JP3764349B2 - Method of forming an alternative conductive metal film for plating using metal fine particle dispersion - Google Patents
Method of forming an alternative conductive metal film for plating using metal fine particle dispersion Download PDFInfo
- Publication number
- JP3764349B2 JP3764349B2 JP2001136077A JP2001136077A JP3764349B2 JP 3764349 B2 JP3764349 B2 JP 3764349B2 JP 2001136077 A JP2001136077 A JP 2001136077A JP 2001136077 A JP2001136077 A JP 2001136077A JP 3764349 B2 JP3764349 B2 JP 3764349B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- particle dispersion
- plating
- film
- oxygen
- 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.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 202
- 239000002184 metal Substances 0.000 title claims description 198
- 238000007747 plating Methods 0.000 title claims description 105
- 239000006185 dispersion Substances 0.000 title claims description 85
- 239000010419 fine particle Substances 0.000 title claims description 81
- 238000000034 method Methods 0.000 title claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 88
- 150000001875 compounds Chemical class 0.000 claims description 53
- 239000002923 metal particle Substances 0.000 claims description 53
- 239000011882 ultra-fine particle Substances 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 45
- 125000004434 sulfur atom Chemical group 0.000 claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 33
- 239000004332 silver Substances 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 21
- 150000007524 organic acids Chemical class 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 229910001111 Fine metal Inorganic materials 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 230000009257 reactivity Effects 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 description 115
- 239000010410 layer Substances 0.000 description 16
- 150000008065 acid anhydrides Chemical class 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- -1 amine compound Chemical class 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 9
- 150000003973 alkyl amines Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 239000012776 electronic material Substances 0.000 description 7
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002103 nanocoating Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229940116411 terpineol Drugs 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 150000000180 1,2-diols Chemical class 0.000 description 1
- PCGDBWLKAYKBTN-UHFFFAOYSA-N 1,2-dithiole Chemical compound C1SSC=C1 PCGDBWLKAYKBTN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、メッキ代替用の導電性金属皮膜の形成方法に関し、より具体的には、金属微粒子分散液を利用して、形成された金属微粒子分散液の塗布膜を加熱処理して、含有される金属微粒子相互を焼結して、メッキ代替用の導電性金属皮膜を形成する方法と、それに利用する金属微粒子分散液に関する。さらには、本発明は、従来のメッキ法により形成される種々の導電性部材に代えて、前記の方法により形成される、メッキ代替用の導電性金属皮膜を用いて、電子部品を基板上に搭載する方法にも関する。
【０００２】
【従来の技術】
電子材料分野においては、種々な用途でメッキ膜が利用されており、その用途に応じて、電気メッキ法、あるいは、無電解メッキ法の使い分けがなされている。電子材料分野におけるメッキの用途には、例えば、スルーホール用メッキ、エッチングレジスト用メッキ、端子用メッキ、ボンディング用メッキ、電気接点用メッキ、ハンダ付け用メッキ、接着用メッキなどがある。これらの用途に応じて、それぞれ下記するような金属皮膜がメッキ法で形成されている
スルーホール用メッキは、多層配線基板において、層間の電気的導通を図るため、基板を貫通して設けるスルーホールに対するメッキである。一般にこのスルーホールを介して導通が図られる表面と裏面側の配線回路に銅の薄膜が用いられ、対応して、スルーホール用メッキには、無電解銅メッキが利用される。多層配線基板を製造する際、スルーホール内壁の導通、ならびに、基板上の配線との導通をも図る必要があり、予め、厚さが１μｍ以下の薄付け無電解銅メッキ処理を行ない、続いて、１０〜５０μｍの厚さの無電解銅メッキを施す手法が一般的に利用されている。
【０００３】
ハンダ付け用メッキは、銅スルーホール配線基板などにおいて、銅配線表面の酸化防止と、ハンダ付け性向上のため、予め、溶融したハンダ中に配線基板を浸漬し、余分なハンダを吹き飛ばし、銅配線表面にのみ薄いハンダ層を被覆し、このハンダ層保護のため、被覆剤皮膜として形成されるものである。一般には、無電解スズメッキ膜が用いられる。近年、薄いハンダ層とその表面の被覆剤皮膜を同時に形成する手法として、有機酸鉛液とスズ粉を塗布後、加熱により銅配線表面ににハンダをプリコートするスーパーソルダー法などの技術が開発されている。
【０００４】
エッチングレジスト用メッキとは、ドライフィルム、液状レジストなどのエッチングレジストに対して用いられるもので、過去には、一般に金メッキが用いられていた。近年、ハンダメッキが主流になり、その他、スズメッキも用いられている。
【０００５】
端子用メッキは、コネクターと電気的接続を行う端子表面に対するメッキであり、低抵抗で、良好な耐食性、耐磨耗性を示す金メッキ、パラジウムメッキ、ロジウムメッキなどを、下地メッキの上に形成して用いられる。一方、この下地メッキは、ニッケルメッキ、パラジウム・ニッケルメッキ、ニッケル・ホウ素無電解ニッケルメッキなどが用いられる。
【０００６】
