、溶融部分の空間的な濃度勾配、およびそれに伴う温度の局部的勾配に起因すると考えられる。従って、形状的には等方的な形状であるよりも異方的形状となりやすく、結果として、針状形状、樹枝形状等の形状になると考えられる。このようにして、生成した導電性組成物の断面を見ると、球状粒子のみを使用した場合でも、針状形状、樹枝形状、いがぐり形状および不定形連結形状等が新たに生じたことが観察されるようになる。針状形状、樹枝形状、いがぐり形状および不定形連結形状等が新たに生じたことは、金属粒子粉Ｂとして針状形状、樹枝形状、いがぐり形状等を有するものを使用した場合にも、導電性組成物の断面における形状が、金属含有組成物中における形状とは異なることで容易に知ることができる。
【００３３】
なお、このような針状形状、樹枝形状、いがぐり形状および不定形連結形状等は粒子間の連結の結果である。従って、ヒートサイクルを受けた場合にも、電気的接続部位内に微細なクラックが生じたり、導電パスが切断されたりすることが防止できることになる。
【００３４】
この結果、本発明に係る金属含有組成物は、熱処理等のエネルギー付与により、導電性と耐久性とにすぐれた電子デバイスの電気的接続用導電性組成物を与えることができる。
【００３５】
ここで、針状形状は、図１〜６に例示するように、棒状または針状の形状１を意味する。図５，６に示すような幅広のものも存在する。
【００３６】
樹枝形状は、折れ曲がった棒状または針状の形状や、図７，８に例示するように３つ以上に分岐した形状２を意味する。
【００３７】
いがぐり形状３は、図９〜１２に例示するように、固まり形状から、棒状または針状の形状１が、ひとつ以上突き出している形状を意味する。なお、上記図中には空隙４が存在する場合もある。
【００３８】
図１３に示すように、不定形連結形状５は、針状形状、樹枝形状、いがぐり形状等が連結して生じた形状と思われる。
【００３９】
針状形状、樹枝形状の折れ曲がり形状または分岐形状、いがぐり形状における突き出し形状のアスペクト比が３以上であることが好ましい。図１〜１２に示す、Ｌ１とＷ１との比がアスペクト比の例である。
【００４０】
長さ（Ｌ）は一様ではないため、アスペクト比は、そのもっとも大きな部位の値を採用している。図８のＬ１，Ｌ２のように長さ（Ｌ）が複数存在すると思われる場合は、大きい方を採用する。
【００４１】
幅（Ｗ）についても一様ではないため、図中のＷ２に示すような端部分の幅やＷ３に示すような微細な突起の幅ではない、もっとも大きな部位の値を採用する。
【００４２】
本発明に係る金属含有組成物には、さらに導電性粒子粉Ｃを含めることができる。
【００４３】
導電性粒子粉Ｃがあると、金属含有組成物の硬化中に、金属粒子粉Ａと金属粒子粉Ｂとの自己成長機構によって形成される金属結合体によって、導電性粒子粉Ｃの粒子間を繋ぐことができるので、導電パスの形成の点から好ましい。導電性粒子粉Ｃ自体は自己成長をする必要がないため、金属、導電性酸化物、導電性カーボン化合物等を使用することができる。なお、本発明において、粒度分布や平均粒径は動的光散乱による測定法によって求められたものである。
【００４４】
本発明に係る金属含有組成物を１６０℃で６０分熱処理して得られる組成物において、任意に選択した０．１ｍｍ２の断面の少なくとも一つに、上記したような、金属または金属と導電性粒子とによって構成される針状形状、樹枝形状、いがぐり形状および不定形連結形状からなる群から選ばれた少なくとも一つの形状が１個以上含まれることが好ましい。導電性組成物として十分な導電性が確保できるからである。
【００４５】
金属含有組成物中の金属粒子粉Ａの濃度をａ質量％、金属粒子粉Ｂの濃度をｂ質量％、導電性粒子粉Ｃの濃度をｃ質量％とした場合、ａ：ｂが３：９７〜９０：１０の間にあり、（ａ＋ｂ）：ｃが１００：０〜６０：４０の間にあり、５０≦（ａ＋ｂ＋ｃ）≦９５であることが好ましい。（ａ＋ｂ）：ｃが１００：０〜６０：４０の間にあると上記自己成長が容易に起こりやすく、ｃが０（ゼロ）でない場合には金属粒子間の連結の促進が期待でき、ａ：ｂが３：９７〜９０：１０の間にあると、針状形状、樹枝形状、いがぐり形状、不定形連結形状等が成長しやすく、５０≦（ａ＋ｂ＋ｃ）≦９５にあると、針状形状、樹枝形状、いがぐり形状、不定形連結形状等の数が多く、導電性を確保しやすくなるからである。上記の条件を満足すると、金属含有組成物中の金属粒子や導電性粒子の濃度を適度に保って流動性を高く保ちつつ、優れた塗布性、印刷性、充填性を実現でき、熱処理等のエネルギー付与により、導電性と耐久性とにすぐれた電子デバイスの電気的接続用導電性組成物を得ることができる。
【００４６】
金属粒子粉Ａと金属粒子粉Ｂとは、それぞれ、Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と当該元素を含む合金粒子との少なくともいずれか一つを含むことが好ましい。
【００４７】
これらの元素の金属の電気抵抗率（比抵抗）は、Ａｇ：１．６３μΩｃｍ，Ａｕ：２．２μΩｃｍ，Ｒｕ：７．３７μΩｃｍ，Ｐｄ：１０．５５μΩｃｍ，Ｐｔ：１０．４２μΩｃｍ，Ｒｅ：１８．７μΩｃｍ，Ｏｓ：９．１３μΩｃｍ，Ｉｒ：５．０７μΩｃｍ，Ｃｕ：１．６９μΩｃｍ，Ｎｉ：３０．６μΩｃｍ、Ｓｎ：１２．６μΩｃｍ、Ａｌ：２．６７μΩｃｍ，Ｚｎ：５．９６μΩｃｍ，Ｉｎ：９．０μΩｃｍ、Ｃｏ：６．２４μΩｃｍ，Ｗ：５．５μΩｃｍ，Ｍｏ：５．７μΩｃｍと低い値を示し、いずれも利用可能である。
【００４８】
本発明に係る金属粒子粉Ａと金属粒子粉Ｂとは、エネルギー付与時に流動性を有するペースト状の金属含有組成物中で、金属粒子同士が連結自己成長をすることが重要である。
【００４９】
金属の接合等の観点より、金属粒子粉Ａと金属粒子粉Ｂとは同一金属原子種もしくは自己成長を阻害しにくい金属の組合せであればよい。同一元素種の場合特に問題はなく、異なる元素種の組合せであったとしても、全率固溶体を形成する組合せであれば好ましい。たとえば、Ａｇ−Ａｕ，Ａｇ−Ｐｄ，Ｐｄ−Ａｕ，Ａｕ−Ｃｕ，Ｒｕ−Ｒｅ等の組合せがある。
【００５０】
また、全率固溶体を形成しない組合せであっても、金属粒子粉Ａの金属粒子に表面融解が生じ、金属粒子粉Ｂの金属粒子の表面に結合しやすい金属種の組み合わせであれば好ましい。
【００５１】
表面溶解した金属種が他の金属粒子へ結合する場合拡散機構を経ることになる。拡散機構によってある金属が異なる金属表面に移行するか否かは吸着エネルギー等から計算できることが知られている（たとえば、非特許文献５参照。）。そのため、これらに基づいて適宜決定することができる。
【００５２】
合金粒子の場合、金属の組合せにより金属単体の場合より電気抵抗率が悪化する場合もあり得るが、実験等で適切なものを容易に選択することが可能である。
【００５３】
たとえば、Ａｕ−Ａｇ（Ａｇ１０質量％）：１０．４μΩｃｍ，Ａｕ−Ｃｕ（Ｃｕ２０質量％）：１４．２μΩｃｍ，Ａｕ−Ｎｉ（Ｎｉ５質量％）：１３．２μΩｃｍ，Ａｕ−Ｐｄ（Ｐｄ４０質量％）：３２μΩｃｍ，Ａｇ−Ｃｕ（Ｃｕ２０質量％）：２．１μΩｃｍ，Ｐｔ−Ｎｉ（Ｎｉ１０質量％）：２７μΩｃｍ，Ｐｔ−Ｐｄ（Ｐｄ２０質量％）：２８μΩｃｍ等を挙げることができる。
【００５４】
本発明に係る導電性粒子粉Ｃは、導電性を有する粒子の粉を意味する。粒子の電気抵抗率が１５０μΩｃｍ以下であることが好ましい。従って金属粒子以外の物質の粒子も導電性粒子の範疇に属する。
【００５５】
導電性粒子粉Ｃとしては、Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と、当該元素を含む合金粒子と、Ｉｎ，Ｒｕ，Ｒｅ，Ｏｓ，Ｉｒ，Ｓｎからなる群から選ばれた少なくともいずれか１種の元素を含む導電性酸化物粒子と、グラファイト、グラファイト構造を有するカーボン化合物およびカーボンナノチューブからなる群から選ばれた少なくともいずれか１種の導電性カーボン化合物との少なくともいずれか一つを含むことが好ましい。
【００５６】
導電性酸化物の場合、組成、結晶構造、酸素欠損状態などに起因し、固有の定まった電気抵抗率はないが、一般には以下の値が知られている（たとえば、非特許文献３，４参照。）。たとえばＳｎがドープされたインジウム酸化物のＩＴＯ：４３μΩｃｍ、酸化錫：７５μΩｃｍ、酸化ルテニウム：４０μΩｃｍ、酸化オスミウム：６０μΩｃｍ、酸化イリジウム：５０μΩｃｍ、酸化レニウム：１００μΩｃｍであり、いずれも利用可能である。
【００５７】
導電性カーボン化合物のうち、グラファイトは六方晶系の６角板状の扁平な結晶で炭素６員環が層状構造を形成しており、層面内の電気抵抗率は４０μΩｃｍ程度であり、利用可能である。また一般に販売されている導電性カーボンのうちでもグラファイト構造が結晶中に１部形成されているものがあり、導電性が高く利用可能である。
【００５８】
カーボンナノチューブは前記グラファイトのシートが筒状に形成された形状をしており、構造上境界条件が発生し、ｔｕｂｅ（ｎ，ｍ）：キラルベクトル表示（グラフェンシートからの構造を規程した場合の表示方法）において，２ｎ＋ｍ＝３となる場合、金属的性質を有するため好ましい。また、形状的にアスペクト比が著しく高いため、導電パスの形成の点からも利用可能である。
【００５９】
従来の導電性組成物が導電性フィラーの物理的な接触で導電パスを形成していたのと異なり、本発明では粒子が硬化物中で樹脂の架橋固着作用によらず、相互に結合した状態を形成しているため、結合が強固であり、導電性も高い。また、その結合した形態が、予め金属含有組成物中に存在していた粒子の形態と異なり、アスペクト比が大きく変化した状態であり、相互にネットワークを形成しやすいため、熱膨張／収縮等のヒートサイクル時の構造安定性にも寄与する。
【００６０】
なお、本発明に係る、金属粒子粉Ａと金属粒子粉Ｂと、場合によってはさらに導電性粒子粉Ｃとを含む電子デバイスの電気的接続用金属含有組成物と同等の効果は、粒子の混合状態で考えた場合、金属粒子と樹脂と、場合によっては導電性粒子とを含み、金属粒子と導電性粒子との総量に対し、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子との量割合が質量比で３：９７〜９０：１０の間にあり、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子とを合計で６０〜１００質量％の割合で含み、２０００ｎｍを超え２０μｍ以下の導電性粒子を４０〜０質量％の割合で含む金属含有組成物で実現できることが判明した。
【００６１】
このような場合に得られる硬化組成物においても、任意に選択した０．１ｍｍ２の断面の少なくとも一つに、上記したような、金属または金属と導電性粒子とによって構成される針状形状、樹枝形状、いがぐり形状および不定形連結形状からなる群から選ばれた少なくとも一つの形状が１個以上新たに生じることが好ましい。
【００６２】
金属粒子と導電性粒子との総量に対し、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子との量割合が質量比で３：９７〜９０：１０の間にあると、針状形状、樹枝形状、いがぐり形状、不定形連結形状等が成長しやすく、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子とを合計で６０質量％以上含むと、金属粒子の自己成長が容易に起こりやすくなり、２０００ｎｍを超え２０μｍ以下の導電性粒子が４０質量％以下の割合で存在すると、金属粒子間の連結が促進されるからである。なお、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子と２０００ｎｍを超え２０μｍ以下の導電性粒子との合計は、金属含有組成物中、５０〜９５質量％であることが好ましい。
【００６３】
上記の条件を満足すると、金属含有組成物中の金属粒子や導電性粒子の濃度を適度に保って流動性を高く保ちつつ、優れた塗布性、印刷性、充填性を実現でき、熱処理等のエネルギー付与により、導電性と耐久性とにすぐれた電子デバイスの電気的接続用導電性組成物を得ることができる。
【００６４】
また、金属含有組成物中に存在する固体粒子の粒度分布の観点から見ると、金属粒子と樹脂と、場合によっては導電性粒子とを含む電子デバイスの電気的接続用金属含有組成物において、当該金属含有組成物中に存在する固体粒子の動的光散乱による測定法による粒度分布のうち、２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域とに、それぞれピークが存在し、場合によってはさらに２０００ｎｍを超え２０μｍ以下の粒径領域にピークが存在する金属含有組成物でも同様の効果を実現することができる。
【００６５】
このような場合に得られる硬化組成物においても、任意に選択した０．１ｍｍ２の断面の少なくとも一つに、上記したような、金属または金属と導電性粒子とによって構成される針状形状、樹枝形状、いがぐり形状および不定形連結形状からなる群から選ばれた少なくとも一つの形状が１個以上新たに生じることが好ましい。
【００６６】
なお、２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域に存在する粒子としては、実質的に金属粒子からなっていることが好ましい。
【００６７】
ここで、金属含有組成物中に存在する固体粒子の粒度分布とは、金属粒子、導電性粒子以外に他の固体状の粒子が存在する場合には、そのような固体粒子を含めて、全固体粒子としての粒度分布を意味する。
【００６８】
２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域とに、それぞれピークが存在すると、針状形状、樹枝形状、いがぐり形状、不定形連結形状等が成長しやすく、また金属粒子の自己成長が容易に起こりやすくなり、さらに２０００ｎｍを超え２０μｍ以下の粒径領域にピークが存在すると、金属粒子間の連結が促進されるからである。このような条件を満足する場合にも、金属含有組成物中の金属粒子や導電性粒子の濃度を適度に保って流動性を高く保ちつつ、優れた塗布性、印刷性、充填性を実現でき、熱処理等のエネルギー付与により、導電性と耐久性とにすぐれた電子デバイスの電気的接続用導電性組成物を得ることができる。
【００６９】
なお、このような場合、金属粒子粉Ａと金属粒子粉Ｂと、場合によっては導電性粒子粉Ｃとの組み合わせのときと同様、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子とが、それぞれ、Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と当該元素を含む合金粒子との少なくともいずれか一つを含み、２０００ｎｍを超え２０μｍ以下の導電性粒子が存在する場合には当該導電性粒子が、Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と、当該元素を含む合金粒子と、Ｉｎ，Ｒｕ，Ｒｅ，Ｏｓ，Ｉｒ，Ｓｎからなる群から選ばれた少なくともいずれか１種の元素を含む導電性酸化物粒子と、グラファイト、グラファイト構造を有するカーボン化合物およびカーボンナノチューブからなる群から選ばれた少なくともいずれか１種の導電性カーボン化合物との少なくともいずれか一つを含むことが好ましい。
【００７０】
本発明の導電性組成物を作るためのエネルギー付与方法としては、加熱、紫外線照射、Ｘ線照射、電子線照射、超音波照射のいずれか少なくとも一種の方法を使用することができる。加熱方法としては、温風加熱、熱輻射等の方法が利用可能である。加熱温度および処理時間は実際に求められる特性に基づいて適宜決定できる。
【００７１】
紫外線照射方法としては、２５４ｎｍを主波長とする低圧ＵＶランプや３６５ｎｍを主波長とする高圧ＵＶランプの使用が可能である。エネルギー的には短波長の紫外線が高エネルギーであるが、照射時間等との兼ね合いで適宜決定することが好ましい。また、紫外線エネルギーを樹脂成分の硬化によりよく利用するため、紫外線に反応し、硬化させる硬化開始剤を金属含有組成物に添加することも可能である。Ｘ線、電子線も高エネルギー放射線であり、エネルギー付与の観点より使用可能である。特に電子線の場合、照射部のみ短時間で熱エネルギーを付与できるため好ましい。また、超音波照射により金属含有組成物内部での粒子および樹脂を振動させ、熱エネルギーを発生させることで硬化させることも可能である。超音波照射の場合、未硬化の金属含有組成物中で気泡を発生させ、この気泡の開裂時の熱エネルギーを利用して硬化させることも可能である。
【００７２】
本発明に用いる樹脂は、金属含有組成物が硬化する前段階で金属含有組成物に流動性を付与し、硬化終了段階で樹脂同士が固化した状態であるものであればよく、熱硬化性樹脂等の硬化性樹脂が好ましいが、熱可塑性樹脂等を併用または単独に使用してもよい。本発明の趣旨に反しない限り他の樹脂を含んでいてもよい。また樹脂自体が固体の場合、有機溶媒、反応性希釈剤中に溶解したものでもよい。
【００７３】
硬化性樹脂としては、エポキシ系硬化性樹脂、フェノール系硬化性樹脂、メラミン系硬化性樹脂およびシリコーン系硬化性樹脂からなる群から選ばれた少なくとも１種の硬化性樹脂が好ましい。熱可塑性樹脂としては、アクリル樹脂、ポリエチレン、ポリスチレン、ポリプロピレン、ポリ塩化ビニル、ポリイミド、ポリアミドおよびポリベンゾイミダゾールからなる群から選ばれた少なくとも１種の熱可塑性樹脂が好ましい。
【００７４】
本発明に係る金属含有組成物には、本発明の趣旨に反しない限り、上記以外の金属粒子や導電性粒子、各種の添加剤等を共存させてもよい。添加剤等としては、エネルギー線硬化や熱硬化等の硬化開始剤や硬化促進剤、増感剤、増粘剤、強度補強剤等を挙げることができる。
【００７５】
本発明に係る金属含有組成物は、回路基板等の電子デバイスの電気的接続部位であるビアホール、スルーホールおよび配線等に利用すると効果が大きい。具体的には、（１）プリント配線板のスルーホールに充填、硬化、表面研磨を行うことで各層間の回路の接続を行う部位、（２）プリント配線板でのレーザービアやフォトビア等で作られる非貫通孔に、充填、硬化、表面研磨を行うことで各層間の回路の接続をする部位、（３）半導体の裏面接続用の貫通孔に、充填、硬化、表面研磨を行うことで回路の接続を図る部位、（４）半導体の放熱用非貫通孔に充填し、硬化する部位、（５）半導体パッケージやプリント配線板において金属含有組成物を印刷し、硬化することで形成されるバンプと呼ばれる突起状の電極部位、（６）プリント配線板の層間接続において内層材の回路上に印刷、硬化により形成される導電性円錐状突起部位、（７）プリント配線板や半導体パッケージの部品の実装時に用いられるハンダ接続の代替として用いられる電気的接続部位、（８）印刷配線板として、導体回路を印刷硬化することにより形成される導体回路部位、（９）部品を内臓したプリント配線板の場合においてレーザーなどを用いて部品の電極に達する非貫通孔を設け、その非貫通孔に充填し、硬化研磨し、部品電極との接続を図る部位への適用を挙げることができる。