電気接点用メッキは、キーボードなどの電気接点を回路内に有する配線基板において、その電気接点に対して施されるメッキであり、やはり、ニッケルメッキを下地メッキとし、その上に形成される金メッキが利用されている。
【０００７】
ボンディング用メッキは、ボンディングを行う際、配線の素地に用いる銅が拡散により、表出することを防止するため、配線の銅表面に施されるメッキであり、ボンディング性に優れた高純度の金メッキが用いられる。
【０００８】
接着用メッキは、多層積層の形成の際、内装銅箔とプリプレグとの接着性向上のために用いられる。通常、プリプレグとの接着性向上のため、銅表面の酸化処理が行われるが、生成する酸化銅が侵されることを防ぐため、表面に無電解銅メッキ、無電解スズメッキが施される。
【０００９】
上述するように、電子材料分野では、様々な用途を有する金属皮膜を形成する際、安定な接合が可能で、良好な作業性、高い量産性を有するため、従来より、メッキ処理による金属皮膜の形成方法が一般に利用されてきた。ただし、上記する用途では、目的とする領域に選択的に金、銀、銅、パラジウム、ニッケルなどのメッキ処理を行う場合、そのメッキを行う前に、下地に対する前処理を施す工程を必要とする。さらに、実際のメッキ工程においては、メッキ浴にはシアン系の溶液を使用することに伴い、メッキ処理に用いた後、これらシアン系溶液の廃液処理が必要となる。また、万全を期して、廃液処理において、酸化などによりシアン化物イオンの無毒化を行うものの、周辺環境に対する配慮から、シアン系化合物など、毒性の強い薬品の使用は次第に敬遠されている。
【００１０】
【発明が解決しようとする課題】
上述するように、電子材料分野において、メッキ法は、湿式で種々の金属皮膜を高い再現性で作製可能な手段として、広い範囲で利用されているものの、前記するシアン系溶液の使用、その後の洗浄工程に伴い、処理すべき廃液が相当量発生するという本質的な課題を有している。かかる課題を回避しつつ、種々の金属皮膜を高い再現性で作製可能な手段を用いて、従来、メッキ法が利用されていた工程の一部を置き換えることが模索されている。
【００１１】
本発明は前記の課題を解決するもので、本発明の目的は、例えば、電子材料分野において、電子部品との接合、配線基板上の回路描画、スルーホールなどにおける導通形成などの各用途に利用される各種メッキに代えて、これらメッキによる金属皮膜と代替可能な、メッキ膜に匹敵する加工精度と信頼性を有し、また、簡便な工程で、高い再現性で導電性金属皮膜を形成する方法を提供することにある。より具体的には、本発明の目的は、目的とする金属からなる金属微粒子分散液を利用して、所望の領域にこの金属微粒子分散液塗布膜を形成し、この塗布膜を加熱処理して、含有される金属微粒子相互を焼結して、メッキ代替用の導電性金属皮膜を形成する方法と、それに利用する金属微粒子分散液を提供することにある。
【００１２】
【課題を解決するための手段】
本発明者らは、上記の課題を解決すべく、鋭意研究・検討を進めたところ、金属微粒子の塗布膜を作製し、その後、この金属微粒子の塗布膜に含有される微粒子相互を焼結させると、メッキ膜と同程度の均一性と導電性を有する金属皮膜を形成することが可能であることに想到した。また、メッキ膜と同程度の加工精度を達成する上では、利用する金属微粒子の平均粒子径を、メッキにより作製される金属皮膜を構成する微細な金属粒子サイズと遜色のない極めて細かなものとすることが必要となり、加えて、そのように極めて微細な金属微粒子が緻密な充填状態とする塗布膜を作製し、更に、その状態で比較的に低温で焼結を達成することが必要となることを見出した。この三つの要件の内、最初の要件は、加工精度に応じて、利用する金属微粒子として、平均粒子径が１〜１００ｎｍの範囲に選択される金属超微粒子を用いることで満たされ、また、最後の要件についても、この金属超微粒子を、その表面に酸化被膜がなく、金属原子が露呈した状態で互いに接触させると、例えば、２５０℃以下の温度で加熱処理を施すことで、容易に焼結させることが可能であることを見出した。しかしながら、第二の要件に関しては、前記金属超微粒子は、その表面に金属原子が露呈した状態で互いに接触させると、室温付近の温度でも、相互に接着（融着）が生じ、比較的に疎な凝集体形成を起こす結果、全体として、メッキ膜と遜色のない緻密な充填状態を高い再現性で達成することが困難であることをも見出した。この課題の解決手段を見出すべく、さらに、検討を進めたところ、金属超微粒子の金属原子表面に、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物１種以上により被覆された状態とすると凝集体形成を回避でき、有機溶剤中に均一に分散させることが可能であり、また、この分散液の塗布膜を形成し、含まれる有機溶剤を蒸散させると、金属超微粒子が緻密に充填された状態とすることが可能であることを見出した。さらに、有機溶剤中に、加熱処理を施す温度において、金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する前記化合物に対して、その窒素、酸素、イオウ原子を含む基と反応性を有する化合物を溶解されておくと、加熱の際、熱的にも徐々に解離する窒素、酸素、イオウ原子を含む基を有する前記化合物とそれに対する反応性を有する化合物との反応が進行し、結果的に、金属超微粒子の表面には金属原子自体が表出し、かかる金属表面相互が直接接触することが可能となり、比較的な低温での処理によっても焼結が起こり、緻密な焼結成形体の金属皮膜が形成可能であることを見出した。本発明者らは、これら一連の知見に基づき、本発明を完成するに至った。
【００１３】
すなわち、本発明のメッキ代替導電性金属膜の形成方法は、金属微粒子分散液を用いて、メッキ代替導電性金属皮膜を形成する方法であって、
メッキ代替導電膜を形成する領域に、前記金属微粒子分散液の塗布層を形成する工程と、
形成された前記金属微粒子分散液の塗布層を２５０℃を超えない温度にて加熱処理し、含有される金属微粒子相互を焼結する工程とを有し、
利用する前記金属微粒子分散液は、分散媒体となる有機溶剤中に平均粒子径が１〜１００ｎｍの範囲に選択される金属超微粒子が分散されており、
金属超微粒子表面は、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物１種以上により被覆されており、
前記加熱処理を施す際、金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する前記化合物の金属超微粒子表面からの解離がなされることを特徴とするメッキ代替導電性金属膜の形成方法である。
【００１４】
かかる本発明のメッキ代替導電性金属膜の形成方法においては、利用する金属微粒子分散液中には、
金属超微粒子表面を被覆している、金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する前記化合物に対して、前記加熱処理を施す温度において、その窒素、酸素、イオウ原子を含む基と反応性を有する化合物が溶解されており、
金属超微粒子表面からの窒素、酸素、イオウ原子を含む基を有する前記化合物の解離は、かかる窒素、酸素、イオウ原子を含む基を有する前記化合物に対する、その窒素、酸素、イオウ原子を含む基と反応性を有する前記化合物との反応により促進されることを特徴とする方法とすることが好ましい。その際、金属微粒子分散液中に含有される、前記窒素、酸素、イオウ原子を含む基と反応性を有する化合物として、有機の酸無水物またはその誘導体あるいは有機酸を用いることが好ましい。
【００１５】
一方、本発明のメッキ代替導電性金属膜の形成方法は、その代替を図るべきメッキ膜の材質に応じて、金属微粒子分散液中に含有される前記金属超微粒子は、金、銀、銅、白金、パラジウム、タングステン、ニッケル、タンタル、ビスマス、鉛、インジウム、錫、亜鉛、チタン、アルミニウムからなる群より選択される、一種類の金属からなる微粒子、または、２種類以上の金属からなる合金の微粒子であることを特徴とする方法とすることができる。
【００１６】
また、本発明は、上述の構成を有するメッキ代替導電性金属膜の形成方法に利用される金属微粒子分散液の発明をも併せて提供するものであり、すなわち、本発明の金属微粒子分散液は、メッキ代替導電膜の形成に利用される金属微粒子分散液であって、
前記金属微粒子分散液は、分散媒体となる有機溶剤中に平均粒子径が１〜１００ｎｍの範囲に選択される金属超微粒子が分散されており、
金属超微粒子表面は、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物１種以上により被覆されており、
金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する前記化合物は、２５０℃を超えない温度にて加熱処理により、金属超微粒子表面からの解離が可能であることを特徴とする金属微粒子分散液である。
【００１７】
本発明の金属微粒子分散液においては、その金属微粒子分散液中には、
金属超微粒子表面を被覆している、金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する前記化合物に対して、前記加熱処理を施す温度において、その窒素、酸素、イオウ原子を含む基と反応性を有する化合物が溶解されていることを特徴とする金属微粒子分散液とすることが好ましい。その際、金属微粒子分散液中に含有される、前記窒素、酸素、イオウ原子を含む基と反応性を有する化合物は、有機の酸無水物またはその誘導体あるいは有機酸であることが好ましい。
【００１８】
一方、本発明の金属微粒子分散液では、その代替を図るべきメッキ膜の材質に応じて、金属微粒子分散液中に含有される前記金属超微粒子は、金、銀、銅、白金、パラジウム、タングステン、ニッケル、タンタル、ビスマス、鉛、インジウム、錫、亜鉛、チタン、アルミニウムからなる群より選択される、一種類の金属からなる微粒子、または、２種類以上の金属からなる合金の微粒子であることを特徴とする金属微粒子分散液とすることができる。
【００１９】
加えて、本発明は、上述する本発明のメッキ代替導電性金属膜の形成方法の実際の利用形態として、このメッキ代替導電性金属膜を活用して、基板上に電子部品を搭載する方法の発明を提供し、すなわち、本発明の電子部品の搭載方法は、基板上に電子部品を搭載する方法であって、
前記電子部品は、導電性金属皮膜を介して導通が図られる、基板上に形成されている配線回路に対して、電気的な接続をとるように搭載する工程を有し、
基板上に形成されている前記導電性金属皮膜は、上述するいずれかの構成を有する本発明のメッキ代替導電性金属膜の形成方法により形成されていることを特徴とする電子部品の搭載方法である。
【００２０】
本発明の電子部品の搭載方法は、例えば、導通を図る導電性金属皮膜は、基板の表面と裏面間のスルーホール用メッキ膜の代替導電性金属膜であることを特徴とする方法とすることができる。また、導通を図る導電性金属皮膜は、基板上に形成されている配線回路の少なくとも一部を構成するメッキ膜の代替導電性金属膜であることを特徴とする方法とすることができる。さらには、導通を図る導電性金属皮膜は、基板上に形成されている配線回路と電子部品の配線との接続がなされるボンディング用メッキ膜の代替導電性金属膜であることを特徴とする方法とすることもできる。
【００２１】
【発明の実施の形態】
以下に、本発明のメッキ代替導電性金属膜の形成方法と、その際に利用するペースト状の金属微粒子分散液をより詳細に説明する。
【００２２】
本発明のメッキ代替導電性金属膜の形成方法は、その主な用途は、電子材料分野において、従来のメッキ法で形成される金属皮膜が利用されている部材において、その金属皮膜として、比較的低温で焼結して作製される金属微粒子の焼結体皮膜による代替である。従って、利用される金属微粒子の焼結体皮膜自体は、その代替すべきメッキ膜中の析出金属粒子サイズと同程度の平均粒子径を有する金属微粒子の焼結体皮膜であることが望ましい。従って、利用するペースト状の金属微粒子分散液中に含有する金属超微粒子は、代替すべきメッキ膜における目標膜厚に応じて、その平均粒子径は１〜１００ｎｍの範囲に選択する。好ましくは、平均粒子径を２〜１０ｎｍの範囲に選択する。
【００２３】
一般に平均粒子径数ｎｍ〜数１０ｎｍ程度の金属超微粒子はその融点よりも格段に低い温度（例えば、銀であれば２００℃）で焼結することが知られている。この低温焼結は、金属の超微粒子においては、十分にその粒子径を小さくすると、粒子表面に存在するエネルギー状態の高い原子の全体に占める割合いが大きくなり、金属原子の表面拡散が無視し得ないほど大きくなる結果、この表面拡散に起因して、粒子相互の界面の延伸がなされ焼結が行われるためである。一方、この性質は、室温近傍においても、金属超微粒子の表面相互が直接接触すると、凝集体を形成するという現象を生じさせる。前記の凝集体形成は、極めて微細な金属微粒子が密な充填状態を形成する結果達成される、厚さの均一性向上効果を損なう要因となる。さらに、密な充填状態を形成することで、全体として、所望の導電性を達成している効果を、予め部分的に凝集体を形成した構造が混入すると、密な充填状態を高い再現性で達成できなくなる一因となる。
【００２４】
それ故、本発明のメッキ代替導電性金属膜の形成方法に利用する金属微粒子分散液は、プリント配線基板などの対象物の表面上にペースト状の金属微粒子分散液の塗布膜を形成する際には、分散液に含まれる金属微粒子の凝集体形成を防止し、均一な分散状態を維持するため、金属超微粒子の表面は、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物１種以上により被覆された状態とする。すなわち、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物１種以上により、金属超微粒子の金属表面を密に被覆した状態とすることで、塗布膜を形成した後、加熱処理を施すまでは、金属超微粒子が互いにその金属表面が直接接触しない状態とする。なお、この被覆層を設けることにより、仮に塗布を行う際など酸素と接しても、金属超微粒子の表面には、酸化膜が実質的に形成されない状態ともなっている。
【００２５】
この表面の被覆に利用される化合物は、金属元素と配位的な結合を形成する際、窒素、酸素、イオウ原子上に孤立電子対を有する基を利用するもので、例えば、窒素原子を含む基として、アミノ基が挙げられる。また、イオウ原子を含む基としては、スルファニル基（−ＳＨ）、スルフィド型のスルファンジイル基（−Ｓ−）が挙げられる。また、酸素原子を含む基としては、ヒドロキシ基、エーテル型のオキシ基（−Ｏ−）が挙げられる。
【００２６】
利用可能なアミノ基を有する化合物の代表として、アルキルアミンを挙げることができる。なお、かかるアルキルアミンは、金属元素と配位的な結合を形成した状態で、通常の保管環境、具体的には、４０℃に達しない範囲では、脱離しないものが好適であり、沸点が６０℃以上の範囲、好ましくは１００℃以上となるものが好ましい。ただし、焼結・合金化を行う際には、速やかに、表面から離脱することが可能であることが必要であり、少なくとも、沸点が３００℃を超えない範囲、通常、２５０℃以下の範囲となるものが好ましい。例えば、アルキルアミンとして、そのアルキル基は、Ｃ４〜Ｃ２０が用いられ、さらに好ましくはＣ８〜Ｃ１８の範囲に選択され、アルキル鎖の末端にアミノ基を有するものが用いられる。例えば、前記Ｃ８〜Ｃ１８の範囲のアルキルアミンは、熱的な安定性もあり、また、その蒸気圧もさほど高くなく、室温等で保管する際、含有率を所望の範囲に維持・制御することが容易であるなど、ハンドリング性の面から好適に用いられる。一般に、かかる配位的な結合を形成する上では、第一級アミン型のものがより高い結合能を示し好ましいが、第二級アミン型、ならびに、第三級アミン型の化合物も利用可能である。また、１，２−ジアミン型、１，３−ジアミン型など、近接する二以上のアミノ基が結合に関与する化合物も利用可能である。
【００２７】
また、利用可能なスルファニル基（−ＳＨ）を有する化合物の代表として、アルカンチオールを挙げることができる。なお、かかるアルカンチオールも、金属元素と配位的な結合を形成した状態で、通常の保管環境、具体的には、４０℃に達しない範囲では、脱離しないものが好適であり、沸点が６０℃以上の範囲、好ましくは１００℃以上となるものが好ましい。ただし、焼結・合金化を行う際には、速やかに、表面から離脱することが可能であることが必要であり、少なくとも、沸点が３００℃を超えない範囲、通常、２５０℃以下の範囲となるものが好ましい。例えば、アルカンチオールとして、そのアルキル基は、Ｃ４〜Ｃ２０が用いられ、さらに好ましくはＣ８〜Ｃ１８の範囲に選択され、アルキル鎖の末端にスルファニル基（−ＳＨ）を有するものが用いられる。例えば、前記Ｃ８〜Ｃ１８の範囲のアルカンチオールは、熱的な安定性もあり、また、その蒸気圧もさほど高くなく、室温等で保管する際、含有率を所望の範囲に維持・制御することが容易であるなど、ハンドリング性の面から好適に用いられる。一般に、第一級チオール型のものがより高い結合能を示し好ましいが、第二級チオール型、ならびに、第三級チオール型の化合物も利用可能である。また、１，２−ジチオール型などの、二以上のスルファニル基（−ＳＨ）が結合に関与するものも、利用可能である。
【００２８】
また、利用可能なヒドロキシ基を有する化合物の代表として、アルカンジオールを挙げることができる。なお、かかるアルカンジオールも、金属元素と配位的な結合を形成した状態で、通常の保管環境、具体的には、４０℃に達しない範囲では、脱離しないものが好適であり、沸点が６０℃以上の範囲、通常、１００℃以下の範囲となるものが好ましい。ただし、焼結・合金化を行う際には、速やかに、表面から離脱することが可能であることが必要であり、少なくとも、沸点が３００℃を超えない範囲、通常、２５０℃以下の範囲となるものが好ましい。例えば、１，２−ジオール型などの、二以上のヒドロキシ基が結合に関与するものなどが、より好適に利用可能である。
【００２９】