【００７６】
これらの半導体デバイスは、たとえば次のようにして作製することができる。
【００７７】
内層銅電極部位を形成してあるプリント基板にレーザー光を照射し、プリント基板内部の銅電極部分まで、孔を空け、レーザー光により溶解蒸発したプリント基板材料である絶縁性樹脂残留物質を除去し、有底銅電極部位を具備してなる非貫通孔を備えたプリント基板を作製する。
【００７８】
ついで、この非貫通孔に前記金属含有組成物をスクリーン印刷にて充填する。この後、熱を付与することにより前記金属含有組成物を硬化させ、更にプリント基板面を研磨処理することにより、当該硬化物により生じていたプリント基板上の凹凸部位を無くし、プリント基板表面の平坦化を図る。
【００７９】
更に、このプリント基板表面に露出している硬化物部位表面に銅メッキ処理を行い電極を付与し、回路部分と接続を図る。
【００８０】
また、上記の銅メッキに代わり、当該金属含有組成物をスクリーン印刷し、熱硬化させ、導電回路（配線）を形成することもできる。
【００８１】
【実施例】
次に本発明の実施例及び比較例を詳述する。例１〜３１、３３，３５は実施例である。例３２，３４中の番号１〜２３は実施例であり、番号２４，２５は比較例である。以下においては、単に％と表示される場合、特に断らない限り、質量％を意味するものとする。Ｚ値とは遠心力場内の１点に作用する力の大小を比較するため、遠心加速度と重力加速度との比として定義した無次元数を意味する。以下の実施例で使用した測定や評価は下記の方法によった。
【００８２】
（粒径測定）
粉末をシクロヘキサンに添加し、日機装社製マイクロトラック９３４０−ＵＰＡを使用し、レーザー光を用いる動的光散乱法により測定した。
【００８３】
透過型電子顕微鏡による観察には日立製作所性透過型電子顕微鏡Ｈ−９０００を使用した。走査型電子顕微鏡による観察には日立製作所製走査型電子顕微鏡Ｓ−８００を使用した。
【００８４】
（金属含有組成物の熱処理）
金属含有組成物の１００質量部に６質量部のイミダゾール系潜在性硬化剤を加え、１６０℃で６０分熱処理して硬化（架橋）組成物を得た。
【００８５】
（硬化組成物の断面観察）
金属含有組成物の熱処理で得た硬化組成物を切断し、０．１ｍｍ２の断面面積上にある金属または金属と導電性粒子とによって構成される針状形状、樹枝形状、いがぐり形状および不定形連結形状等の形状を、日立製作所製走査型電子顕微鏡Ｓ８００を使用し、５００倍、１０００倍、５０００倍、１００００倍のいずれかの倍率で観察した。
【００８６】
［例１］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＡｇ超微粒子粉を次のようにして調製した。ガラス容器内で、蒸留水１０００ｇに硫酸鉄（ＩＩ）七水和物１９４ｇとクエン酸三ナトリウム二水和物３６２ｇとを溶解した。これに１０％の硝酸銀水溶液６２５ｇを添加し撹拌した。添加直後にＡｇ超微粒子が生成した。
【００８７】
その後、この液を５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物に蒸留水１０００ｇを加え、再解膠を施した。
【００８８】
この解膠液に１８％のクエン酸三ナトリウム水溶液１００ｇを添加し、沈殿操作を行った。この沈殿物を含む液を５０００ｒｐｍで３分間遠心分離処理し、前記と同様な方法により沈殿固形物と上澄みとを分離し、得られた固形物に蒸留水５００ｇを添加した後に限外濾過により脱塩濃縮処理を行い、Ａｇ固形分換算で９．８％のＡｇゾル液３７５ｇを得た。
【００８９】
このゾル液に５％濃度のステアリン酸のエタノール溶液を３７５ｇ添加し、撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ａｇ超微粒子の粉末を得た。
【００９０】
この粉末の粒径を測定したところ、平均粒径は１０ｎｍであった。図１４には、その粒度分布を示す。図１５に例示する透過型電子顕微鏡により観察された観察像（５０万倍）もこの平均粒径によく一致していた。
【００９１】
［例２］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＰｄ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに硫酸鉄（ＩＩ）七水和物９７０ｇとクエン酸三ナトリウム二水和物１８００ｇとを溶解した。これに１％の硝酸パラジウム（ＩＩ）水溶液２０００ｇを添加し撹拌した。添加１０分後にＰｄ超微粒子が生成した。
【００９２】
その後限外濾過により脱塩濃縮処理を行い、Ｐｄ固形分換算で１．５％のＰｄゾル液５００ｇを得た。このゾル液に２％濃度のステアリン酸のエタノール溶液を５００ｇ添加し、撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｐｄ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【００９３】
［例３］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＡｕ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに塩化金酸を１０．４ｇ、ヒドロキシプロピルセルロース（平均分子量２５０００）を１ｇ溶解した。これに１．１２％濃度の水酸化カリウム水溶液９５０ｇおよび３６％濃度のホルムアルデヒド水溶液１５０ｇの混合物を添加し撹拌した。添加直後にＡｕ超微粒子が生成した。
【００９４】
その後、溶液を４０℃に加温し１時間撹拌して、さらに限外濾過により脱塩濃縮処理を行い、Ａｕ固形分換算で１．２％のＡｕゾル液３００ｇを得た。
【００９５】
このゾル液に１％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ａｕ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【００９６】
［例４］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＲｕ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに塩化ルテニウム三水和物（Ｒｕ４０％）を１２．５ｇ溶解した。これに３％の水素化ホウ素ナトリウム水溶液１０００ｇを添加し撹拌した。添加直後にＲｕ超微粒子が生成した。
【００９７】
その後、限外濾過により脱塩濃縮処理を行い、Ｒｕ固形分換算で１．５％のＲｕゾル液３１０ｇを得た。このゾル液に３％濃度のステアリン酸のエタノール溶液を２７０ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｒｕ超微粒子の粉末を得た。この粉末の平均粒径は５ｎｍであった。
【００９８】
［例５］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＡｇ−Ｐｄ超微粒子（合金）を次のようにして調製した。ガラス容器内で、蒸留水１０００ｇに硫酸鉄（ＩＩ）七水和物１９４ｇとクエン酸三ナトリウム二水和物３６２ｇとを溶解した。これに１０％の硝酸銀水溶液６２５ｇと１％の硝酸パラジウム（ＩＩ）水溶液２００ｇとの混合溶液を添加し撹拌した。添加直後にＡｇ−Ｐｄ超微粒子が生成した。
【００９９】
その後、溶液を５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離を行い、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物に蒸留水１０００ｇを加え、再解膠を施した。
【０１００】
さらにこの解膠溶液に１８％のクエン酸三ナトリウム水溶液１００ｇを添加し、沈殿操作を行った。この沈殿物を含む溶液を５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、前記と同様な方法により沈殿固形物と上澄みを分離し、得られた固形物に蒸留水５００ｇを添加した後に、限外濾過により脱塩濃縮処理を行い、固形分換算で８．５％のＡｇ−Ｐｄゾル液８０ｇを得た。
【０１０１】
このゾル液に８％濃度のステアリン酸のエタノール溶液を１６０ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ａｇ−Ｐｄ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１０２】
［例６］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＰｔ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに硫酸鉄（ＩＩ）七水和物９７０ｇとクエン酸三ナトリウム二水和物１８００ｇを溶解した。これに１％の塩化白金酸水溶液２０００ｇを添加し撹拌した。添加１５分後にＰｔ超微粒子が生成した。
【０１０３】
その後限外濾過により脱塩濃縮処理を行い、Ｐｔ固形分換算で１．５％のＰｄゾル液３００ｇを得た。このゾル液に５％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｐｔ超微粒子の粉末を得た。この粉末の平均粒径は８ｎｍであった。
【０１０４】
［例７］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＲｅ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに三塩化レニウム（Ｒｅ４０％）を１０．５ｇ溶解した。これに３％の水素化ホウ素ナトリウム水溶液１０００ｇを添加し撹拌した。添加直後にＲｅ超微粒子が生成した。
【０１０５】
その後、限外濾過により脱塩濃縮処理を行い、Ｒｅ固形分換算で１．５％のＲｅゾル液１６０ｇを得た。このゾル液に５％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｒｅ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１０６】
［例８］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＯｓ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに三塩化オスミウム三水和物（Ｏｓ含有量６４％）を１０．５ｇ溶解した。これに３％の水素化ホウ素ナトリウム水溶液１０００ｇを添加し撹拌した。添加直後にＯｓ超微粒子が生成した。
【０１０７】
その後、限外濾過により脱塩濃縮処理を行い、Ｏｓ固形分換算で１．５％のＯｓゾル液２８０ｇを得た。このゾル液に５％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｏｓ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１０８】
［例９］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＩｒ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに三塩化イリジウム水和物（Ｉｒ含有量５３％）を１０．５ｇ溶解した。これに３％の水素化ホウ素ナトリウム水溶液１０００ｇを添加し撹拌した。添加直後にＩｒｒ超微粒子が生成した。
【０１０９】
その後、限外濾過により脱塩濃縮処理を行い、Ｉｒ固形分換算で１．５％のＩｒゾル液２００ｇを得た。このゾル液に５％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｉｒ超微粒子の粉末を得た。この粉末の平均粒径は１５ｎｍであった。
【０１１０】
［例１０］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＡｕ−Ｒｕ超微粒子（合金）を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに塩化ルテニウム三水和物（Ｒｕ４０％）１２．５ｇと塩化金酸１０．４ｇとを溶解した。これに３％の水素化ホウ素ナトリウム水溶液２０００ｇを添加し撹拌した。添加直後にＡｕ−Ｒｕ超微粒子が生成した。
【０１１１】
その後、限外濾過により脱塩濃縮処理を行い、Ａｕ−Ｒｕ固形分換算で１．５％のＡｕ−Ｒｕゾル液３５０ｇを得た。このゾル液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ａｕ−Ｒｕ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１１２】
［例１１］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＡｕ−Ｐｄ超微粒子（合金）を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに塩化金酸１０．４ｇを溶解した。これに１％の硝酸パラジウム（ＩＩ）水溶液２０００ｇを添加し撹拌した。さらに、この混合溶液に、３％の水素化ホウ素ナトリウム水溶液２０００ｇを添加し撹拌した。添加直後にＡｕ−Ｐｄ超微粒子が生成した。
【０１１３】
その後、限外濾過により脱塩濃縮処理を行い、Ａｕ−Ｐｄ固形分換算で１．５％のＡｕ−Ｐｄゾル液３００ｇを得た。このゾル液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ａｕ−Ｐｄ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１１４】
［例１２］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＡｕ−Ａｇ超微粒子（合金）を次のようにして調製した。ガラス容器内で、カリウムによりｐＨを１３に調整したアルカリ性溶液１０００ｇに水酸化金１０．５ｇを溶解した。これに５％濃度の硝酸銀水溶液２００ｇを添加し撹拌した。さらに、この混合溶液に、クエン酸三ナトリウム二水和物３０ｇを添加し撹拌した。この溶液を９５℃まで加温し、撹拌したところ、Ａｕ−Ａｇ超微粒子が生成した。
【０１１５】
その後、限外濾過により脱塩濃縮処理を行い、Ａｕ−Ａｇ固形分換算で１．５％のＡｕ−Ａｇゾル液１００ｇを得た。このゾル液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ａｕ−Ａｇ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１１６】
［例１３］
（金属粒子粉Ａの調製）
金属粒子粉ＡとしてのＩｎ超微粒子を次のようにして調製した。ガラス容器内で、蒸留水１００００ｇに三塩化ルテニウム三水和物１２．５ｇを溶解した。この溶液を９０℃に加熱し、撹拌しながら、３％の水素化ホウ素ナトリウム水溶液２０００ｇを添加した。添加直後にＩｎ超微粒子が生成した。
【０１１７】
その後、限外濾過により脱塩濃縮処理を行い、Ｉｎ固形分換算で１．５％のＩｎゾル液２５０ｇを得た。このゾル液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出し、この固形物を減圧室温乾燥し、Ｉｎ超微粒子の粉末を得た。この粉末の平均粒径は１０ｎｍであった。
【０１１８】
［例１４］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＡｇ粒子を次のようにして調製した。比表面積が０．６ｍ２／ｇのＡｇ粉１０ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで２００分間解膠処理を行い、Ａｇ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に、３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し、撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離を行い、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ａｇ粒子の粉末を得た。この粉末の平均粒径は９００ｎｍであった。走査型電子顕微鏡により観察された観察像もこの平均粒径によく一致していた。
【０１１９】
［例１５］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＲｕ粒子を次のようにして調製した。比表面積が０．１ｍ２／ｇのＲｕ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｒｕ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｒｕの粉末を得た。この粉末の平均粒径は１０００ｎｍであった。
【０１２０】
［例１６］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＮｉ粒子を次のようにして調製した。カルボニルニッケルの分解によって生成した比表面積が０．１４ｍ２／ｇのＮｉ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｎｉ懸濁液９０ｇを得た。得られた懸濁液を１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｎｉの粉末を得た。この粉末の平均粒径は１５００ｎｍであった。
【０１２１】
［例１７］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＳｎ粒子を次のようにして調製した。アトマイズ法によって生成した比表面積が０．３ｍ２／ｇのＳｎ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｓｎ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｓｎの粉末を得た。この粉末の平均粒径は１２００ｎｍであった。