加えて、上述する金属超微粒子の表面を被覆している金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物に対して、加熱した際、その窒素、酸素、イオウ原子を含む基との反応性を有する化合物成分、例えば、有機の酸無水物または酸無水物誘導体あるいは有機酸を、金属超微粒子分散液中に添加することができる。この窒素、酸素、イオウ原子を含む基との反応性を有する化合物は、加熱した際、上述する金属超微粒子の表面を被覆する、金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物による付着層を除去するために利用される。すなわち、加熱に伴い、室温付近では付着層を形成している被覆化合物中の、窒素、酸素、イオウ原子を含む基と反応する結果、その反応後、前記窒素、酸素、イオウ原子を含む基は、金属超微粒子表面において、表面の金属原子と配位的な結合を形成することが困難となり、結果的に除去がなされる。この除去機能は、ペースト状の金属微粒子分散液の塗布膜形成がなされる、室温近傍では発揮されず、その後、塗布膜に対する加熱処理の過程において、初めて発揮されるものとなる。
【００３０】
具体的には、添加されている酸無水物または酸無水物誘導体は、加熱に伴い、前記窒素、酸素、イオウ原子を含む基を有する化合物、例えば、アミン化合物、チオール化合物、ジオール化合物などと反応し、アミド、チオエステル、エステルを形成するために利用される。このアミド、チオエステル、エステルを形成すると、金属原子と配位的な結合を形成することが困難となり、結果的に、金属超微粒子の表面被覆層の除去がなされる。従って、極めて微細な金属超微粒子は、元々均一に分散しており、塗布膜中に含まれる有機溶剤が蒸散するに伴い、緻密な充填状態を採りつつ、その金属表面を直接接触させて加熱処理が進み、比較的に低温でも互いに焼結する。最終的に、塗布膜中の金属超微粒子全体は、緻密な焼結体皮膜となり、メッキ膜と比較しても、その緻密度は遜色のないものとなる。従って、この酸無水物または酸無水物誘導体の含有量は、上記アミン化合物、チオール化合物、ジオール化合物などに含まれる末端アミノ基、スルファニル基（−ＳＨ）、ヒドロキシ基の総和に応じて、少なくとも、それと等量となる量を超えて添加すると好ましい。なお、酸無水物または酸無水物誘導体は、加熱した際、場合によっては、塩基性を有する金属酸化物の皮膜とも反応して、カルボン酸の金属塩を生成する機能も有するため、その反応性をも考慮に入れ、若干過剰な量が適宜選択される。
【００３１】
前記の反応性を示す限り、利用される有機の酸無水物またはその誘導体あるいは有機酸は特に限定されるものではない。例えば、利用可能な有機酸としては、ギ酸、酢酸、プロピオン酸、ブタン酸、ヘキサン酸、オクチル酸などのＣ１〜Ｃ１０の直鎖または分岐した飽和カルボン酸、ならびにアクリル酸、メタクリル酸、クロトン酸、ケイ皮酸、安息香酸、ソルビン酸などの不飽和カルボン酸、ならびに、シュウ酸、マロン酸、セバシン酸、マレイン酸、フマル酸、イタコン酸などの二塩基酸など、種々のカルボン酸に加えて、カルボキシル基に代えて、リン酸基（−O-P(O)（OH）2）あるいは、スルホ基（−SO3H）を有する、リン酸エステル、スルホン酸などのその他の有機酸を挙げることができる。
【００３２】
また、好適に利用できる有機の酸無水物もしくは酸無水物の誘導体として、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、エチレングリコールビス（アンヒドロトリメリテート）、グリセロールトリス（アンヒドロトリメリテート）などの芳香族酸無水物、無水マレイン酸、無水コハク酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、アルケニル無水コハク酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルシクロヘキセンテトラカルボン酸無水物などの環状脂肪族酸無水物、ポリアジピン酸無水物、ポリアゼライン酸無水物、ポリセバシン酸無水物などの脂肪族酸無水物を挙げることができる。この中でも、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、およびこれらの誘導体は、本発明が目的とする比較的に低い加熱処理（焼結）温度においても、例えば、アミン化合物の末端アミノ基などに対して適度な反応性を有することから好適に用いられる。
【００３３】
本発明のメッキ代替導電性金属膜の形成方法において、利用するペースト状の金属微粒子分散液は、塗布後に加熱処理を行うものの、その塗布する際には、前記表面に分子の被覆層を設けた金属超微粒子を分散する分散溶媒として、有機溶剤一種以上を含有したものとする。この有機溶剤中には、上記の窒素、酸素、イオウ原子を含む基との反応性を有する化合物成分、例えば、有機の酸無水物または酸無水物誘導体あるいは有機酸が均一に溶解した状態とすることが好ましい。一方、ペースト状の金属微粒子分散液を長期にわたり保管する間も、表面に分子の被覆層を設けた金属超微粒子が均一な分散状態を維持する上では、用いる金属超微粒子の表面を被覆している、アミン化合物などの化合物の付着層を溶出することのない有機溶剤が好適に利用される。
【００３４】
この二種の用途・目的に用いられる有機溶剤は、異なる種類のものを用いることもできるが、同じ有機溶剤を用いることが好ましい。なお、前記の二種の用途に利用できる限り、その種類は限定されるものではないが、金属超微粒子の表面に付着層を形成している化合物、例えば、アルキルアミンなどの溶解性が高すぎ、金属超微粒子表面の付着層が消失するような高い極性を有する溶剤ではなく、非極性溶剤あるいは低極性溶剤を選択することが好ましい。
【００３５】
加えて、本発明のメッキ代替導電性金属膜の形成方法では、塗布後、焼結のため、加熱処理を行う温度において、かかる有機溶剤は、比較的速やかに蒸散でき、その間に熱分解などを起こすことがない程度には熱的な安定性を有することが好ましい。また、微細なラインを形成する際、その塗布の工程において、金属微粒子分散液を所望とする膜厚の塗布膜としてスクリーン印刷法などで塗布するため、好適な液粘度範囲に維持することも必要となる。そのハンドリング性の面を考慮すると、室温付近では容易に蒸散することのない、比較的に高沸点な非極性溶剤あるいは低極性溶剤、例えば、テルピネオール、ミネラルスピリット、キシレン、トルエン、エチルベンゼン、メシチレンなどが好適に利用でき、さらには、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、シクロヘキサン、シクロオクタンなども用いることができる。
【００３６】
かかる有機溶剤の含有量は、それが溶解すべき、窒素、酸素、イオウ原子を含む基との反応性を有する化合物、例えば、有機の酸無水物またはその誘導体あるいは有機酸などの量に拠って選択される。また、分散される金属超微粒子の量、その分散密度に応じて、含有比率を選択する。その際、通常、ペースト状の金属微粒子分散液中、分散媒質の金属超微粒子１００質量部当たり、前記有機溶剤の含有量を５〜１００質量部の範囲に選択することが好ましい。なお、適正な塗布性能、例えば、線幅精度、膜厚の制御性に応じて、ペースト状の金属微粒子分散液の液粘度を調製する必要があり、例えば、有機溶剤の添加量を調整して、最終液粘度を、１〜５００Ｐａ・ｓの範囲、好ましくは、２〜２００Ｐａ・ｓの範囲に選択することが望ましい。
【００３７】
一方、ペースト状の金属微粒子分散液中に含有される、微細な平均粒子径の金属超微粒子は、形成すべき導電性金属膜が代替するメッキ膜の用途、その材質に応じて、例えば、銀、銅、白金、パラジウム、タングステン、ニッケル、タンタル、ビスマス、鉛、インジウム、錫、亜鉛、チタン、アルミニウムからなる群より選択される、一種類の金属からなる微粒子、または、２種類以上の金属からなる合金の微粒子を、適宜選択することができる。通常の目的では、金、銀、銅、白金など、それ自体の電気伝導性に優れる金属からなる微粒子を利用することが多い。なお、合金微粒子を用いる際には、通常、焼結のための加熱処理温度より、かかる合金の融点が高いものを用いる際に、本発明の効果が発揮されるものとなる。
【００３８】
また、本発明の電子部品の搭載方法は、上述するメッキ代替導電性金属膜の形成方法を採用して作製される導電性金属膜を、従来はメッキ膜を利用している電子材料部材に新たに利用することで、その実装基板上への電子部品の実装・搭載を行う方法である。電子部品の搭載用部材においては、種々のメッキ膜が利用されているが、その内、通常のメッキ法と異なり、本発明のメッキ代替導電性金属膜の形成方法における特徴的で必須な工程である、金属超微粒子の低温焼結工程の加熱処理が何らかの不具合を生じることのない範囲で、メッキ膜の代替が可能である。特に、本発明のメッキ代替導電性金属膜の形成方法においては、メッキと異なり、水性試薬を用いる湿式工程を必要としないことの利点が発揮される形態がより好適である。
【００３９】
例えば、特定の領域にのみ、選択的な導電性金属膜を形成することを要する場合により適するものとなる。従って、基板上に電子部品を搭載する一連の工程は、電子部品を、導電性金属皮膜を介して導通が図られる、基板上に形成されている配線回路に対して、電気的な接続をとるように搭載する工程を含むが、その際、基板上に形成されている導電性金属皮膜は、本発明のメッキ代替導電性金属膜の形成方法を用いることで、必要部分のみに選択的に形成される場合が好ましいものとなる。
【００４０】
一例として、導通を図る導電性金属皮膜が、基板の表面と裏面間のスルーホール用メッキ膜の代替導電性金属膜として利用される場合、あるいは、基板上に形成されている配線回路の少なくとも一部を構成するメッキ膜の代替導電性金属膜として利用される場合が挙げられる。加えて、導通を図る導電性金属皮膜が、基板上に形成されている配線回路と電子部品の配線との接続がなされるボンディング用メッキ膜の代替導電性金属膜として利用される場合をも一例として挙げられる。また、本発明のペースト状の金属微粒子分散液を基板に塗布後、その塗布膜部分にチップなどの電子部品を搭載し、２５０℃以下のの低温にて加熱焼結することで、信頼性の高い電子部品の接合を行うことも可能となる。
【００４１】
加えて、本発明の電子部品の搭載方法においては、利用するペースト状の金属微粒子分散液は、金属微粒子相互の電気的な導通と、成形・固化には、有機バインダーを利用しておらず、有機バインダーを利用している導電性金属ペーストと異なり、かかる導電性金属膜に対して、ハンダ剤を更に利用して、複数の電子部品を実装する形態とすることも可能である。
【００４２】
【実施例】
以下に、実施例を示し、本発明をより具体的に説明する。この実施例は、本発明の最良の実施の形態の一例ではあるものの、本発明はこの実施例により限定を受けるものではない。
【００４３】
（実施例１）
市販されている銀の超微粒子分散液（商品名：独立分散超微粒子パーフェクトシルバー、真空冶金（株））、具体的には、銀微粒子１００質量部、アルキルアミンとして、ドデシルアミン１５質量部、有機溶剤として、ターピネオール７５質量部を含む平均粒径８ｎｍの銀微粒子の分散液を利用して、ペースト状の銀超微粒子の分散液を調製した。
【００４４】
ペースト状の銀超微粒子分散液は、前記銀微粒子の分散液に、その分散液中の銀微粒子１００質量部当たり、加熱時にドデシルアミンと反応する成分となる、酸無水物として、メチルヘキサヒドロ無水フタル酸（Ｍｅ−ＨＨＰＡ）１０質量部を添加し、攪拌脱泡機で十分に攪拌して、均一化を図った。なお、調製されたペースト状の銀超微粒子分散液の液粘度は、６０Ｐａ・ｓである。
【００４５】
調製したペースト状の銀超微粒子分散液を、銅張り積層板の銅箔面上に塗布し、この８０μｍ厚さの塗布膜上に、半導体部品の金配線を置き、不活性雰囲気下、１５０℃×３０分、＋２１０℃×６０分の温度条件で加熱処理を施した。この加熱処理により、塗布膜に含まれる銀超微粒子の焼結がなされ、銅張り積層板の銅箔面と半導体部品の金配線との間に、ボンディング用メッキ膜の代替層として形成される銀超微粒子の焼結体膜を介して、固定と、電気的な導通が形成された。その際、ボンディングされた金配線と積層板（銅箔面）間の接続抵抗値は、１．２×１０-6Ωであった。
【００４６】
（実施例２）
実施例１と同様に、ペースト状の銀超微粒子分散液を調製した。平均粒径８ｎｍの銀微粒子１００質量部当たり、アルキルアミンとして、ドデシルアミン１５質量部、有機溶剤として、ターピネオール７５質量部を含む分散液を利用して、その分散液中の銀微粒子１００質量部当たり、含有されるドデシルアミンと加熱時に反応する成分となる、酸無水物として、メチルヘキサヒドロ無水フタル酸（Ｍｅ−ＨＨＰＡ）１０質量部を添加し、攪拌脱泡機で十分に攪拌して、均一化を図った。なお、調製されたペースト状の銀超微粒子分散液の液粘度は、６０Ｐａ・ｓである。
【００４７】
調製されたペースト状の銀超微粒子分散液をプリント配線基板面上にスクリーン印刷により、回路パターン状の印刷塗布した。この５０μｍ厚さの塗布膜に、不活性雰囲気下、１５０℃×３０分、＋２１０℃×６０分の温度条件で加熱処理を施した。この加熱処理により、塗布膜に含まれる銀超微粒子の焼結がなされ、プリント配線基板の表面に、メッキ膜の代替層として形成される銀超微粒子の焼結体膜からなる回路配線が形成された。得られた回路の抵抗値（面抵抗率）は７．５×１０-6Ω・□であった。
【００４８】
（実施例３）
実施例１と同様に、ペースト状の銀超微粒子分散液を調製した。平均粒径８ｎｍの銀微粒子１００質量部当たり、アルキルアミンとして、ドデシルアミン１５質量部、有機溶剤として、ターピネオール７５質量部を含む分散液を利用して、その分散液中の銀微粒子１００質量部当たり、含有されるドデシルアミンと加熱時に反応する成分となる、酸無水物として、メチルヘキサヒドロ無水フタル酸（Ｍｅ−ＨＨＰＡ）１０質量部を添加し、攪拌脱泡機で十分に攪拌して、均一化を図った。なお、調製されたペースト状の銀超微粒子分散液の液粘度は、６０Ｐａ・ｓである。
【００４９】
調製されたペースト状の銀超微粒子分散液を、スクリーン印刷により、基板厚さ１．６ｍｍの両面配線基板の内径０．５ｍｍのスルーホールを埋め込むように、印刷した。この平面部分での厚さ５０μｍの塗布膜に、不活性雰囲気下、１５０℃×３０分、＋２１０℃×６０分の温度条件で加熱処理を施した。この加熱処理により、塗布膜に含まれる銀超微粒子の焼結がなされ、両面配線基板を貫通するスルーホールの内壁面に、スルーホール用メッキ膜の代替層として形成される銀超微粒子の焼結体膜が形成された。得られたスルーホールを介する導通路の抵抗値（層間の接続抵抗値）は、１つのスルーホール当たり、９．１×１０-6Ωであった。
【００５０】
【発明の効果】
本発明の金属微粒子分散液を用いたメッキ代替導電性金属皮膜の形成方法では、利用する金属微粒子分散液中に分散させる金属微粒子として、平均粒子径１〜１００ｎｍの金属超微粒子を利用し、その金属超微粒子の表面には、その金属元素と配位的な結合が可能な基として、窒素、酸素、イオウ原子を含む基を有する化合物１種以上による緻密な分子被覆層を設けることで、塗布・印刷までの間は、この金属超微粒子の凝集、融着を抑制するものである。加えて、緻密な分子被覆層は、金属超微粒子表面の自然酸化をも抑制して、この金属微粒子分散液の長期にわたる保管と、品質維持、分散特性の維持を可能ともする。一方、金属超微粒子を分散している有機溶媒中には、加熱処理を施す温度において、窒素、酸素、イオウ原子を含む基と反応性を有する化合物を添加しておくことで、金属超微粒子表面を覆う、窒素、酸素、イオウ原子を含む基を有する化合物の被覆層の除去を可能としている。優れた圧縮性、成形性を保持して、有機溶媒中に均一に分散している金属微粒子は、塗布膜中において、最終的には、緻密な充填状態をとり、その清浄な金属超微粒子表面を互いに接し、加熱処理される間に低温焼結され、メッキ膜と比較しても遜色のない緻密な金属皮膜が高い再現性で形成できる。加えて、一般の導電性金属ペーストとは異なり、本発明のペースト状の金属微粒子分散液は、本質的に有機バインダー成分を含まず、金属超微粒子相互の焼結により、その形状、導電性を達成するものであるので、塗布される部分の表面形状、隙間間隔などに依らず、均質な導電性皮膜を与えることを可能としている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of forming a conductive metal film for plating substitution, and more specifically, the coating film of the formed metal fine particle dispersion is heat-treated using the metal fine particle dispersion and contained. The present invention relates to a method of sintering metal fine particles to form a conductive metal film as a substitute for plating, and a metal fine particle dispersion used therefor. Furthermore, the present invention provides an electronic component on a substrate using a conductive metal film for plating instead of various conductive members formed by the conventional plating method. It also relates to the method of mounting.