【０１２２】
［例１８］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＡｌ粒子を次のようにして調製した。アトマイズ法によって生成した比表面積が０．１ｍ２／ｇのＡｌ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ａｌ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ａｌの粉末を得た。この粉末の平均粒径は１５００ｎｍであった。
【０１２３】
［例１９］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＺｎ粒子を次のようにして調製した。アトマイズ法によって生成した比表面積が０．１ｍ２／ｇのＺｎ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｚｎ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｚｎの粉末を得た。この粉末の平均粒径は１５００ｎｍであった。
【０１２４】
［例２０］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＷ粒子を次のようにして調製した。電解還元析出法によって生成した比表面積が０．１ｍ２／ｇのＷ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｗ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｗの粉末を得た。この粉末の平均粒径は１９００ｎｍであった。
【０１２５】
［例２１］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＩｎ粒子を次のようにして調製した。電解析出法によって生成した比表面積が０．１ｍ２／ｇのＩｎ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｉｎ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を８００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｉｎの粉末を得た。この粉末の平均粒径は１８００ｎｍであった。
【０１２６】
［例２２］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＣｕ粒子を次のようにして調製した。電解析出法によって生成した比表面積が０．２ｍ２／ｇのＣｕ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｃｕ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を５００ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｃｕの粉末を得た。この粉末の平均粒径は１５００ｎｍであった。
【０１２７】
［例２３］
（金属粒子粉Ｂの調製）
金属粒子粉ＢとしてのＣｏ粒子を次のようにして調製した。還元析出法によって生成した比表面積が０．２ｍ２／ｇのＣｏ粉８ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで５００分間解膠処理を行い、Ｃｏ懸濁液９０ｇを得た。得られた懸濁液を、１０００ｒｐｍ（Ｚ値１１０）で３分間遠心分離処理を行い、粗大粒子を沈降させ、上澄み懸濁液を分離した。この上澄み懸濁液に３％濃度のステアリン酸のエタノール溶液を４５０ｇ添加し撹拌を行った後、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、Ｃｏの粉末を得た。この粉末の平均粒径は１９００ｎｍであった。
【０１２８】
［例２４］
（導電性粒子粉Ｃの調製）
導電性粒子粉ＣとしてのＡｇ粒子を次のようにして調製した。比表面積が０．０２ｍ２／ｇのＡｇ粉１０ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで３０分間解膠処理を行い、Ａｇ懸濁液９０ｇを得た。得られた懸濁液を、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理を行い、粒子を沈降させた。この沈殿物を３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のＡｇ粉末を得た。この粉末の平均粒径は５μｍであった。走査型電子顕微鏡により観察された観察像もこの平均粒径によく一致していた。
【０１２９】
［例２５］
（導電性粒子粉Ｃの調製）
導電性粒子粉ＣとしてのＲｕ粒子を次のようにして調製した。比表面積が０．０３ｍ２／ｇのＲｕ粉１０ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで３０分間解膠処理を行い、Ｒｕ懸濁液９０ｇを得た。得られた懸濁液を５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理を行い、粒子を沈降させた。この沈殿物を３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のＲｕ粉末を得た。この粉末の平均粒径は１６μｍであった。
【０１３０】
［例２６］
（導電性粒子粉Ｃの調製）
導電性粒子粉ＣとしてのＣｕ粒子を次のようにして調製した。比表面積が０．０４ｍ２／ｇの電解析出法により生成されたＣｕ粉１０ｇにアルコール８０ｇ、アセチルアセトン５ｇを加え、サンドミルで３０分間解膠処理を行い、Ｃｕ懸濁液９０ｇを得た。得られた懸濁液を、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理を行い、粒子を沈降させた。この沈殿物を３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のＣｕ粉末を得た。この粉末の平均粒径は２０μｍであった。
【０１３１】
［例２７］
（導電性粒子粉Ｃの調製）
導電性粒子粉ＣとしてのＩＴＯ（錫固溶型酸化インジウム）粒子を次のようにして調製した。ガラス容器内で、蒸留水１０００ｇに塩化錫（ＩＶ）（無水）５ｇを加え溶解液とした。また、別の蒸留水１０００ｇに三塩化インジウム（無水）４０ｇを加え溶解液とした。この２種類の溶解液を混合した後、４０℃に保った１．１２％の水酸化カリウム水溶液中に混合液を滴下添加し、水酸化物を得た。この水酸化物を含有する溶液をさらに、９０℃に加温し６時間撹拌した。この加温処理により溶液中の水酸化物は凝集構造を形成した。
【０１３２】
得られた凝集構造を形成したインジウム−錫水酸化物から不純イオン分を脱塩操作により除去した後、窒素雰囲気下で８００℃で２時間焼成し、錫含有酸化インジウム粉を得た。得られた錫含有酸化インジウム粉１０ｇをｐＨ５．５に調整した硝酸酸性水溶液５０ｇに添加後、サンドミルで５分間解膠処理を行い、錫含有酸化インジウム固形分換算で１２％の錫含有酸化インジウム懸濁液４０ｇを得た。
【０１３３】
得られた懸濁液を、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理を行い、粒子を沈降させた。この沈殿物を３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のＩＴＯ粉末を得た。この粉末の平均粒径は２μｍであった。
【０１３４】
［例２８］
（導電性粒子粉Ｃの調製）
導電性粒子粉ＣであるＡＴＯ（アンチモン固溶型酸化錫）粒子を次のようにして調製した。ガラス容器内で、蒸留水１０００ｇに酒石酸カリウムアンチモニル５ｇを加え溶解液とした。また、別の蒸留水１０００ｇに塩化錫（ＩＶ）（無水）４０ｇを加え溶解液とした。この２種類の溶解液を混合した後、４０℃に保った１．５％の水酸化カリウム水溶液中に混合液を滴下添加し、錫−アンチモン水酸化物を得た。この水酸化物を含有する溶液をさらに、９０℃に加温し６時間撹拌した。この加温処理により溶液中の水酸化物は凝集構造を形成した。
【０１３５】
得られた凝集構造を形成した水酸化物から不純イオン分を脱塩操作により除去した後、大気雰囲気下で５５０℃で２時間焼成し、アンチモン含有酸化錫粉を得た。
【０１３６】
得られたアンチモン含有酸化錫粉１０ｇをｐＨ４．５に調整した硝酸酸性水溶液５０ｇに添加後、サンドミルで５分間解膠処理を行い、アンチモン含有酸化錫固形分換算で１６％のアンチモン含有酸化錫粒子ゾル液３５ｇを得た。
【０１３７】
得られた懸濁液を、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理を行い、粗大粒子を沈降させた。この沈殿物を３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のＡＴＯ粉末を得た。この粉末の平均粒径は３μｍであった。
【０１３８】
［例２９］
（導電性粒子粉Ｃの調製）
導電性粒子粉ＣであるＲｕＯ２（酸化ルテニウム）粒子を次のようにして調製した。ガラス容器内で、蒸留水１０００ｇに塩化ルテニウム三水和物（Ｒｕ４０％）を１２．５ｇ加え溶解液とした。４０℃に保った１．５％の水酸化ナトリウム水溶液中に、塩化ルテニウムの溶解液を滴下添加し、水酸化物を得た。この水酸化物を含有する溶液をさらに、９０℃に加温し６時間撹拌した。この加温処理により溶液中の水酸化物は凝集構造を形成した。
【０１３９】
得られた凝集構造を形成したルテニウム水酸化物から不純イオン分を脱塩操作により除去した後、大気下で８００℃で２時間焼成し、酸化ルテニウム粉を得た。得られた酸化ルテニウム粉５ｇをｐＨ５．５に調整した硝酸酸性水溶液５０ｇに添加後、サンドミルで５分間解膠処理を行い、酸化ルテニウム固形分換算で３％の酸化ルテニウム懸濁液４０ｇを得た。得られた懸濁液を、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理を行い、粗大粒子を沈降させた。
【０１４０】
この沈殿物を３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のＲｕＯ２（酸化ルテニウム）粉末を得た。この粉末の平均粒径は１０μｍであった。
【０１４１】
［例３０］
（導電性粒子粉Ｃの調製）
導電性粒子粉Ｃであるカーボンナノチューブを次のようにして調製した。アーク放電法によって得られたカーボンナノチューブ（チューブ長さ０．５μｍ〜２５μｍ、直径０．３〜２ｎｍ）のカーボンナノチューブ粉１０ｇを３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、導電性粒子のカーボンナノチューブ粉末を得た。この粉末の平均粒径は１９μｍであった。
【０１４２】
［例３１］
（導電性粒子粉Ｃの調製）
導電性粒子粉Ｃであるグラファイト構造を一部有する導電性カーボンを次のようにして調製した。粒子中に一部グラファイト構造を有する導電性カーボン（商品名：ケッチェンブラック）の１０ｇを３％濃度のステアリン酸のエタノール溶液８００ｇに添加し、超音波で１００分分散処理を行ったあと、５０００ｒｐｍ（Ｚ値２７４２）で３分間遠心分離処理し、上澄み液を廃棄し、沈殿した固形物を取り出した。この固形物を減圧室温乾燥し、グラファイト構造を一部有する導電性カーボンの粉末を得た。この粉末の平均粒径は３μｍであった。
【０１４３】
［例３２］
（電気的接続用金属含有組成物の調製）
前記記載の金属粒子粉末Ａと、金属粒子粉末Ｂと、樹脂と、場合によっては導電性粒子粉Ｃとを、表１の組成比率で混合し、自動乳鉢で１時間粗混練を行った。
【０１４４】
その後、３本ロールによる混練を６０分間実施し、さらに遠心脱泡装置で１時間脱泡処理を行い、電子デバイスの電気的接続用金属含有組成物を調製した。
【０１４５】
番号１〜２３は、粘度が８００ｄＰａ・ｓ程度の範囲にあり、流動性に優れていた。
【０１４６】
なお、粒度分布を測定した結果、番号１〜２３の例は、粒径が２０ｎｍ以下の金属粒子の濃度と、粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子の濃度と、粒径が２０００ｎｍを超え２０μｍ以下の導電性粒子の濃度とに関する、上記態様３の要件を満たしていた。
【０１４７】
また、これらの粒度分布には、番号３についての図１６の累積粒度分布の変曲点の位置からから理解できるように、２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域とにそれぞれピークが存在し、場合によってはさらに２０００ｎｍを超え２０μｍ以下の粒径領域にもピークが存在していた。
【０１４８】
［例３３］
（電気的接続用金属含有組成物の、塗布性、印刷性、充填性評価）
表１の番号１〜８について、スクリーン印刷により、深さ３０μｍ、直径５０μｍのビアホールを有する、線幅が１５μｍの配線パターンを作製したが、いずれも良好なパターンが得られた。
【０１４９】
［例３４］
（硬化組成物の評価）
図２３の側面図，図２４の平面図に示すように、厚さ５．０ｍｍのガラスエポキシ基板に設けられた、２個の孔の組みごとに厚さ１５μｍの銅電極１０１で連結してなる孔径５０μｍ、深さ６０μｍのビアホール１０２に表１に示す組成の金属含有組成物のぺ一ストをスクリーン印刷法により充填し、上記「硬化組成物の作製」の条件に従い、処理し、硬化（架橋）組成物を適用した基板を得た。
【０１５０】
その後、研磨により基板上の余分なペ一ストを除去し、化学銅メッキ、電気銅メッキ、配線パターン化を順に行い、厚さ３０μｍの銅電極１０３を作製し、３０００孔が直列に連結したデージーチェーン回路基板を形成した。
【０１５１】
得られたデージーチェーン回路基板について、上記３０００孔の端同士の抵抗値を測定することにより、孔に充填された硬化組成物の抵抗値（初期抵抗値）を測定した。
【０１５２】
また、冷風吹き込み式恒温槽と吹き込み式熱風恒温槽とを使用し、デージーチェーン回路基板について、１サイクルが−６５℃×３０分と１２５℃×３０分との組み合わせよりなる冷熱衝撃試験を１０００サイクル実施した後、上記３０００孔の端同士の抵抗値を測定した。−６５℃×３０分と１２５℃×３０分との切り替えは自動的に行われ、１回の切り替えに要する時間は３秒／回程度であった。
【０１５３】
得られた初期抵抗値と冷熱衝撃試験後の抵抗値の変化率とを表２に示す。実施例は比較例に比し、いずれも導電性と耐久性とに優れていることが理解できる。
【０１５４】
なお、硬化組成物の抵抗値は、具体的には次のようにして求めた。
【０１５５】
（ａ）上記３０００孔の端同士の抵抗値をペーストが充填されている孔の数（３０００）で除して、１個のビア孔に埋められた硬化組成物の抵抗値を算出する。
【０１５６】
（ｂ）１個のビア孔あたりの抵抗値に、電気が流れる方向に垂直となる面の断面積（すなわち直径が５０μｍのビア孔の断面積）を乗じ、電気が流れる方向に平行となる方向の距離（すなわちビア孔の深さ方向の距離である６０μｍ）で除して、ビア孔一個に充填された硬化組成物の抵抗値を算出する。
【０１５７】
［例３５］
（硬化組成物の断面観察）
本発明に係る金属含有組成物の熱処理で得た硬化組成物を切断し、０．１ｍｍ２の断面面積上を観察した結果、図１〜１３に示したような、針状形状、樹枝形状、いがぐり形状および不定形連結形状が観察された。図１７〜２２は、日立製作所製走査型電子顕微鏡Ｓ−８００を使用して撮影した断面写真である。図１７は１０００倍、図１８は１００００倍、図１９は５０００倍、図２０〜２２は１００００倍の倍率で撮影した。
【０１５８】
【表１】
【表２】
【表３】
【表４】
【発明の効果】
本発明により、流動性が高く、塗布性、印刷性、充填性に優れ、熱処理等のエネルギー付与により、導電性と耐久性とにすぐれた電子デバイスの電気的接続用導電性組成物を与えることができる金属含有組成物が得られる。
【図面の簡単な説明】
【図１】針状形状の金属結合体を例示するモデル図。
【図２】針状形状の金属結合体を例示する他のモデル図。
【図３】針状形状の金属結合体を例示する他のモデル図。
【図４】針状形状の金属結合体を例示する他のモデル図。
【図５】針状形状の金属結合体を例示する他のモデル図。
【図６】針状形状の金属結合体を例示する他のモデル図。
【図７】樹枝形状の金属結合体を例示するモデル図。
【図８】樹枝形状の金属結合体を例示する他のモデル図。
【図９】いがぐり形状の金属結合体を例示するモデル図。
【図１０】いがぐり形状の金属結合体を例示する他のモデル図。
【図１１】いがぐり形状の金属結合体を例示する他のモデル図。
【図１２】いがぐり形状の金属結合体を例示する他のモデル図。
【図１３】不定形連結形状の金属結合体を例示する他のモデル図。
【図１４】金属粒子粉ＡとしてのＡｇ微粒子粉の粒度分布図。
【図１５】金属粒子粉ＡとしてのＡｇ微粒子粉の透過型電子顕微鏡による観察像の写真。
【図１６】２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域と、さらに２０００ｎｍを超え２０μｍ以下の粒径領域とにピークが存在している様子を示す粒度分布図。
【図１７】本発明に係る金属含有組成物の熱処理で得た硬化組成物の他の断面写真。
【図１８】本発明に係る金属含有組成物の熱処理で得た硬化組成物の他の断面写真。
【図１９】本発明に係る金属含有組成物の熱処理で得た硬化組成物の他の断面写真。
【図２０】本発明に係る金属含有組成物の熱処理で得た硬化組成物の他の断面写真。
【図２１】本発明に係る金属含有組成物の熱処理で得た硬化組成物の他の断面写真。
【図２２】本発明に係る金属含有組成物の熱処理で得た硬化組成物の他の断面写真。
【図２３】硬化組成物の評価用基板の側面モデル図。
【図２４】硬化組成物の評価用基板の平面モデル図。
【符号の説明】
１ 棒状または針状の形状
２ ３つに分岐した形状
３ いがぐり形状
４ 空隙
５ 不定形連結形状
１０１ （下部）銅電極
１０２ ビアホール
１０３ （上部）銅電極[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal-containing composition for electrical connection of electronic devices.
[0002]
[Prior art]
Conventionally, a conductive composition such as silver powder and a metal-containing composition containing a resin (sometimes referred to as a conductive paste) is applied, printed or filled, and cured to form a conductive composition, a printed wiring board, A method of forming an electric circuit (wiring conductor) such as an electronic component or a contact hole filling member is generally known. (For example, refer
[0003]
In an electrical connection site formed using such a metal-containing composition, physical contact occurs between metal particles such as silver particles in the conductive composition, and conductivity is expressed by the formed conductive path. ing. For this reason, formation of a conductive path is indispensable in order to increase conductivity. From the viewpoint of forming a conductive path, the ratio of the conductive filler in the metal-containing composition is increased, or the shape of the conductive filler is flattened. Attempts to further increase the contact between fillers are known (for example, see Patent Document 1).
[0004]
However, in general, a metal-containing composition is composed of a conductive filler that is a powder, a resin, a diluent, and the like. If the ratio of the conductive filler is increased too much, the amount of resin and diluent decreases, and the metal-containing composition itself Loses fluidity or becomes powdery, making application, printing and filling difficult. Moreover, since the tap density of the flat or dendritic conductive filler is lower than that of the spherical shape, the additive concentration in the metal-containing composition is lower than that of the spherical conductive filler. Furthermore, since the requirement of the fluidity | liquidity with respect to metal-containing composition itself becomes so high that the circuit formation part becomes fine, such a fault becomes more remarkable with the trend of the miniaturization of an electronic device.
[0005]
On the other hand, there is a demand for suppression of deterioration, that is, improvement in durability, for a circuit made of a conductive composition obtained by heat-treating a metal-containing composition or an electrical connection site in a contact hole. As the deterioration of the electrical connection portion made of the conductive composition in the circuit or contact hole, the thermal expansion coefficient of the constituent material in the conductive composition is not uniform, It is known that a fine crack is generated in the connection site and the conductive path is cut.
[0006]
The conductive composition is obtained by solidifying and connecting conductive fillers with a resin, and a conductive path is formed by physical contact between the conductive fillers. The thermal expansion coefficients of copper and silver, which are representative conductive filler materials, are 17 × 10 respectively. -6 ℃ -1 19 × 10 -6 ℃ -1 And the thermal expansion coefficient of the epoxy resin generally used is 50 × 10 -6 ~ 100 × 10 -6 ℃ -1 In view of the above, it can be said that the conventional metal-containing composition that relies solely on the physical contact of the filler with respect to the heat cycle of thermal expansion / contraction has a limit in improving the durability.
[0007]
[Patent Document 1]
JP-A-9-92026 (paragraph number 0016)
[0008]
[Non-Patent Document 1]
“Electronic Materials”, Industrial Research Committee, October 1994, p. 42-46
[0009]
[Non-Patent Document 2]
“J. Sol-Gel Science Technology” (Netherlands), Kluwer Academic Publishers, 2001, Vol. 22, p. 151-166
[0010]
[Non-Patent Document 3]
Tsuda Shigeo, “Electrically Conductive Oxide”, Augmented Third Edition, Hanafusa, July 25, 1987, p. 9-11
[0011]
[Non-Patent Document 4]
"Technology of transparent conductive film", 1st edition, published by Ohm, March 30, 1990, p. 51
[0012]
[Non-Patent Document 5]
“Surface Science”, Elsevier Science Publishers, 1992, vol. 260, p. 116-128
[0013]
[Problems to be solved by the invention]
The present invention provides a conductive composition for electrical connection of electronic devices having high fluidity, excellent coating properties, printability, filling properties, and excellent electrical conductivity and durability by applying energy such as heat treatment. It is an object to provide a metal-containing composition that can be used.
[0014]
Still other objects and advantages of the present invention will become apparent from the following description.
[0015]
[Means for Solving the Problems]
The first aspect of the present invention is a metal particle powder having an average particle size of 20 nm or less (hereinafter, “metal particle powder having an average particle size of 20 nm or less” is also referred to as “metal particle powder A”) and an average particle size of 50 nm. Metal particle powder having a particle size of 2000 nm or less (hereinafter, “metal particle powder having an average particle size of 50 nm or more and 2000 nm or less” is also referred to as “metal particle powder B”), a resin, and in some cases, the average particle size may be more than 2000 nm and 20 μm. A metal-containing composition for electrical connection of an electronic device, comprising the following conductive particle powder (hereinafter, “conductive particle powder having an average particle diameter of more than 2000 nm and not more than 20 μm” is also referred to as “conductive particle powder C”): It is a thing.
[0016]
In the second aspect of the present invention, the concentration of the metal particle powder A in the metal-containing composition is a mass%, the concentration of the metal particle powder B is b mass%, and the concentration of the conductive particle powder C is c mass%. If
a: b is between 3:97 and 90:10,
(A + b): c is between 100: 0 and 60:40,
50 ≦ (a + b + c) ≦ 95
It is a metal containing composition of the said
[0017]
The third aspect of the present invention includes metal particles, a resin, and optionally conductive particles,
The mass ratio of the metal particles having a particle size of 20 nm or less and the metal particles having a particle size of 50 nm or more and 2000 nm or less to the total amount of the metal particles and the conductive particles is in the range of 3:97 to 90:10. , Including metal particles having a particle size of 20 nm or less and metal particles having a particle size of 50 nm or more and 2000 nm or less in a ratio of 60 to 100% by mass, and containing 40 to 0% by mass of conductive particles exceeding 2000 nm and 20 μm or less Including as a percentage,
A metal-containing composition for electrical connection of an electronic device.
[0018]
According to a fourth aspect of the present invention, in the metal-containing composition for electrical connection of an electronic device comprising metal particles, a resin, and optionally conductive particles,
Among the particle size distribution by the measurement method based on dynamic light scattering of the solid particles present in the metal-containing composition, there are peaks in the particle size region of 20 nm or less and the particle size region of 50 nm or more and 2000 nm or less,
In some cases, there is a peak in the particle size region of more than 2000 nm and 20 μm or less.
A metal-containing composition for electrical connection of an electronic device.
[0019]
In the fifth aspect of the present invention, the metal particle powder A and the metal particle powder B are respectively Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In. , Including at least one of metal particles of at least one element selected from the group consisting of Co, W, and Mo and alloy particles containing the element,
When the conductive particle powder C is present, the conductive particle powder C is
Metal particles of at least one element selected from the group consisting of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo When,
Alloy particles containing the element;
Conductive oxide particles containing at least one element selected from the group consisting of In, Ru, Re, Os, Ir, and Sn;
At least one conductive carbon compound selected from the group consisting of graphite, carbon compounds having a graphite structure, and carbon nanotubes;
It is a metal containing composition of the said
[0020]
In a sixth aspect of the present invention, metal particles having a particle size of 20 nm or less and metal particles having a particle size of 50 nm or more and 2000 nm or less are respectively Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu. , Ni, Sn, Al, Zn, In, Co, W and at least any one of metal particles of an element selected from the group consisting of Mo and alloy particles containing the element,
In the case where conductive particles of more than 2000 nm and 20 μm or less are present, the conductive particles are
Metal particles of at least one element selected from the group consisting of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo When,
Alloy particles containing the element;
Conductive oxide particles containing at least one element selected from the group consisting of In, Ru, Re, Os, Ir, and Sn;
At least one conductive carbon compound selected from the group consisting of graphite, carbon compounds having a graphite structure, and carbon nanotubes;
It is a metal containing composition of the said
[0021]
In the seventh aspect of the present invention, the resin is an epoxy curable resin, a phenol curable resin, a melamine curable resin, a silicone curable resin, an acrylic resin, polyethylene, polystyrene, polypropylene, polyvinyl chloride, polyimide. The metal-containing composition according to any one of the
[0022]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings, tables, examples and the like. In addition, these figures, tables, examples, etc., and explanations are only examples of the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.
[0023]
The metal-containing composition for electrical connection of an electronic device according to the present invention is a paste-like composition containing metal particle powder A, metal particle powder B, and resin.
[0024]
The metal-containing composition according to the present invention can be made into a paste having an appropriate viscosity, can be sufficiently filled into a fine via hole having a diameter of 50 μm or less, and has a line width of 20 μm by coating, printing or the like. The following fine circuit wiring can also be formed satisfactorily. As the viscosity of the metal-containing composition, for example, a 10-2000 dPa · s paste having good handleability, applicability, printability, and fillability can be easily produced.
[0025]
The metal-containing composition according to the present invention is a conductive composition obtained by filling a via hole, forming a wiring pattern, applying energy, curing a curable resin, and softening or melting a thermoplastic resin. In this case, surface melting occurs in metal particles having a particle size of 20 nm or less. In addition, since the particle size distribution is sharp at this level of fine particles, there is no inconvenience even if it is actually considered that surface melting occurs in the metal particle powder A.
[0026]
In the following, as the resin contained in the metal-containing composition, mainly the curable resin or the combination of the curable resin and the thermoplastic resin has been described, but the resin contained in the metal-containing composition according to the present invention. As a case, only a thermoplastic resin may be used. When only the thermoplastic resin is used in this way, for example, “cured” is read as “solidified” and “cured composition” is read as “solidified composition” within the scope of the gist of the present invention. .
[0027]
At this time, when the metal particle powder B is in the vicinity of the melting portion, when energy is applied, the connection between the metal particles is accelerated, and the metal combined body starts self-growth while entraining the metal particle powder B. . This self-growth mechanism ends when the surface energy of the metal particles of the metal particle powder A becomes stable.
[0028]
The surface melting of the metal particles occurs due to abnormal lattice vibrations of the particle surface elements, and the surface melting temperature decreases as the average particle size decreases and the surface atomic ratio increases. The surface atomic ratio (the ratio of the atoms present on the particle surface among the total number of particles) is calculated to be 20% for particles having a diameter of 10 nm, 10% for particles having a diameter of 20 nm, and 3% or less for particles having a diameter of 70 nm. It becomes. Due to this, in the case of silver, the melting point of the bulk body is 961 ° C., but in the case of particles having a diameter of 10 nm, surface melting is observed at around 160 ° C. (For example, refer
[0029]
At this time, when there is no metal particle powder B in the metal-containing composition and the metal-containing composition is prepared only with the metal particle powder A and the resin, the metal particles present therein are fine, In many cases, the connection is insufficient. Further, in order to facilitate metal bonding between particles, when a paste-like metal-containing composition having high fluidity is prepared with the metal particle powder A and a solvent, the connection between the particles is improved, but the solvent is improved. It is necessary to heat the product to the boiling point or higher, and the process cost is high, and the quality of other electronic components is likely to deteriorate. Such behavior can be easily observed, for example, with fine Ag particles.
[0030]
Furthermore, when a paste-like metal-containing composition was prepared using only the metal particle powder A, a large metal particle powder having an average particle diameter exceeding 2000 nm, and a resin, the average of the surface after the metal particle powder A was melted. Self-growth is difficult to occur while entraining metal particle powder having a particle size exceeding 2000 nm. This is because the surface melting of the fine metal particles depends on the abnormal lattice vibration of atoms existing on the surface, and after the surface melting occurs in the fine metal particles, the average particle size exceeds 2000 nm. This is because the surface atomic ratio is significantly reduced and the melting phenomenon stops.
[0031]
In the metal-containing composition according to the present invention, by arranging the particles of the metal particle powder B in the vicinity of the fine metal particles, after the fine metal particles are melted on the surface, the bonded body itself can be bonded to the metal particle powder B. Since it is not yet sufficiently large, it is not stable in terms of surface energy, and it is considered that self-growth can be continued while entraining particles existing in the vicinity thereof.
[0032]
The mechanism of self-growth is not necessarily clear, but is thought to be due to the effect of surface melting of nano-order particles by particle size, the spatial concentration gradient of the melted portion, and the accompanying local temperature gradient. Accordingly, it is likely that the shape is more anisotropic than the isotropic shape, and as a result, the shape is a needle shape, a dendritic shape, or the like. Thus, looking at the cross section of the conductive composition thus produced, it was observed that even when only spherical particles were used, a needle-like shape, a dendritic shape, a corrugated shape, an irregularly connected shape, and the like were newly generated. Become so. The new occurrence of needle-like shape, dendritic shape, cormorant shape, irregularly connected shape, etc. is that even when the metal particle powder B has an acicular shape, dendritic shape, corrugated shape, etc., it is conductive. It can be easily known that the shape in the cross section of the composition is different from the shape in the metal-containing composition.
[0033]
In addition, such needle-like shape, dendritic shape, burrow shape, and irregular connection shape are the results of connection between particles. Therefore, even when subjected to a heat cycle, it is possible to prevent a fine crack from being generated in the electrical connection portion or the conductive path from being cut.
[0034]
As a result, the metal-containing composition according to the present invention can provide a conductive composition for electrical connection of an electronic device having excellent conductivity and durability by applying energy such as heat treatment.
[0035]
Here, the needle-like shape means a rod-like or needle-
[0036]
The tree shape means a bent rod-like or needle-like shape or a
[0037]
As illustrated in FIGS. 9 to 12, the
[0038]
As shown in FIG. 13, the
[0039]
It is preferable that the aspect ratio of the protruding shape in the needle-like shape, the bent shape of the dendritic shape, the branched shape, or the counterbored shape is 3 or more. The ratio between L1 and W1 shown in FIGS. 1 to 12 is an example of the aspect ratio.
[0040]
Since the length (L) is not uniform, the aspect ratio adopts the value of the largest part. When it seems that there are a plurality of lengths (L) like L1 and L2 in FIG. 8, the larger one is adopted.
[0041]
Since the width (W) is not uniform, the value of the largest portion is employed, not the width of the end portion as shown by W2 in the figure or the width of the fine protrusion as shown by W3.
[0042]
The metal-containing composition according to the present invention may further contain conductive particle powder C.
[0043]
When there is the conductive particle powder C, during the curing of the metal-containing composition, the metal particles formed by the self-growth mechanism of the metal particle powder A and the metal particle powder B cause the gap between the particles of the conductive particle powder C. Since it can connect, it is preferable from the point of formation of a conductive path. Since the conductive particle powder C itself does not need to self-grow, a metal, a conductive oxide, a conductive carbon compound, or the like can be used. In the present invention, the particle size distribution and the average particle size are determined by a measurement method using dynamic light scattering.