[0002]
[Prior art]
In the field of electronic materials, a plating film is used for various purposes, and an electroplating method or an electroless plating method is selectively used depending on the use. Examples of plating applications in the field of electronic materials include through-hole plating, etching resist plating, terminal plating, bonding plating, electrical contact plating, soldering plating, and adhesive plating. Depending on these applications, the following metal films are formed by plating.
Through-hole plating is plating for through-holes provided through a substrate in order to achieve electrical conduction between layers in a multilayer wiring board. In general, a copper thin film is used for the wiring circuits on the front surface and the back surface that are conductive through the through hole. Correspondingly, electroless copper plating is used for plating for the through hole. When manufacturing a multilayer wiring board, it is necessary to conduct the inner wall of the through hole and the wiring on the board, and in advance, a thin electroless copper plating process having a thickness of 1 μm or less is performed, A method of applying electroless copper plating with a thickness of 10 to 50 μm is generally used.
[0003]
Solder plating is used to prevent oxidation of the copper wiring surface and improve solderability in copper through-hole wiring boards, etc., soak the wiring board in molten solder in advance and blow off the excess solder. A thin solder layer is coated only on the surface, and is formed as a coating film for protecting the solder layer. In general, an electroless tin plating film is used. In recent years, as a method for simultaneously forming a thin solder layer and a coating film on its surface, techniques such as the super solder method have been developed, in which an organic acid lead solution and tin powder are applied and then solder is pre-coated on the copper wiring surface by heating. ing.
[0004]
Etching resist plating is used for etching resists such as dry film and liquid resist, and gold plating has been generally used in the past. In recent years, solder plating has become mainstream, and tin plating is also used.
[0005]
The terminal plating is a plating on the terminal surface that is electrically connected to the connector, and it is formed on the base plating with gold plating, palladium plating, rhodium plating, etc. showing low resistance and good corrosion resistance and wear resistance. Used. On the other hand, for the base plating, nickel plating, palladium / nickel plating, nickel / boron electroless nickel plating, or the like is used.
[0006]
The electrical contact plating is a plating applied to the electrical contact in a circuit board having an electrical contact such as a keyboard in the circuit. Again, a nickel plating is used as a base plating, and a gold plating formed thereon is used. It's being used.
[0007]
Bonding plating is a plating applied to the copper surface of the wiring to prevent the copper used for the wiring substrate from being exposed due to diffusion during bonding, and is a high-purity gold plating with excellent bonding properties. Is used.
[0008]
Adhesive plating is used to improve the adhesion between the interior copper foil and the prepreg when forming a multilayer stack. Usually, the copper surface is oxidized to improve adhesion to the prepreg, but the surface is subjected to electroless copper plating and electroless tin plating to prevent the generated copper oxide from being attacked.
[0009]
As described above, in the field of electronic materials, when forming a metal film having various uses, stable bonding is possible, good workability, and high mass productivity. Formation methods have been commonly used. However, in the above-described application, when a plating treatment of gold, silver, copper, palladium, nickel, or the like is selectively performed on a target region, a step of performing a pretreatment on the base is required before the plating is performed. . Further, in an actual plating process, a cyan solution is used in the plating bath, and after using the plating solution, a waste solution treatment of these cyan solutions is required. In addition, in the treatment of waste liquids, cyanide ions are detoxified by oxidation or the like in the waste liquid treatment, but due to consideration for the surrounding environment, the use of highly toxic chemicals such as cyanide compounds is gradually avoided.
[0010]
[Problems to be solved by the invention]
As described above, in the field of electronic materials, the plating method is used in a wide range as a means capable of producing various metal films with high reproducibility, but the use of the above-described cyan solution, Along with the cleaning process, there is an essential problem that a considerable amount of waste liquid to be treated is generated. While avoiding such problems, it has been sought to replace a part of the process in which the plating method has been conventionally used by using means capable of producing various metal films with high reproducibility.
[0011]
The present invention solves the above-mentioned problems, and the object of the present invention is used in various applications such as bonding to electronic components, circuit drawing on a wiring board, and conduction formation in a through hole in the field of electronic materials. In place of various platings that can be used, these metal films can be replaced by plating, which has processing accuracy and reliability comparable to plating films, and forms conductive metal films with high reproducibility in a simple process. It is to provide a method. More specifically, the object of the present invention is to form a metal fine particle dispersion coating film in a desired region using a metal fine particle dispersion liquid made of the target metal, and heat-treat the coating film. An object of the present invention is to provide a method for forming a conductive metal film as a substitute for plating by sintering metal fine particles contained therein and a metal fine particle dispersion used therefor.
[0012]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have conducted extensive research and examination. As a result, a coating film of metal fine particles is produced, and then the fine particles contained in the coating film of metal fine particles are sintered together. It was conceived that a metal film having the same degree of uniformity and conductivity as the plated film can be formed. In order to achieve the same level of processing accuracy as the plating film, the average particle diameter of the metal fine particles to be used is extremely fine, comparable to the size of the fine metal particles that make up the metal film produced by plating. In addition, it is necessary to produce a coating film in which such extremely fine metal fine particles are densely packed, and to achieve sintering at a relatively low temperature in that state. I found out. Among these three requirements, the first requirement is satisfied by using metal ultrafine particles whose average particle diameter is selected in the range of 1 to 100 nm as the metal fine particles to be used, depending on the processing accuracy. The ultrafine metal particles can be easily sintered by, for example, performing a heat treatment at a temperature of 250 ° C. or lower when the metal ultrafine particles are brought into contact with each other in a state where there is no oxide film on the surface and metal atoms are exposed. I found out that it is possible. However, regarding the second requirement, when the metal ultrafine particles are brought into contact with each other with the metal atoms exposed on the surface thereof, they are bonded (fused) to each other even at a temperature near room temperature, and are relatively sparse. As a result of the formation of agglomerated aggregates, it has also been found that, as a whole, it is difficult to achieve a dense filling state comparable to the plating film with high reproducibility. In order to find a solution to this problem, further studies have been conducted. As a group capable of coordinative bonding with the metal element contained in the ultrafine metal particles, nitrogen, oxygen, In addition, when it is covered with one or more compounds having a group containing a sulfur atom, formation of aggregates can be avoided, and the dispersion can be uniformly dispersed in an organic solvent, and a coating film of this dispersion can be formed. And when the organic solvent contained was evaporated, it discovered that it was possible to set it as the state with which the metal ultrafine particle was densely packed. Furthermore, as a group capable of coordinative bonding with a metal element at a temperature at which heat treatment is performed in an organic solvent, the nitrogen, oxygen, When a compound having reactivity with a group containing a sulfur atom is dissolved, it reacts with the compound having a group containing nitrogen, oxygen and sulfur atoms which gradually dissociates thermally during heating. The reaction with the compound proceeds, and as a result, the metal atoms themselves appear on the surface of the ultrafine metal particles, and the metal surfaces can be in direct contact with each other. As a result, it was found that a dense metal film of a sintered compact can be formed. Based on these series of findings, the present inventors have completed the present invention.
[0013]
That is, the plating substitute conductive metal film forming method of the present invention is a method of forming a plating substitute conductive metal film using a metal fine particle dispersion,
Forming a coating layer of the metal fine particle dispersion in a region where the plating alternative conductive film is formed;
Heat-treating the formed coating layer of the metal fine particle dispersion at a temperature not exceeding 250 ° C., and sintering the contained metal fine particles.
The metal fine particle dispersion to be used has dispersed therein ultrafine metal particles having an average particle diameter of 1 to 100 nm in an organic solvent serving as a dispersion medium,
The surface of the metal ultrafine particle is coated with one or more compounds having a group containing nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with the metal element contained in the metal ultrafine particle.