[0044]
In the composition obtained by heat-treating the metal-containing composition according to the present invention at 160 ° C. for 60 minutes, arbitrarily selected 0.1 mm 2 At least one shape selected from the group consisting of a needle shape, a dendritic shape, a counterbored shape, and an irregularly connected shape, as described above, in at least one of the cross sections of It is preferable that 1 or more is contained. This is because sufficient conductivity can be secured as the conductive composition.
[0045]
When the concentration of the metal particle powder A in the metal-containing composition is a mass%, the concentration of the metal particle powder B is b mass%, and the concentration of the conductive particle powder C is c mass%, a: b is 3:97. ˜90: 10, (a + b): c is preferably between 100: 0 and 60:40, and preferably 50 ≦ (a + b + c) ≦ 95. (A + b): When c is between 100: 0 and 60:40, the self-growth is likely to occur easily. When c is not 0 (zero), the connection between metal particles can be promoted, and a: When b is between 3:97 and 90:10, a needle-like shape, a dendritic shape, a cormorant shape, an irregularly connected shape and the like are easy to grow, and when 50 ≦ (a + b + c) ≦ 95, This is because there are a large number of dendritic shapes, corrugated shapes, irregularly connected shapes, etc., and it becomes easy to ensure conductivity. If the above conditions are satisfied, it is possible to achieve excellent coating properties, printability, and filling properties while maintaining a high fluidity by appropriately maintaining the concentration of metal particles and conductive particles in the metal-containing composition, such as heat treatment. By applying energy, a conductive composition for electrical connection of an electronic device having excellent conductivity and durability can be obtained.
[0046]
The metal particle powder A and the metal particle powder B are each composed of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo. It is preferable to include at least one of metal particles of at least one element selected from the above and alloy particles containing the element.
[0047]
The electrical resistivity (specific resistance) of these elements is as follows: Ag: 1.63 μΩcm, Au: 2.2 μΩcm, Ru: 7.37 μΩcm, Pd: 10.55 μΩcm, Pt: 10.42 μΩcm, Re: 18.7 μΩcm , Os: 9.13 μΩcm, Ir: 5.07 μΩcm, Cu: 1.69 μΩcm, Ni: 30.6 μΩcm, Sn: 12.6 μΩcm, Al: 2.67 μΩcm, Zn: 5.96 μΩcm, In: 9.0 μΩcm, Co : 6.24 μΩcm, W: 5.5 μΩcm, Mo: 5.7 μΩcm, showing low values, both of which can be used.
[0048]
In the metal particle powder A and the metal particle powder B according to the present invention, it is important that the metal particles are connected to each other and self-growth in a paste-like metal-containing composition having fluidity when energy is applied.
[0049]
From the viewpoint of metal bonding or the like, the metal particle powder A and the metal particle powder B may be the same metal atomic species or a combination of metals that hardly inhibit self-growth. In the case of the same element type, there is no particular problem, and even if it is a combination of different element types, it is preferable if it is a combination that forms a complete solid solution. For example, there are combinations of Ag—Au, Ag—Pd, Pd—Au, Au—Cu, Ru—Re, and the like.
[0050]
Moreover, even if it is a combination which does not form a complete solid solution, it is preferable if it is a combination of metal species in which surface melting occurs in the metal particles of the metal particle powder A and it is easy to bond to the surface of the metal particles of the metal particle powder B.
[0051]
When the surface-dissolved metal species are bonded to other metal particles, a diffusion mechanism is passed. It is known that whether or not a certain metal moves to a different metal surface by a diffusion mechanism can be calculated from adsorption energy or the like (see, for example, Non-Patent Document 5). Therefore, it can determine suitably based on these.
[0052]
In the case of alloy particles, the electrical resistivity may be worse than in the case of a single metal depending on the combination of metals, but it is possible to easily select an appropriate one through experiments or the like.
[0053]
For example, Au-Ag (
[0054]
The electroconductive particle powder C which concerns on this invention means the powder of the particle | grains which have electroconductivity. The electrical resistivity of the particles is preferably 150 μΩcm or less. Therefore, particles of substances other than metal particles also belong to the category of conductive particles.
[0055]
The conductive particle powder C is at least any selected from the group consisting of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo. Conductive oxide particles containing at least one element selected from the group consisting of metal particles of one element, alloy particles containing the element, and In, Ru, Re, Os, Ir, and Sn And at least one selected from the group consisting of graphite, a carbon compound having a graphite structure, and a carbon nanotube.
[0056]
In the case of a conductive oxide, there is no specific electrical resistivity due to the composition, crystal structure, oxygen deficiency, etc., but generally the following values are known (for example,
[0057]
Of the conductive carbon compounds, graphite is a hexagonal hexagonal plate-like flat crystal with a carbon 6-membered ring forming a layered structure. is there. Further, among conductive carbons that are generally sold, there are those in which a part of the graphite structure is formed in the crystal, which is highly conductive and can be used.
[0058]
The carbon nanotube has a shape in which the graphite sheet is formed into a cylindrical shape, and a boundary condition occurs in the structure, and tube (n, m): chiral vector display (display when the structure from the graphene sheet is defined) In the method), 2n + m = 3 is preferable because it has metallic properties. Further, since the aspect ratio is remarkably high in shape, it can be used from the viewpoint of forming a conductive path.
[0059]
Unlike the conventional conductive composition in which the conductive path is formed by physical contact with the conductive filler, in the present invention, the particles are bonded to each other in the cured product regardless of the cross-linking and fixing action of the resin. , The bond is strong and the conductivity is high. In addition, the combined form is different from the form of particles that existed in advance in the metal-containing composition, and the aspect ratio is greatly changed, and it is easy to form a network with each other. Also contributes to structural stability during heat cycle.
[0060]
In addition, the effect equivalent to the metal-containing composition for electrical connection of an electronic device including the metal particle powder A, the metal particle powder B, and optionally the conductive particle powder C according to the present invention is the mixing of particles. When considered in a state, the metal particles and the resin, and in some cases, include conductive particles, the metal particles having a particle size of 20 nm or less and the particle size of 50 nm to 2000 nm with respect to the total amount of the metal particles and the conductive particles. The total amount of the metal particles having a particle size of 20 nm or less and the metal particles having a particle size of 50 nm or more and 2000 nm or less is 60 to 100 mass. It has been found that it can be realized with a metal-containing composition containing conductive particles with a ratio of 40% to 20% by mass exceeding 2000 nm and 20 μm or less.
[0061]
Also in the cured composition obtained in such a case, arbitrarily selected 0.1 mm 2 At least one shape selected from the group consisting of a metal, or a needle-like shape, a dendritic shape, a counterbored shape, and an irregularly connected shape, as described above, in at least one of the cross sections of It is preferable that one or more of is newly generated.
[0062]
The mass ratio of the metal particles having a particle size of 20 nm or less and the metal particles having a particle size of 50 nm or more and 2000 nm or less is in a mass ratio of 3:97 to 90:10 with respect to the total amount of the metal particles and the conductive particles. And a needle-like shape, a dendritic shape, a cormorant shape, an irregularly connected shape, etc. are easy to grow, and include 60% by mass or more in total of metal particles having a particle size of 20 nm or less and metal particles having a particle size of 50 nm to 2000 nm. This is because the self-growth of the metal particles easily occurs, and the connection between the metal particles is promoted when conductive particles having a diameter of more than 2000 nm and not more than 20 μm are present at a ratio of 40% by mass or less. The total of the metal particles having a particle size of 20 nm or less, the metal particles having a particle size of 50 nm or more and 2000 nm or less, and the conductive particles exceeding 2000 nm and 20 μm or less is 50 to 95% by mass in the metal-containing composition. Is preferred.
[0063]
If the above conditions are satisfied, it is possible to achieve excellent coating properties, printability, and filling properties while maintaining high fluidity by appropriately maintaining the concentration of metal particles and conductive particles in the metal-containing composition, such as heat treatment. By applying energy, a conductive composition for electrical connection of an electronic device having excellent conductivity and durability can be obtained.
[0064]
Further, from the viewpoint of the particle size distribution of the solid particles present in the metal-containing composition, in the metal-containing composition for electrical connection of an electronic device comprising metal particles, a resin, and optionally conductive particles, Of the particle size distribution measured by dynamic light scattering of solid particles present in the metal-containing composition, there are peaks in the particle size region of 20 nm or less and the particle size region of 50 nm or more and 2000 nm or less, respectively. The same effect can be realized even with a metal-containing composition having a peak in a particle size region exceeding 2000 nm and not more than 20 μm.
[0065]
Also in the cured composition obtained in such a case, arbitrarily selected 0.1 mm 2 At least one shape selected from the group consisting of a needle shape, a dendritic shape, a counterbored shape, and an irregularly connected shape, as described above, in at least one of the cross sections of It is preferable that one or more of is newly generated.
[0066]
The particles existing in the particle size region of 20 nm or less and the particle size region of 50 nm or more and 2000 nm or less are preferably substantially composed of metal particles.
[0067]
Here, the particle size distribution of the solid particles present in the metal-containing composition means that when other solid particles exist in addition to the metal particles and conductive particles, Means particle size distribution as solid particles.
[0068]
If there are peaks in the particle size region of 20 nm or less and the particle size region of 50 nm or more and 2000 nm or less, needle-like shapes, dendritic shapes, corrugated shapes, irregularly connected shapes, etc. easily grow, and self-growth of metal particles This is because, when a peak exists in a particle size region of more than 2000 nm and not more than 20 μm, the connection between the metal particles is promoted. Even when these conditions are satisfied, excellent coating properties, printability, and fillability can be realized while maintaining high fluidity by maintaining the concentration of metal particles and conductive particles in the metal-containing composition at an appropriate level. By applying energy such as heat treatment, it is possible to obtain a conductive composition for electrical connection of an electronic device having excellent conductivity and durability.
[0069]
In such a case, as in the case of the combination of the metal particle powder A, the metal particle powder B, and the conductive particle powder C in some cases, the metal particle having a particle size of 20 nm or less and the particle size of 50 nm or more and 2000 nm or less. And at least any one selected from the group consisting of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo. Or at least one of metal particles of one element and alloy particles containing the element, and when there are conductive particles of more than 2000 nm and 20 μm or less, the conductive particles are Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and metal particles of at least one element selected from the group consisting of Mo, and Alloy particles containing element, conductive oxide particles containing at least one element selected from the group consisting of In, Ru, Re, Os, Ir, Sn, graphite, a carbon compound having a graphite structure, and It is preferable to include at least one of at least one conductive carbon compound selected from the group consisting of carbon nanotubes.
[0070]
As an energy imparting method for producing the conductive composition of the present invention, at least one of heating, ultraviolet irradiation, X-ray irradiation, electron beam irradiation, and ultrasonic irradiation can be used. As a heating method, methods such as warm air heating and heat radiation can be used. The heating temperature and the treatment time can be appropriately determined based on the actually required characteristics.
[0071]
As the ultraviolet irradiation method, a low pressure UV lamp having a main wavelength of 254 nm or a high pressure UV lamp having a main wavelength of 365 nm can be used. In terms of energy, ultraviolet rays having a short wavelength are high energy, but it is preferable to determine appropriately in consideration of irradiation time and the like. Further, since ultraviolet energy is often used for curing the resin component, it is also possible to add a curing initiator that reacts and cures to ultraviolet light to the metal-containing composition. X-rays and electron beams are also high-energy radiation, and can be used from the viewpoint of imparting energy. In particular, an electron beam is preferable because only the irradiated portion can apply heat energy in a short time. Further, it is possible to cure the particles and the resin inside the metal-containing composition by irradiating with ultrasonic waves to generate heat energy. In the case of ultrasonic irradiation, it is possible to generate bubbles in an uncured metal-containing composition, and to cure using thermal energy at the time of the cleavage of the bubbles.
[0072]
The resin used in the present invention may be any resin as long as it imparts fluidity to the metal-containing composition at the stage before the metal-containing composition is cured, and the resin is solidified at the stage of completion of curing. However, a thermoplastic resin or the like may be used in combination or independently. Other resins may be included as long as not departing from the spirit of the present invention. Further, when the resin itself is solid, it may be dissolved in an organic solvent or a reactive diluent.
[0073]
The curable resin is preferably at least one curable resin selected from the group consisting of an epoxy curable resin, a phenol curable resin, a melamine curable resin, and a silicone curable resin. The thermoplastic resin is preferably at least one thermoplastic resin selected from the group consisting of acrylic resin, polyethylene, polystyrene, polypropylene, polyvinyl chloride, polyimide, polyamide and polybenzimidazole.
[0074]
In the metal-containing composition according to the present invention, metal particles other than those described above, conductive particles, various additives, and the like may coexist unless the object of the present invention is contrary. Examples of the additives include curing initiators such as energy beam curing and heat curing, curing accelerators, sensitizers, thickeners, and strength reinforcing agents.
[0075]
The metal-containing composition according to the present invention is highly effective when used for via holes, through holes, wirings, and the like, which are electrical connection sites of electronic devices such as circuit boards. Specifically, (1) parts that connect circuits between layers by filling through holes in the printed wiring board, curing, and surface polishing, and (2) laser vias and photo vias on the printed wiring board. The part where the circuit between each layer is connected by filling, curing, and surface polishing in the non-through hole, and (3) The circuit by filling, curing, and surface polishing in the through-hole for connecting the back surface of the semiconductor (4) A portion that fills and cures a non-through hole for heat dissipation of a semiconductor, and (5) A bump that is formed by printing and curing a metal-containing composition on a semiconductor package or printed wiring board (6) Conductive conical protrusions formed by printing and curing on the circuit of the inner layer material at the interlayer connection of the printed wiring board, (7) The components of the printed wiring board and the semiconductor package Implementation In the case of an electrical connection part used as an alternative to the solder connection used in the case of (8) a conductor circuit part formed by printing and curing a conductor circuit as a printed wiring board, and (9) a printed wiring board with a built-in component In the method, a non-through hole reaching a component electrode using a laser or the like is provided, and the non-through hole is filled, hardened and polished, and applied to a part to be connected to the component electrode.
[0076]
These semiconductor devices can be manufactured, for example, as follows.
[0077]
The printed circuit board on which the inner layer copper electrode part is formed is irradiated with laser light, a hole is made up to the copper electrode part inside the printed circuit board, and the insulating resin residual material, which is the printed circuit board material dissolved and evaporated by the laser light, is removed. Then, a printed circuit board having a non-through hole having a bottomed copper electrode portion is produced.
[0078]
Next, the metal-containing composition is filled into the non-through holes by screen printing. Thereafter, the metal-containing composition is cured by applying heat, and the printed circuit board surface is further polished to eliminate uneven portions on the printed circuit board caused by the cured product, and the printed circuit board surface is flattened. Plan
[0079]
Further, the surface of the cured product exposed on the surface of the printed board is subjected to a copper plating process to provide an electrode to be connected to the circuit portion.
[0080]
Further, instead of the above copper plating, the metal-containing composition can be screen-printed and thermally cured to form a conductive circuit (wiring).
[0081]
【Example】
Next, examples and comparative examples of the present invention will be described in detail. Examples 1-31, 33, and 35 are examples.
[0082]
(Particle size measurement)
The powder was added to cyclohexane, and measurement was performed by a dynamic light scattering method using laser light using Microtrack 9340-UPA manufactured by Nikkiso Co., Ltd.
[0083]
A Hitachi transmission electron microscope H-9000 was used for observation with a transmission electron microscope. For observation with a scanning electron microscope, a scanning electron microscope S-800 manufactured by Hitachi, Ltd. was used.
[0084]
(Heat treatment of metal-containing composition)
6 parts by mass of an imidazole-based latent curing agent was added to 100 parts by mass of the metal-containing composition, and a cured (crosslinked) composition was obtained by heat treatment at 160 ° C. for 60 minutes.
[0085]
(Cross section observation of cured composition)
Cut the cured composition obtained by heat treatment of the metal-containing composition, 0.1 mm 2 Using a scanning electron microscope S800 manufactured by Hitachi, a shape such as a needle-like shape, a dendritic shape, a cormorant shape, and an irregularly connected shape composed of a metal or a metal and conductive particles on the cross-sectional area of Observation was performed at any magnification of 1000 times, 1000 times, 5000 times, and 10,000 times.
[0086]
[Example 1]
(Preparation of metal particle powder A)
Ag ultrafine particle powder as metal particle powder A was prepared as follows. In a glass container, 194 g of iron (II) sulfate heptahydrate and 362 g of trisodium citrate dihydrate were dissolved in 1000 g of distilled water. To this, 625 g of a 10% silver nitrate aqueous solution was added and stirred. Immediately after the addition, Ag ultrafine particles were formed.
[0087]
Thereafter, the liquid was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant liquid was discarded, the precipitated solid was taken out, 1000 g of distilled water was added to the solid, and re-peptization was performed.
[0088]
To this peptizer solution was added 100 g of an 18% aqueous solution of trisodium citrate and a precipitation operation was performed. The liquid containing the precipitate is centrifuged at 5000 rpm for 3 minutes, the precipitated solid and the supernatant are separated by the same method as described above, 500 g of distilled water is added to the obtained solid, and the solution is removed by ultrafiltration. Salt concentration treatment was performed to obtain 375 g of a 9.8% Ag sol solution in terms of Ag solid content.
[0089]
To this sol solution, 375 g of a 5% strength stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was removed. The solid was dried at room temperature under reduced pressure to obtain ultrafine Ag powder.
[0090]
When the particle size of this powder was measured, the average particle size was 10 nm. FIG. 14 shows the particle size distribution. The observation image (500,000 times) observed with the transmission electron microscope illustrated in FIG. 15 also agreed well with this average particle diameter.
[0091]
[Example 2]
(Preparation of metal particle powder A)
Pd ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 970 g of iron (II) sulfate heptahydrate and 1800 g of trisodium citrate dihydrate were dissolved in 10000 g of distilled water. To this, 2000 g of 1% palladium nitrate (II) aqueous solution was added and stirred. Pd ultrafine particles were formed 10 minutes after the addition.
[0092]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 500 g of a 1.5% Pd sol solution in terms of Pd solid content. To this sol solution, 500 g of an ethanol solution of 2% concentration of stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was taken out The solid was dried at room temperature under reduced pressure to obtain ultrafine Pd powder. The average particle size of this powder was 10 nm.
[0093]
[Example 3]
(Preparation of metal particle powder A)
Au ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 10.4 g of chloroauric acid and 1 g of hydroxypropylcellulose (average molecular weight 25000) were dissolved in 10000 g of distilled water. A mixture of 950 g of a 1.12% strength aqueous potassium hydroxide solution and 150 g of a 36% strength aqueous formaldehyde solution was added thereto and stirred. Immediately after the addition, Au ultrafine particles were formed.
[0094]
Thereafter, the solution was heated to 40 ° C. and stirred for 1 hour, and further desalted and concentrated by ultrafiltration to obtain 300 g of 1.2% Au sol solution in terms of Au solid content.
[0095]
After adding 500 g of 1% ethanolic stearic acid solution to this sol solution and stirring, it was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, The solid was dried at room temperature under reduced pressure to obtain Au ultrafine powder. The average particle size of this powder was 10 nm.
[0096]
[Example 4]
(Preparation of metal particle powder A)
Ru ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 12.5 g of ruthenium chloride trihydrate (
[0097]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 310 g of a Ru sol solution of 1.5% in terms of Ru solid content. To this sol solution, 270 g of a 3% strength stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, This solid was dried at room temperature under reduced pressure to obtain Ru ultrafine powder. The average particle size of this powder was 5 nm.
[0098]
[Example 5]
(Preparation of metal particle powder A)
Ag-Pd ultrafine particles (alloy) as the metal particle powder A were prepared as follows. In a glass container, 194 g of iron (II) sulfate heptahydrate and 362 g of trisodium citrate dihydrate were dissolved in 1000 g of distilled water. A mixed solution of 625 g of a 10% silver nitrate aqueous solution and 200 g of a 1% palladium nitrate (II) aqueous solution was added thereto and stirred. Immediately after the addition, Ag-Pd ultrafine particles were formed.
[0099]
Thereafter, the solution was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, 1000 g of distilled water was added to the solid, and re-peptization was performed.
[0100]
Furthermore, 100 g of 18% trisodium citrate aqueous solution was added to this peptizing solution, and precipitation operation was performed. The solution containing this precipitate was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the precipitated solid and the supernatant were separated by the same method as described above, and after adding 500 g of distilled water to the obtained solid, Desalination concentration treatment was performed by ultrafiltration to obtain 80 g of an Ag-Pd sol solution of 8.5% in terms of solid content.
[0101]
160 g of an ethanol solution of 8% strength stearic acid was added to this sol solution and stirred, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken The solid was dried at room temperature under reduced pressure to obtain Ag-Pd ultrafine powder. The average particle size of this powder was 10 nm.
[0102]
[Example 6]
(Preparation of metal particle powder A)
Pt ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 970 g of iron (II) sulfate heptahydrate and 1800 g of trisodium citrate dihydrate were dissolved in 10000 g of distilled water. To this, 2000 g of 1% chloroplatinic acid aqueous solution was added and stirred. Pt ultrafine particles were formed 15 minutes after the addition.
[0103]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 300 g of a 1.5% Pd sol solution in terms of Pt solid content. To this sol solution, 500 g of an ethanol solution of 5% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was taken This solid was dried at room temperature under reduced pressure to obtain ultrafine Pt powder. The average particle size of this powder was 8 nm.
[0104]
[Example 7]
(Preparation of metal particle powder A)
Re ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 10.5 g of rhenium trichloride (Re40%) was dissolved in 10000 g of distilled water. To this, 1000 g of 3% aqueous sodium borohydride solution was added and stirred. Immediately after the addition, Re ultrafine particles were formed.
[0105]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 160 g of a Re sol solution of 1.5% in terms of Re solid content. To this sol solution, 500 g of an ethanol solution of 5% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was taken This solid was dried at room temperature under reduced pressure to obtain ultra fine Re powder. The average particle size of this powder was 10 nm.
[0106]
[Example 8]
(Preparation of metal particle powder A)
Os ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 10.5 g of osmium trichloride trihydrate (Os content 64%) was dissolved in 10000 g of distilled water. To this, 1000 g of 3% aqueous sodium borohydride solution was added and stirred. Os ultrafine particles were formed immediately after the addition.
[0107]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 280 g of a 1.5% Os sol solution in terms of Os solid content. To this sol solution, 500 g of an ethanol solution of 5% strength stearic acid was added and stirred, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, The solid was dried at room temperature under reduced pressure to obtain Os ultrafine powder. The average particle size of this powder was 10 nm.
[0108]
[Example 9]
(Preparation of metal particle powder A)
Ir ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 10.5 g of iridium trichloride hydrate (Ir content 53%) was dissolved in 10000 g of distilled water. To this, 1000 g of 3% aqueous sodium borohydride solution was added and stirred. Immediately after the addition, Irr ultrafine particles were formed.
[0109]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 200 g of a 1.5% Ir sol solution in terms of Ir solid content. To this sol solution, 500 g of an ethanol solution of 5% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was taken This solid was dried at room temperature under reduced pressure to obtain Ir ultrafine powder. The average particle size of this powder was 15 nm.
[0110]
[Example 10]
(Preparation of metal particle powder A)
Au-Ru ultrafine particles (alloy) as the metal particle powder A were prepared as follows. In a glass container, 12.5 g of ruthenium chloride trihydrate (
[0111]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 350 g of a 1.5% Au-Ru sol solution in terms of Au-Ru solid content. To this sol solution, 800 g of a 3% strength stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, This solid was dried at room temperature under reduced pressure to obtain Au-Ru ultrafine particle powder. The average particle size of this powder was 10 nm.
[0112]
[Example 11]
(Preparation of metal particle powder A)
Au-Pd ultrafine particles (alloy) as metal particle powder A were prepared as follows. In a glass container, 10.4 g of chloroauric acid was dissolved in 10000 g of distilled water. To this, 2000 g of 1% palladium nitrate (II) aqueous solution was added and stirred. Further, 2000 g of 3% aqueous sodium borohydride solution was added to this mixed solution and stirred. Immediately after the addition, Au—Pd ultrafine particles were formed.
[0113]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 300 g of a 1.5% Au-Pd sol solution in terms of Au-Pd solid content. To this sol solution, 800 g of a 3% strength stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, The solid was dried at room temperature under reduced pressure to obtain Au-Pd ultrafine powder. The average particle size of this powder was 10 nm.
[0114]
[Example 12]
(Preparation of metal particle powder A)
Au-Ag ultrafine particles (alloy) as the metal particle powder A were prepared as follows. In a glass container, 10.5 g of gold hydroxide was dissolved in 1000 g of an alkaline solution whose pH was adjusted to 13 with potassium. To this, 200 g of a 5% concentration silver nitrate aqueous solution was added and stirred. Furthermore, 30 g of trisodium citrate dihydrate was added to this mixed solution and stirred. When this solution was heated to 95 ° C. and stirred, Au—Ag ultrafine particles were produced.
[0115]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 100 g of a 1.5% Au-Ag sol solution in terms of Au-Ag solid content. To this sol solution, 800 g of a 3% strength stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, This solid was dried at room temperature under reduced pressure to obtain Au-Ag ultrafine powder. The average particle size of this powder was 10 nm.
[0116]
[Example 13]
(Preparation of metal particle powder A)
In ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 12.5 g of ruthenium trichloride trihydrate was dissolved in 10000 g of distilled water. The solution was heated to 90 ° C. and 2000 g of 3% aqueous sodium borohydride solution was added while stirring. In ultrafine particles were formed immediately after the addition.
[0117]
Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 250 g of a 1.5% In sol solution in terms of In solid content. To this sol solution, 800 g of a 3% strength stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, This solid was dried at room temperature under reduced pressure to obtain In ultrafine powder. The average particle size of this powder was 10 nm.
[0118]
[Example 14]
(Preparation of metal particle powder B)
Ag particles as metal particle powder B were prepared as follows. Specific surface area is 0.6m 2 80 g of alcohol and 5 g of acetylacetone were added to 10 g of Ag powder / g, and peptization was performed for 200 minutes with a sand mill to obtain 90 g of Ag suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 800 g of 3% stearic acid ethanol solution was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid The thing was taken out. This solid was dried at room temperature under reduced pressure to obtain a powder of Ag particles. The average particle size of this powder was 900 nm. The observed image observed with a scanning electron microscope also agreed well with this average particle size.
[0119]
[Example 15]
(Preparation of metal particle powder B)
Ru particles as metal particle powder B were prepared as follows. Specific surface area is 0.1m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of Ru powder of / g, and peptization was performed for 500 minutes with a sand mill to obtain 90 g of Ru suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 500 g of an ethanol solution of 3% strength stearic acid was added and stirred, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes. The supernatant was discarded, and the precipitated solid was I took it out. This solid was dried at room temperature under reduced pressure to obtain Ru powder. The average particle size of this powder was 1000 nm.
[0120]
[Example 16]
(Preparation of metal particle powder B)
Ni particles as metal particle powder B were prepared as follows. Specific surface area produced by decomposition of carbonyl nickel is 0.14 m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of Ni powder / g, and peptization was performed for 500 minutes with a sand mill to obtain 90 g of Ni suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. After adding 800 g of 3% stearic acid ethanol solution to the supernatant suspension and stirring, the mixture was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was removed. I took it out. This solid was dried at room temperature under reduced pressure to obtain Ni powder. The average particle size of this powder was 1500 nm.
[0121]
[Example 17]
(Preparation of metal particle powder B)
Sn particles as metal particle powder B were prepared as follows. Specific surface area generated by atomization method is 0.3m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of / g Sn powder, and peptization was performed for 500 minutes with a sand mill to obtain 90 g of Sn suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 800 g of an ethanol solution of 3% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was I took it out. This solid was dried at room temperature under reduced pressure to obtain Sn powder. The average particle size of this powder was 1200 nm.
[0122]
[Example 18]
(Preparation of metal particle powder B)
Al particles as metal particle powder B were prepared as follows. Specific surface area generated by atomization method is 0.1m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of Al powder / g, and peptization was performed for 500 minutes with a sand mill to obtain 90 g of Al suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 800 g of an ethanol solution of 3% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was I took it out. This solid was dried at room temperature under reduced pressure to obtain Al powder. The average particle size of this powder was 1500 nm.
[0123]
[Example 19]
(Preparation of metal particle powder B)
Zn particles as metal particle powder B were prepared as follows. Specific surface area generated by atomization method is 0.1m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of Zn powder / g, and peptization was performed with a sand mill for 500 minutes to obtain 90 g of Zn suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 800 g of an ethanol solution of 3% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was I took it out. This solid was dried at room temperature under reduced pressure to obtain Zn powder. The average particle size of this powder was 1500 nm.
[0124]
[Example 20]
(Preparation of metal particle powder B)
W particles as metal particle powder B were prepared as follows. The specific surface area produced by the electrolytic reduction deposition method is 0.1 m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of W powder of / g, and peptization was performed with a sand mill for 500 minutes to obtain 90 g of W suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to settle coarse particles, and the supernatant suspension was separated. After adding 800 g of 3% stearic acid ethanol solution to the supernatant suspension and stirring, the mixture was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was removed. I took it out. This solid was dried at room temperature under reduced pressure to obtain W powder. The average particle size of this powder was 1900 nm.
[0125]
[Example 21]
(Preparation of metal particle powder B)
In particles as metal particle powder B were prepared as follows. The specific surface area produced by the electrolytic deposition method is 0.1 m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of In powder of / g, and peptization was performed for 500 minutes with a sand mill to obtain 90 g of In suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 800 g of an ethanol solution of 3% strength stearic acid was added and stirred, then centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was I took it out. This solid was dried at room temperature under reduced pressure to obtain In powder. The average particle size of this powder was 1800 nm.
[0126]
[Example 22]
(Preparation of metal particle powder B)
Cu particles as metal particle powder B were prepared as follows. Specific surface area produced by electrolytic deposition is 0.2m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of Cu powder / g, and peptization treatment was performed for 500 minutes with a sand mill to obtain 90 g of Cu suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 500 g of an ethanol solution of 3% strength stearic acid was added and stirred, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes. The supernatant was discarded, and the precipitated solid was I took it out. This solid was dried at room temperature under reduced pressure to obtain a Cu powder. The average particle size of this powder was 1500 nm.
[0127]
[Example 23]
(Preparation of metal particle powder B)
Co particles as metal particle powder B were prepared as follows. The specific surface area produced by the reduction precipitation method is 0.2 m 2 80 g of alcohol and 5 g of acetylacetone were added to 8 g of Co powder / g, and peptization treatment was performed for 500 minutes with a sand mill to obtain 90 g of Co suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. To this supernatant suspension, 450 g of a 3% strength stearic acid ethanol solution was added and stirred, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes. The supernatant was discarded, and the precipitated solid was removed. I took it out. This solid was dried at room temperature under reduced pressure to obtain Co powder. The average particle size of this powder was 1900 nm.
[0128]
[Example 24]
(Preparation of conductive particle powder C)
Ag particles as conductive particle powder C were prepared as follows. Specific surface area is 0.02m 2 80 g of alcohol and 5 g of acetylacetone were added to 10 g of Ag powder / g, and peptization was performed for 30 minutes with a sand mill to obtain 90 g of Ag suspension. The obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate the particles. This precipitate was added to 800 g of a 3% strength stearic acid ethanol solution, subjected to ultrasonic dispersion for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid was dried at room temperature under reduced pressure to obtain Ag powder of conductive particles. The average particle size of this powder was 5 μm. The observed image observed with a scanning electron microscope also agreed well with this average particle size.