When the heat treatment is performed, the compound having a group containing nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with a metal element is dissociated from the surface of the metal ultrafine particles. This is a method of forming a plating substitute conductive metal film.
[0014]
In the method for forming a plating substitute conductive metal film of the present invention, in the metal fine particle dispersion to be used,
At the temperature at which the heat treatment is performed on the compound having a group containing nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with a metal element that coats the surface of the metal ultrafine particle, A compound reactive with a group containing nitrogen, oxygen, or sulfur atoms is dissolved,
Dissociation of the compound having a group containing nitrogen, oxygen, and sulfur atoms from the surface of the ultrafine metal particles is a group containing the nitrogen, oxygen, and sulfur atoms with respect to the compound having the group containing nitrogen, oxygen, and sulfur atoms. It is preferable to use a method characterized by being promoted by a reaction with the reactive compound. At that time, it is preferable to use an organic acid anhydride, a derivative thereof, or an organic acid as the compound that is reactive with the group containing nitrogen, oxygen, and sulfur atoms contained in the metal fine particle dispersion.
[0015]
On the other hand, according to the method of forming a plating substitute conductive metal film of the present invention, the metal ultrafine particles contained in the metal fine particle dispersion are gold, silver, copper, Selected from the group consisting of platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum, or a fine particle composed of one kind of metal, or an alloy composed of two or more kinds of metals. The method can be characterized by being fine particles.
[0016]
The present invention also provides an invention of a metal fine particle dispersion used in the method for forming a plating-substitute conductive metal film having the above-described configuration. That is, the metal fine particle dispersion of the present invention includes: , A metal fine particle dispersion used for forming a plating alternative conductive film,
In the metal fine particle dispersion, metal ultrafine particles having an average particle diameter selected in the range of 1 to 100 nm are dispersed in an organic solvent serving as a dispersion medium.
The surface of the metal ultrafine particle is coated with one or more compounds having a group containing nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with the metal element contained in the metal ultrafine particle.
As a group capable of coordinative bonding with a metal element, the compound having a group containing nitrogen, oxygen, or sulfur atom can be dissociated from the surface of ultrafine metal particles by heat treatment at a temperature not exceeding 250 ° C. It is a metal fine particle dispersion characterized by the above.
[0017]
In the fine metal particle dispersion of the present invention, the fine metal particle dispersion contains
At the temperature at which the heat treatment is performed on the compound having a group containing nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with a metal element that coats the surface of the metal ultrafine particle, A metal fine particle dispersion characterized by dissolving a compound reactive with a group containing nitrogen, oxygen and sulfur atoms is preferred. At that time, the compound having reactivity with the group containing nitrogen, oxygen and sulfur atoms contained in the metal fine particle dispersion is preferably an organic acid anhydride, a derivative thereof or an organic acid.
[0018]
On the other hand, in the metal fine particle dispersion of the present invention, the metal ultrafine particles contained in the metal fine particle dispersion are gold, silver, copper, platinum, palladium, tungsten, depending on the material of the plating film to be replaced. Selected from the group consisting of nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum, fine particles made of one type of metal, or fine particles of an alloy made of two or more types of metals. It can be set as the metal fine particle dispersion characterized.
[0019]
In addition, the present invention provides a method for mounting an electronic component on a substrate by utilizing the plating substitute conductive metal film as an actual utilization form of the plating substitute conductive metal film of the present invention described above. Provided invention, that is, a mounting method of an electronic component of the present invention is a method of mounting an electronic component on a substrate,
The electronic component has a step of mounting so as to be electrically connected to a wiring circuit formed on the substrate, which is electrically connected through a conductive metal film,
The method of mounting an electronic component, wherein the conductive metal film formed on the substrate is formed by the plating substitute conductive metal film forming method of the present invention having any one of the above-described configurations. is there.
[0020]
The electronic component mounting method of the present invention is, for example, a method characterized in that the conductive metal film that is conductive is an alternative conductive metal film for the through-hole plating film between the front surface and the back surface of the substrate. Can do. Further, the conductive metal film for conducting can be a method characterized in that the conductive metal film is an alternative conductive metal film for the plating film constituting at least a part of the wiring circuit formed on the substrate. Furthermore, the conductive metal film that conducts is a conductive metal film that is an alternative to the bonding plating film that connects the wiring circuit formed on the substrate and the wiring of the electronic component. It can also be.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Below, the formation method of the plating substitute electroconductive metal film of this invention and the paste-form metal fine particle dispersion used in that case are demonstrated in detail.
[0022]
The method for forming a plating substitute conductive metal film of the present invention is mainly used in the field of electronic materials in a member in which a metal film formed by a conventional plating method is used. It is an alternative to sintered metal film of metal fine particles produced by sintering at low temperature. Therefore, it is desirable that the metal fine particle sintered body coating itself is a metal fine particle sintered body film having an average particle size comparable to the size of the deposited metal particle in the plating film to be replaced. Accordingly, the average particle diameter of the ultrafine metal particles contained in the paste-like fine metal particle dispersion to be used is selected in the range of 1 to 100 nm according to the target film thickness of the plating film to be replaced. Preferably, the average particle size is selected in the range of 2 to 10 nm.
[0023]
In general, it is known that ultrafine metal particles having an average particle diameter of several nanometers to several tens of nanometers are sintered at a temperature much lower than the melting point (for example, 200 ° C. for silver). In this low-temperature sintering, if the particle size of metal ultrafine particles is sufficiently reduced, the proportion of the high energy state atoms present on the particle surface will increase and the surface diffusion of metal atoms will be ignored. This is because, as a result of being unacceptably large, due to the surface diffusion, the interface between the particles is stretched and sintered. On the other hand, this property causes a phenomenon that aggregates are formed when the surfaces of metal ultrafine particles are in direct contact with each other even near room temperature. The formation of the agglomerates is a factor that impairs the effect of improving the thickness uniformity, which is achieved as a result of extremely fine metal fine particles forming a dense packing state. Furthermore, by forming a densely packed state, the effect of achieving the desired conductivity as a whole is mixed with the structure in which the agglomerates are partially formed in advance. It becomes a cause that cannot be achieved.
[0024]
Therefore, the metal fine particle dispersion used in the method for forming a plating substitute conductive metal film of the present invention is used when forming a coating film of a paste-like metal fine particle dispersion on the surface of an object such as a printed wiring board. Prevents the formation of agglomerates of fine metal particles contained in the dispersion and maintains a uniform dispersion state, so that the surface of the ultrafine metal particles can be coordinated with the metal elements contained in the ultrafine metal particles. As such a group, a state in which it is covered with one or more compounds having a group containing nitrogen, oxygen and sulfur atoms is used. That is, the metal surface of the ultrafine metal particles is densely coated with one or more compounds having groups containing nitrogen, oxygen, and sulfur atoms as groups capable of coordinative bonding with the metal elements contained in the ultrafine metal particles. In this state, the metal ultrafine particles are not in direct contact with each other until the heat treatment is performed after the coating film is formed. By providing this coating layer, an oxide film is not substantially formed on the surface of the metal ultrafine particles even if it is in contact with oxygen, such as when coating is performed.
[0025]
The compound used for coating the surface uses a group having a lone pair on a nitrogen, oxygen, or sulfur atom when forming a coordinate bond with a metal element, and includes, for example, a nitrogen atom. Examples of the group include an amino group. Examples of the group containing a sulfur atom include a sulfanyl group (—SH) and a sulfide type sulfanediyl group (—S—). Examples of the group containing an oxygen atom include a hydroxy group and an ether type oxy group (—O—).