[0129]
[Example 25]
(Preparation of conductive particle powder C)
Ru particles as conductive particle powder C were prepared as follows. Specific surface area is 0.03m 2 80 g of alcohol and 5 g of acetylacetone were added to 10 g of Ru powder of / g, and peptization was performed with a sand mill for 30 minutes to obtain 90 g of Ru suspension. The obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate the particles. This precipitate was added to 800 g of a 3% strength stearic acid ethanol solution, subjected to ultrasonic dispersion for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid was dried at room temperature under reduced pressure to obtain Ru powder of conductive particles. The average particle size of this powder was 16 μm.
[0130]
[Example 26]
(Preparation of conductive particle powder C)
Cu particles as conductive particle powder C were prepared as follows. Specific surface area is 0.04m 2 80 g of alcohol and 5 g of acetylacetone were added to 10 g of Cu powder produced by the / g electrolytic deposition method, and peptization was performed for 30 minutes with a sand mill to obtain 90 g of Cu suspension. The obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate the particles. This precipitate was added to 800 g of a 3% strength stearic acid ethanol solution, subjected to ultrasonic dispersion for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid was dried at room temperature under reduced pressure to obtain Cu powder of conductive particles. The average particle size of this powder was 20 μm.
[0131]
[Example 27]
(Preparation of conductive particle powder C)
ITO (tin solid solution type indium oxide) particles as conductive particle powder C were prepared as follows. In a glass container, 5 g of tin (IV) chloride (anhydrous) was added to 1000 g of distilled water to obtain a solution. In addition, 40 g of indium trichloride (anhydrous) was added to another 1000 g of distilled water to obtain a solution. After mixing these two types of solution, the mixture was added dropwise to a 1.12% aqueous potassium hydroxide solution maintained at 40 ° C. to obtain a hydroxide. The solution containing the hydroxide was further heated to 90 ° C. and stirred for 6 hours. By this heating treatment, the hydroxide in the solution formed an aggregated structure.
[0132]
Impurity ions were removed from the resulting indium-tin hydroxide having an agglomerated structure by a desalting operation, followed by firing at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain tin-containing indium oxide powder. After adding 10 g of the obtained tin-containing indium oxide powder to 50 g of an acidic aqueous solution of nitric acid adjusted to pH 5.5, peptization treatment was performed for 5 minutes with a sand mill, and 12% tin-containing indium oxide suspension in terms of solid content of tin-containing indium oxide. 40 g of a turbid liquid was obtained.
[0133]
The obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate the particles. This precipitate was added to 800 g of a 3% strength stearic acid ethanol solution, subjected to ultrasonic dispersion for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid was dried at room temperature under reduced pressure to obtain ITO powder of conductive particles. The average particle size of this powder was 2 μm.
[0134]
[Example 28]
(Preparation of conductive particle powder C)
ATO (antimony solid solution type tin oxide) particles as conductive particle powder C were prepared as follows. In a glass container, 5 g of potassium antimonyl tartrate was added to 1000 g of distilled water to obtain a solution. Further, 40 g of tin (IV) chloride (anhydrous) was added to 1000 g of another distilled water to obtain a solution. After mixing these two types of solution, the mixture was added dropwise to a 1.5% aqueous potassium hydroxide solution maintained at 40 ° C. to obtain tin-antimony hydroxide. The solution containing the hydroxide was further heated to 90 ° C. and stirred for 6 hours. By this heating treatment, the hydroxide in the solution formed an aggregated structure.
[0135]
Impurity ions were removed from the resulting hydroxide having an agglomerated structure by a desalting operation, followed by firing at 550 ° C. for 2 hours in an air atmosphere to obtain an antimony-containing tin oxide powder.
[0136]
After adding 10 g of the obtained antimony-containing tin oxide powder to 50 g of an acidic aqueous solution of nitric acid adjusted to pH 4.5, a peptization treatment is performed for 5 minutes with a sand mill, and antimony-containing tin oxide particles of 16% in terms of solid content of antimony-containing tin oxide 35 g of sol solution was obtained.
[0137]
The obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate coarse particles. This precipitate was added to 800 g of a 3% strength stearic acid ethanol solution, subjected to ultrasonic dispersion for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid was dried at room temperature under reduced pressure to obtain ATO powder of conductive particles. The average particle size of this powder was 3 μm.
[0138]
[Example 29]
(Preparation of conductive particle powder C)
RuO which is conductive particle powder C 2 (Ruthenium oxide) particles were prepared as follows. In a glass container, 12.5 g of ruthenium chloride trihydrate (
[0139]
Impurity ions were removed from the resulting ruthenium hydroxide having an agglomerated structure by a desalting operation, followed by firing at 800 ° C. for 2 hours in the atmosphere to obtain ruthenium oxide powder. After adding 5 g of the obtained ruthenium oxide powder to 50 g of an acidic aqueous solution of nitric acid adjusted to pH 5.5, a peptization treatment was performed for 5 minutes with a sand mill to obtain 40 g of a 3% ruthenium oxide suspension in terms of ruthenium oxide solid content. . The obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate coarse particles.
[0140]
This precipitate was added to 800 g of a 3% strength stearic acid ethanol solution, subjected to ultrasonic dispersion for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid material is dried at room temperature under reduced pressure, and RuO of conductive particles is obtained. 2 (Ruthenium oxide) powder was obtained. The average particle size of this powder was 10 μm.
[0141]
[Example 30]
(Preparation of conductive particle powder C)
The carbon nanotube which is the electroconductive particle powder C was prepared as follows. 10 g of carbon nanotube powder of carbon nanotubes (tube length: 0.5 μm to 25 μm, diameter: 0.3 to 2 nm) obtained by the arc discharge method is added to 800 g of a 3% ethanol solution of stearic acid and 100 ultrasonically. After the dispersion treatment, the mixture was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was taken out. This solid was dried at room temperature under reduced pressure to obtain carbon nanotube powder of conductive particles. The average particle size of this powder was 19 μm.
[0142]
[Example 31]
(Preparation of conductive particle powder C)
A conductive carbon having a part of the graphite structure as the conductive particle powder C was prepared as follows. After adding 10 g of conductive carbon (trade name: Ketjen Black) partially having a graphite structure in the particles to 800 g of ethanol solution of stearic acid with a concentration of 3%, and carrying out dispersion treatment with ultrasonic waves for 100 minutes, 5000 rpm (Z value 2742) was centrifuged for 3 minutes, the supernatant was discarded, and the precipitated solid was taken out. The solid was dried at room temperature under reduced pressure to obtain conductive carbon powder having a part of the graphite structure. The average particle size of this powder was 3 μm.
[0143]
[Example 32]
(Preparation of metal-containing composition for electrical connection)
The above-described metal particle powder A, metal particle powder B, resin, and, in some cases, conductive particle powder C were mixed at the composition ratio shown in Table 1, and rough kneaded for 1 hour in an automatic mortar.
[0144]
Thereafter, kneading with three rolls was carried out for 60 minutes, and further, defoaming treatment was performed with a centrifugal defoaming apparatus for 1 hour to prepare a metal-containing composition for electrical connection of an electronic device.
[0145]
[0146]
As a result of measuring the particle size distribution, the examples of Nos. 1 to 23 show that the concentration of metal particles having a particle size of 20 nm or less, the concentration of metal particles having a particle size of 50 nm or more and 2000 nm or less, and the particle size exceeding 2000 nm to 20 μm. The requirements of the
[0147]
Further, in these particle size distributions, as can be understood from the position of the inflection point of the cumulative particle size distribution in FIG. 16 for the
[0148]
[Example 33]
(Evaluation of coatability, printability, and fillability of the metal-containing composition for electrical connection)
For
[0149]
[Example 34]
(Evaluation of cured composition)
As shown in the side view of FIG. 23 and the plan view of FIG. 24, each set of two holes provided on a glass epoxy substrate having a thickness of 5.0 mm is connected by a
[0150]
Then, excess paste on the substrate is removed by polishing, chemical copper plating, electrolytic copper plating, and wiring patterning are sequentially performed to produce a
[0151]
About the obtained daisy chain circuit board, the resistance value (initial resistance value) of the hardening composition with which the hole was filled was measured by measuring the resistance value of the said 3000 hole ends.
[0152]
In addition, using a cold air blowing type thermostatic bath and a blowing type hot air thermostatic bath, 1000 cycles of a thermal shock test consisting of a combination of −65 ° C. × 30 minutes and 125 ° C. × 30 minutes for one cycle of a daisy chain circuit board After the implementation, the resistance value between the ends of the 3000 holes was measured. Switching between −65 ° C. × 30 minutes and 125 ° C. × 30 minutes was performed automatically, and the time required for one switching was about 3 seconds / time.
[0153]
Table 2 shows the obtained initial resistance value and the change rate of the resistance value after the thermal shock test. It can be understood that each of the examples is superior in conductivity and durability as compared with the comparative example.
[0154]
Specifically, the resistance value of the cured composition was determined as follows.
[0155]
(A) The resistance value of the cured composition filled in one via hole is calculated by dividing the resistance value between the ends of the 3000 holes by the number of holes (3000) filled with paste.
[0156]
(B) Multiplying the resistance value per via hole by the cross-sectional area of the surface perpendicular to the direction in which electricity flows (that is, the cross-sectional area of the via hole having a diameter of 50 μm) and parallel to the direction in which electricity flows The resistance value of the cured composition filled in one via hole is calculated by dividing by the distance (that is, 60 μm which is the distance in the depth direction of the via hole).
[0157]
[Example 35]
(Cross section observation of cured composition)
Cutting the cured composition obtained by heat treatment of the metal-containing composition according to the present invention, 0.1 mm 2 As a result of observing the cross-sectional area, a needle-like shape, a dendritic shape, a cormorant shape and an indeterminately connected shape as shown in FIGS. 1 to 13 were observed. 17 to 22 are cross-sectional photographs taken using a scanning electron microscope S-800 manufactured by Hitachi, Ltd. 17 was taken at a magnification of 1000, FIG. 18 was taken at a magnification of 10,000, FIG. 19 was taken at a magnification of 5000, and FIGS.
[0158]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
【The invention's effect】
According to the present invention, it is possible to provide a conductive composition for electrical connection of an electronic device having high fluidity, excellent coating properties, printing properties, filling properties, and excellent electrical conductivity and durability by applying energy such as heat treatment. A metal-containing composition that can be obtained is obtained.
[Brief description of the drawings]
FIG. 1 is a model diagram illustrating a needle-like metal bonded body.
FIG. 2 is another model diagram illustrating a needle-like metal bonded body.
FIG. 3 is another model view illustrating a needle-like metal bonded body.
FIG. 4 is another model diagram illustrating a needle-like metal bonded body.
FIG. 5 is another model diagram illustrating a needle-like metal bonded body.
FIG. 6 is another model diagram illustrating a needle-like metal bonded body.
FIG. 7 is a model diagram illustrating a dendritic metal combination.
FIG. 8 is another model diagram illustrating a dendritic metal combination.
FIG. 9 is a model diagram illustrating a sawtooth-shaped metal combination.
FIG. 10 is another model view illustrating a sawtooth-shaped metal combination.
FIG. 11 is another model diagram illustrating a sawtooth-shaped metal combination.
FIG. 12 is another model diagram illustrating a sawtooth-shaped metal combination.
FIG. 13 is another model diagram illustrating a metal coupling body having an irregular connection shape.
14 is a particle size distribution diagram of Ag fine particle powder as metal particle powder A. FIG.
FIG. 15 is a photograph of an observation image of an Ag fine particle powder as the metal particle powder A by a transmission electron microscope.
FIG. 16 is a particle size distribution diagram showing a peak in a particle size region of 20 nm or less, a particle size region of 50 nm or more and 2000 nm or less, and a particle size region of more than 2000 nm and 20 μm or less.
FIG. 17 is another cross-sectional photograph of a cured composition obtained by heat treatment of a metal-containing composition according to the present invention.
FIG. 18 is another cross-sectional photograph of a cured composition obtained by heat treatment of a metal-containing composition according to the present invention.
FIG. 19 is another cross-sectional photograph of the cured composition obtained by heat treatment of the metal-containing composition according to the present invention.
FIG. 20 is another cross-sectional photograph of the cured composition obtained by heat treatment of the metal-containing composition according to the present invention.
FIG. 21 is another cross-sectional photograph of the cured composition obtained by heat treatment of the metal-containing composition according to the present invention.
FIG. 22 is another cross-sectional photograph of the cured composition obtained by heat treatment of the metal-containing composition according to the present invention.
FIG. 23 is a side model diagram of a substrate for evaluation of a cured composition.
FIG. 24 is a plan model diagram of a substrate for evaluation of a cured composition.
[Explanation of symbols]
1 Rod or needle shape
2 Shapes branched into three
3 Igaruri shape
4 gaps
5 irregularly connected shape
101 (Lower) Copper electrode
102 Beer hole
103 (Upper) Copper electrode
Claims (7)
ａ：ｂが３：９７〜９０：１０の間にあり、
（ａ＋ｂ）：ｃが１００：０〜６０：４０の間にあり、
５０≦（ａ＋ｂ＋ｃ）≦９５である
請求項１に記載の金属含有組成物。When the concentration of the metal particle powder A in the metal-containing composition is a mass%, the concentration of the metal particle powder B is b mass%, and the concentration of the conductive particle powder C is c mass%,
a: b is between 3:97 and 90:10,
(A + b): c is between 100: 0 and 60:40,
The metal-containing composition according to claim 1, wherein 50 ≦ (a + b + c) ≦ 95.
金属粒子と導電性粒子との総量に対し、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子との量割合が質量比で３：９７〜９０：１０の間にあり、粒径が２０ｎｍ以下の金属粒子と粒径が５０ｎｍ以上２０００ｎｍ以下の金属粒子とを合計で６０〜１００質量％の割合で含み、２０００ｎｍを超え２０μｍ以下の導電性粒子を４０〜０質量％の割合で含む、
電子デバイスの電気的接続用金属含有組成物。Including metal particles and resin, and in some cases conductive particles,
The mass ratio of the metal particles having a particle size of 20 nm or less and the metal particles having a particle size of 50 nm or more and 2000 nm or less is between 3:97 and 90:10 by mass ratio with respect to the total amount of the metal particles and the conductive particles. , Including metal particles having a particle size of 20 nm or less and metal particles having a particle size of 50 nm or more and 2000 nm or less in a ratio of 60 to 100% by mass, and containing 40 to 0% by mass of conductive particles exceeding 2000 nm and 20 μm or less. Including as a percentage,
Metal-containing composition for electrical connection of electronic devices.
当該金属含有組成物中に存在する固体粒子の動的光散乱による測定法による粒度分布のうち、２０ｎｍ以下の粒径領域と５０ｎｍ以上２０００ｎｍ以下の粒径領域とにそれぞれピークが存在し、
場合によってはさらに２０００ｎｍを超え２０μｍ以下の粒径領域にピークが存在する
電子デバイスの電気的接続用金属含有組成物。In the metal-containing composition for electrical connection of an electronic device comprising metal particles and a resin, and possibly conductive particles,
Among the particle size distribution by the measurement method based on dynamic light scattering of the solid particles present in the metal-containing composition, there are peaks in the particle size region of 20 nm or less and the particle size region of 50 nm or more and 2000 nm or less,
In some cases, a metal-containing composition for electrical connection of an electronic device having a peak in a particle size region of more than 2000 nm and not more than 20 μm.
導電性粒子粉Ｃが存在する場合には当該導電性粒子粉Ｃが、
Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と、
当該元素を含む合金粒子と、
Ｉｎ，Ｒｕ，Ｒｅ，Ｏｓ，Ｉｒ，Ｓｎからなる群から選ばれた少なくともいずれか１種の元素を含む導電性酸化物粒子と、
グラファイト、グラファイト構造を有するカーボン化合物およびカーボンナノチューブからなる群から選ばれた少なくともいずれか１種の導電性カーボン化合物と
の少なくともいずれか一つを含む、請求項１または２に記載の金属含有組成物。Metal particle powder A and metal particle powder B are made of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W and Mo, respectively. Including at least one of metal particles of at least one element selected from and alloy particles containing the element,
When the conductive particle powder C is present, the conductive particle powder C is
Metal particles of at least one element selected from the group consisting of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo When,
Alloy particles containing the element;
Conductive oxide particles containing at least one element selected from the group consisting of In, Ru, Re, Os, Ir, and Sn;
3. The metal-containing composition according to claim 1, comprising at least one of graphite, a carbon compound having a graphite structure, and at least one conductive carbon compound selected from the group consisting of carbon nanotubes. .
２０００ｎｍを超え２０μｍ以下の導電性粒子が存在する場合には当該導電性粒子が、
Ａｇ，Ａｕ，Ｒｕ，Ｐｄ，Ｐｔ，Ｒｅ，Ｏｓ，Ｉｒ，Ｃｕ，Ｎｉ、Ｓｎ、Ａｌ，Ｚｎ，Ｉｎ，Ｃｏ，ＷおよびＭｏからなる群から選ばれた少なくともいずれか１種の元素の金属粒子と、
当該元素を含む合金粒子と、
Ｉｎ，Ｒｕ，Ｒｅ，Ｏｓ，Ｉｒ，Ｓｎからなる群から選ばれた少なくともいずれか１種の元素を含む導電性酸化物粒子と、
グラファイト、グラファイト構造を有するカーボン化合物およびカーボンナノチューブからなる群から選ばれた少なくともいずれか１種の導電性カーボン化合物と
の少なくともいずれか一つを含む、請求項３または４に記載の金属含有組成物。Metal particles having a particle size of 20 nm or less and metal particles having a particle size of 50 nm or more and 2000 nm or less are respectively Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, Including at least one of metal particles of at least one element selected from the group consisting of In, Co, W and Mo and alloy particles containing the element,
In the case where conductive particles of more than 2000 nm and 20 μm or less are present, the conductive particles are
Metal particles of at least one element selected from the group consisting of Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W, and Mo When,
Alloy particles containing the element;
Conductive oxide particles containing at least one element selected from the group consisting of In, Ru, Re, Os, Ir, and Sn;
5. The metal-containing composition according to claim 3, comprising at least one of graphite, a carbon compound having a graphite structure, and at least one conductive carbon compound selected from the group consisting of carbon nanotubes. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002273233A JP2004111254A (en) | 2002-09-19 | 2002-09-19 | Metal contained composition for electrical connection of electronic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002273233A JP2004111254A (en) | 2002-09-19 | 2002-09-19 | Metal contained composition for electrical connection of electronic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004111254A true JP2004111254A (en) | 2004-04-08 |
Family
ID=32270037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002273233A Withdrawn JP2004111254A (en) | 2002-09-19 | 2002-09-19 | Metal contained composition for electrical connection of electronic device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004111254A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004111253A (en) * | 2002-09-19 | 2004-04-08 | Noda Screen:Kk | Conductive composition for electrical connection of electronic device, and electron device |
| JP2004168966A (en) * | 2002-11-22 | 2004-06-17 | Hitachi Chem Co Ltd | Conductive resin composition and electronic part by using the same |
| JP2005183144A (en) * | 2003-12-18 | 2005-07-07 | Alps Electric Co Ltd | Conductive composition and manufacturing method of same |
| JP2005294254A (en) * | 2004-03-12 | 2005-10-20 | Sumitomo Electric Ind Ltd | Conductive silver paste and electromagnetic wave shielding member using it |
| JP2006070300A (en) * | 2004-08-31 | 2006-03-16 | Mitsubishi Materials Corp | Metal particulate-containing composition and its application |
| JP2008239381A (en) * | 2007-03-26 | 2008-10-09 | Ngk Insulators Ltd | Composite joint material and joint body |
| JP2010108696A (en) * | 2008-10-29 | 2010-05-13 | Mitsuboshi Belting Ltd | Resistive paste, and resistor |
| JP2011058041A (en) * | 2009-09-09 | 2011-03-24 | Osaka Municipal Technical Research Institute | Silver-copper based mixed powder and joining method using the same |
| WO2011040521A1 (en) * | 2009-10-02 | 2011-04-07 | 戸田工業株式会社 | Fine silver particles, method for producing same, conductive paste containing the fine silver particles, conductive film, and electronic device |
| WO2011062072A1 (en) * | 2009-11-19 | 2011-05-26 | 株式会社 村田製作所 | Electronic device |
| JP2011165668A (en) * | 2010-02-12 | 2011-08-25 | Giga Solar Materials Corp | Conductive aluminum paste and its manufacturing method, solar cell, and its module |
| JP2013055127A (en) * | 2011-09-01 | 2013-03-21 | Ishifuku Metal Ind Co Ltd | Magnetic thin film |
| JP2013219542A (en) * | 2012-04-09 | 2013-10-24 | River Eletec Kk | Piezoelectric vibrator |
| WO2013187518A1 (en) * | 2012-06-14 | 2013-12-19 | 日立化成株式会社 | Adhesive composition and semiconductor device using same |
| JP5390408B2 (en) * | 2008-02-06 | 2014-01-15 | ナミックス株式会社 | Thermosetting conductive paste and multilayer ceramic electronic component having external electrodes formed using the same |
| JP2015105406A (en) * | 2013-11-29 | 2015-06-08 | Ｄｏｗａエレクトロニクス株式会社 | Silver-coated copper powder, and conductive paste |
| JP2015161536A (en) * | 2014-02-26 | 2015-09-07 | 住友金属鉱山株式会社 | Evaluation method for coarse particle in conductive powder included in conductive paste |
| JP2016204686A (en) * | 2015-04-17 | 2016-12-08 | 住友金属鉱山株式会社 | Copper powder and conductive paste using the same, conductive coating and conductive sheet |
| US9620840B2 (en) | 2014-06-27 | 2017-04-11 | Tdk Corporation | High-frequency transmission line, antenna and electronic circuit board |
| US9627737B2 (en) | 2014-06-27 | 2017-04-18 | Tdk Corporation | High-frequency transmission line, antenna and electronic circuit board |
| JP2018076597A (en) * | 2017-12-27 | 2018-05-17 | Ｄｏｗａエレクトロニクス株式会社 | Silver coated copper powder and conductive paste, as well as production method thereof |
| KR20180129888A (en) * | 2016-05-13 | 2018-12-05 | 헤레우스 도이칠란트 게엠베하 운트 코. 카게 | Method for producing particulate ruthenium |
| JP2020200504A (en) * | 2019-06-10 | 2020-12-17 | 日本電産株式会社 | Electric contact material powder, and method of producing electric contact material powder |
| WO2022045263A1 (en) * | 2020-08-31 | 2022-03-03 | 株式会社大阪ソーダ | Electroconductive adhesive |
| WO2024204650A1 (en) * | 2023-03-31 | 2024-10-03 | 株式会社 東芝 | Tungsten alloy, structure, and rhenium powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1021744A (en) * | 1996-06-28 | 1998-01-23 | Mitsuboshi Belting Ltd | Copper conductor paste and substrate printed therewith |
| WO2002035554A1 (en) * | 2000-10-25 | 2002-05-02 | Harima Chemicals, Inc. | Electroconductive metal paste and method for production thereof |
| JP2004111253A (en) * | 2002-09-19 | 2004-04-08 | Noda Screen:Kk | Conductive composition for electrical connection of electronic device, and electron device |
-
2002
- 2002-09-19 JP JP2002273233A patent/JP2004111254A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1021744A (en) * | 1996-06-28 | 1998-01-23 | Mitsuboshi Belting Ltd | Copper conductor paste and substrate printed therewith |
| WO2002035554A1 (en) * | 2000-10-25 | 2002-05-02 | Harima Chemicals, Inc. | Electroconductive metal paste and method for production thereof |
| JP2004111253A (en) * | 2002-09-19 | 2004-04-08 | Noda Screen:Kk | Conductive composition for electrical connection of electronic device, and electron device |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004111253A (en) * | 2002-09-19 | 2004-04-08 | Noda Screen:Kk | Conductive composition for electrical connection of electronic device, and electron device |
| JP2004168966A (en) * | 2002-11-22 | 2004-06-17 | Hitachi Chem Co Ltd | Conductive resin composition and electronic part by using the same |
| JP2005183144A (en) * | 2003-12-18 | 2005-07-07 | Alps Electric Co Ltd | Conductive composition and manufacturing method of same |
| JP2005294254A (en) * | 2004-03-12 | 2005-10-20 | Sumitomo Electric Ind Ltd | Conductive silver paste and electromagnetic wave shielding member using it |
| JP2006070300A (en) * | 2004-08-31 | 2006-03-16 | Mitsubishi Materials Corp | Metal particulate-containing composition and its application |
| JP4517230B2 (en) * | 2004-08-31 | 2010-08-04 | 三菱マテリアル株式会社 | Composition containing fine metal particles and use thereof |
| JP2008239381A (en) * | 2007-03-26 | 2008-10-09 | Ngk Insulators Ltd | Composite joint material and joint body |
| JP5390408B2 (en) * | 2008-02-06 | 2014-01-15 | ナミックス株式会社 | Thermosetting conductive paste and multilayer ceramic electronic component having external electrodes formed using the same |
| JP2010108696A (en) * | 2008-10-29 | 2010-05-13 | Mitsuboshi Belting Ltd | Resistive paste, and resistor |
| JP2011058041A (en) * | 2009-09-09 | 2011-03-24 | Osaka Municipal Technical Research Institute | Silver-copper based mixed powder and joining method using the same |
| JP2011080094A (en) * | 2009-10-02 | 2011-04-21 | Toda Kogyo Corp | Fine silver particle, method for producing same, conductive paste containing the fine silver particles, conductive film, and electronic device |
| WO2011040521A1 (en) * | 2009-10-02 | 2011-04-07 | 戸田工業株式会社 | Fine silver particles, method for producing same, conductive paste containing the fine silver particles, conductive film, and electronic device |
| WO2011062072A1 (en) * | 2009-11-19 | 2011-05-26 | 株式会社 村田製作所 | Electronic device |
| JP5339222B2 (en) * | 2009-11-19 | 2013-11-13 | 株式会社村田製作所 | Electronic devices |
| JP2011165668A (en) * | 2010-02-12 | 2011-08-25 | Giga Solar Materials Corp | Conductive aluminum paste and its manufacturing method, solar cell, and its module |
| JP2013055127A (en) * | 2011-09-01 | 2013-03-21 | Ishifuku Metal Ind Co Ltd | Magnetic thin film |
| JP2013219542A (en) * | 2012-04-09 | 2013-10-24 | River Eletec Kk | Piezoelectric vibrator |
| WO2013187518A1 (en) * | 2012-06-14 | 2013-12-19 | 日立化成株式会社 | Adhesive composition and semiconductor device using same |
| US10174226B2 (en) | 2012-06-14 | 2019-01-08 | Hitachi Chemical Company, Ltd. | Adhesive composition and semiconductor device using same |
| JP2013258122A (en) * | 2012-06-14 | 2013-12-26 | Hitachi Chemical Co Ltd | Adhesive composition and semiconductor device using the same |
| JP2015105406A (en) * | 2013-11-29 | 2015-06-08 | Ｄｏｗａエレクトロニクス株式会社 | Silver-coated copper powder, and conductive paste |
| JP2015161536A (en) * | 2014-02-26 | 2015-09-07 | 住友金属鉱山株式会社 | Evaluation method for coarse particle in conductive powder included in conductive paste |
| US9620840B2 (en) | 2014-06-27 | 2017-04-11 | Tdk Corporation | High-frequency transmission line, antenna and electronic circuit board |
| US9627737B2 (en) | 2014-06-27 | 2017-04-18 | Tdk Corporation | High-frequency transmission line, antenna and electronic circuit board |
| JP2016204686A (en) * | 2015-04-17 | 2016-12-08 | 住友金属鉱山株式会社 | Copper powder and conductive paste using the same, conductive coating and conductive sheet |
| JP2019515136A (en) * | 2016-05-13 | 2019-06-06 | ヘレウス ドイチェラント ゲーエムベーハー ウント カンパニー カーゲー | Method of producing granular ruthenium |
| KR20180129888A (en) * | 2016-05-13 | 2018-12-05 | 헤레우스 도이칠란트 게엠베하 운트 코. 카게 | Method for producing particulate ruthenium |
| US10913120B2 (en) | 2016-05-13 | 2021-02-09 | Heraeus Deutschland GmbH & Co. KG | Process for production of particulate ruthenium |
| KR102279617B1 (en) | 2016-05-13 | 2021-07-20 | 헤레우스 도이칠란트 게엠베하 운트 코. 카게 | Method for producing particulate ruthenium |
| JP2018076597A (en) * | 2017-12-27 | 2018-05-17 | Ｄｏｗａエレクトロニクス株式会社 | Silver coated copper powder and conductive paste, as well as production method thereof |
| JP2020200504A (en) * | 2019-06-10 | 2020-12-17 | 日本電産株式会社 | Electric contact material powder, and method of producing electric contact material powder |
| WO2022045263A1 (en) * | 2020-08-31 | 2022-03-03 | 株式会社大阪ソーダ | Electroconductive adhesive |
| WO2024204650A1 (en) * | 2023-03-31 | 2024-10-03 | 株式会社 東芝 | Tungsten alloy, structure, and rhenium powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2004111254A (en) | Metal contained composition for electrical connection of electronic device | |
| JP2004111253A (en) | Conductive composition for electrical connection of electronic device, and electron device | |
| KR20170075748A (en) | Conductive composition and electronic component using same | |
| KR100678533B1 (en) | Conductive powder and method for preparing the same | |
| WO1996024938A1 (en) | Composite conductive powder, conductive paste, method of producing conductive paste, electric circuit and method of fabricating electric circuit | |
| JP2008293821A (en) | Conductive paste, circuit board using the same, and electronic/electric device | |
| JP2018040056A (en) | Silver-coated alloy powder, conductive paste, electronic component and electric device | |
| JPWO2013161966A1 (en) | Conductive composition | |
| JP5622127B2 (en) | Reduction precipitation type spherical NiP fine particles and method for producing the same | |
| JP2013196936A (en) | Conductive paste, conductor, base material with conductive film, and manufacturing method therefor | |
| KR101945056B1 (en) | Conductive paste and method for preparing conductive paste | |
| JP4922793B2 (en) | Mixed conductive powder and method for producing the same, conductive paste and method for producing the same | |
| JP2005093105A (en) | Conductive structure and its manufacturing method | |
| JP6197504B2 (en) | Conductive paste and substrate with conductive film | |
| JPH0992026A (en) | Complex conductive powder, conductive paste, manufacture of conductive paste, electric circuit, and manufacture of electric circuit | |
| JP2006131978A (en) | SPHERICAL NiP FINE PARTICLE, METHOD FOR PRODUCING THE SAME AND ELECTRICALLY CONDUCTIVE PARTICLE FOR ANISOTROPIC ELECTRICALLY CONDUCTIVE FILM | |
| JP2012136771A (en) | Method of producing surface-modified copper particle, method of producing composition for forming conductor, method of producing conductor film, and article having the conductor film | |
| JP2002298654A (en) | Conductive powder and conductive composite | |
| JP2017130393A (en) | Conductive paste and method for forming silver film | |
| JP2020113545A (en) | Conductive particle, conductive material and connection structure | |
| JPH0662900B2 (en) | Conductive paint | |
| JP2006111807A (en) | Electronic part and method for producing the same | |
| JP2004193250A (en) | Conductive paste and semiconductor device using it | |
| JP2014086243A (en) | Paste for forming an electroconductive film, electroconductive film, method for manufacturing an electroconductive film, and article | |
| JP5534745B2 (en) | Conductive fine particles, anisotropic conductive material, and connection structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050906 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080422 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080513 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20080521 |