[0026]
A representative example of the compound having an amino group that can be used is an alkylamine. Such an alkylamine is preferably one that does not desorb in a normal storage environment, specifically in a range not reaching 40 ° C., in a state in which a coordinate bond is formed with the metal element, and has a boiling point. A range of 60 ° C. or higher, preferably 100 ° C. or higher is preferable. However, when carrying out sintering / alloying, it is necessary to be able to detach from the surface promptly, at least in a range where the boiling point does not exceed 300 ° C., usually in the range of 250 ° C. or less. Is preferred. For example, as the alkylamine, C4 to C20 is used as the alkyl group, more preferably C8 to C18 is selected, and an alkyl group having an amino group at the terminal is used. For example, the alkylamine in the range of C8 to C18 has thermal stability and its vapor pressure is not so high, and when it is stored at room temperature or the like, its content is maintained and controlled within a desired range. It is preferably used from the viewpoint of handling properties. In general, in forming such a coordination bond, the primary amine type is preferable because it shows higher binding ability, but secondary amine type and tertiary amine type compounds can also be used. is there. In addition, compounds in which two or more adjacent amino groups are involved in bonding, such as 1,2-diamine type and 1,3-diamine type, can also be used.
[0027]
Moreover, alkanethiol can be mentioned as a typical example of a compound having a sulfanyl group (—SH) that can be used. In addition, such alkanethiol is preferably in a state in which a coordinate bond is formed with a metal element and does not desorb in a normal storage environment, specifically, in a range not reaching 40 ° C., and has a boiling point. A range of 60 ° C. or higher, preferably 100 ° C. or higher is preferable. However, when carrying out sintering / alloying, it is necessary to be able to detach from the surface promptly, at least in a range where the boiling point does not exceed 300 ° C., usually in the range of 250 ° C. or less. Is preferred. For example, as the alkanethiol, C4-C20 is used as the alkyl group, and more preferably C8-C18 is selected, and an alkyl chain having a sulfanyl group (—SH) is used. For example, the alkanethiol in the range of C8 to C18 has thermal stability and its vapor pressure is not so high, and when it is stored at room temperature or the like, the content rate is maintained and controlled within a desired range. It is preferably used from the viewpoint of handling properties. In general, primary thiol type compounds are preferred because they exhibit higher binding ability, but secondary thiol type and tertiary thiol type compounds can also be used. In addition, those in which two or more sulfanyl groups (—SH) are involved in binding, such as 1,2-dithiol type, can also be used.
[0028]
Moreover, alkanediol can be mentioned as a representative of the compound which has a hydroxyl group which can be utilized. In addition, such alkanediols are preferably those that do not desorb in a normal storage environment, specifically in a range that does not reach 40 ° C., in a state in which a coordinate bond is formed with the metal element. A range of 60 ° C. or higher, usually 100 ° C. or lower, is preferred. However, when carrying out sintering / alloying, it is necessary to be able to detach from the surface promptly, at least in a range where the boiling point does not exceed 300 ° C., usually in the range of 250 ° C. or less. Is preferred. For example, those involving two or more hydroxy groups, such as 1,2-diol type, can be used more suitably.
[0029]
In addition, when a compound having a group containing nitrogen, oxygen, or sulfur atoms as a group capable of coordinative bonding with the metal element covering the surface of the metal ultrafine particles described above is heated, A compound component having reactivity with a group containing nitrogen, oxygen and sulfur atoms, for example, an organic acid anhydride, an acid anhydride derivative, or an organic acid can be added to the ultrafine metal particle dispersion. The compound having reactivity with a group containing nitrogen, oxygen, and sulfur atoms, when heated, covers the surface of the above-mentioned metal ultrafine particles, as a group capable of coordinative bonding with a metal element, nitrogen, It is used for removing an adhesion layer formed by a compound having a group containing oxygen and sulfur atoms. That is, as a result of reaction with a group containing nitrogen, oxygen, and sulfur atoms in the coating compound forming an adhesion layer near room temperature with heating, the group containing nitrogen, oxygen, and sulfur atoms after the reaction is On the surface of the ultrafine metal particles, it becomes difficult to form a coordinate bond with the metal atoms on the surface, resulting in removal. This removal function is not exhibited in the vicinity of room temperature when the coating film is formed of the paste-like metal fine particle dispersion, and is only exhibited for the first time in the course of the heat treatment for the coating film.
[0030]
Specifically, the added acid anhydride or acid anhydride derivative reacts with a compound having a group containing nitrogen, oxygen, or sulfur atoms, for example, an amine compound, a thiol compound, or a diol compound, upon heating. And used to form amides, thioesters and esters. When this amide, thioester or ester is formed, it becomes difficult to form a coordinate bond with the metal atom, and as a result, the surface coating layer of the ultrafine metal particles is removed. Accordingly, extremely fine metal ultrafine particles are originally uniformly dispersed, and as the organic solvent contained in the coating film evaporates, the metal surface is brought into direct contact with the metal surface while being heat-treated. And sinter together even at relatively low temperatures. Eventually, the entire metal ultrafine particles in the coating film become a dense sintered body film, and the density is inferior to that of the plating film. Therefore, the content of the acid anhydride or acid anhydride derivative is at least according to the sum of the terminal amino group, sulfanyl group (-SH), and hydroxy group contained in the amine compound, thiol compound, diol compound, etc. It is preferable to add it in an amount exceeding that amount. The acid anhydride or acid anhydride derivative also has a function of reacting with a basic metal oxide film to form a metal salt of a carboxylic acid when heated. In consideration of the above, a slightly excessive amount is appropriately selected.
[0031]
The organic acid anhydride or its derivative or organic acid to be used is not particularly limited as long as it exhibits the above reactivity. For example, usable organic acids include C1-C10 linear or branched saturated carboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, hexanoic acid, octylic acid, and acrylic acid, methacrylic acid, crotonic acid, In addition to various carboxylic acids such as unsaturated carboxylic acids such as cinnamic acid, benzoic acid, sorbic acid, and dibasic acids such as oxalic acid, malonic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, Instead of carboxyl groups, phosphate groups (-OP (O) (OH) 2 ) Or a sulfo group (—SO Three Mention may be made of other organic acids such as phosphate esters, sulfonic acids, etc. having H).
[0032]
In addition, organic acid anhydrides or acid anhydride derivatives that can be suitably used include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), Aromatic acid anhydrides such as glycerol tris (anhydro trimellitate), maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride And cyclic aliphatic acid anhydrides such as methylhexahydrophthalic anhydride and methylcyclohexene tetracarboxylic acid anhydride, and aliphatic acid anhydrides such as polyadipic acid anhydride, polyazeline acid anhydride, and polysebacic acid anhydride. it can. Among these, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and derivatives thereof are, for example, terminal amino groups of amine compounds even at a relatively low heat treatment (sintering) temperature intended by the present invention. It is suitably used because it has an appropriate reactivity with respect to the above.
[0033]
In the method for forming a plating-substitute conductive metal film of the present invention, the paste-like fine metal particle dispersion to be used is subjected to a heat treatment after coating, but when coated, a molecular coating layer is provided on the surface. As a dispersion solvent for dispersing the ultrafine metal particles, one or more organic solvents are contained. In this organic solvent, a compound component having reactivity with the above-mentioned group containing nitrogen, oxygen and sulfur atoms, for example, an organic acid anhydride or an acid anhydride derivative or an organic acid is uniformly dissolved. It is preferable. On the other hand, in order to maintain a uniform dispersion state of the ultrafine metal particles provided with a molecular coating layer on the surface while the paste-like fine metal particle dispersion is stored for a long period of time, the surface of the ultrafine metal particles used is coated. An organic solvent that does not elute an adhesion layer of a compound such as an amine compound is preferably used.
[0034]
Different types of organic solvents can be used for these two applications and purposes, but it is preferable to use the same organic solvent. The type is not limited as long as it can be used for the two types of applications described above, but the solubility of a compound that forms an adhesion layer on the surface of the ultrafine metal particles, such as alkylamine, is too high. It is preferable to select a non-polar solvent or a low-polar solvent instead of a solvent having a high polarity so that the adhesion layer on the surface of the metal ultrafine particles disappears.
[0035]
In addition, in the method for forming a plating-substitute conductive metal film of the present invention, the organic solvent can evaporate relatively quickly at the temperature at which heat treatment is performed for sintering after coating, and thermal decomposition or the like is performed during that time. It is preferable to have thermal stability to the extent that it does not occur. In addition, when forming a fine line, the metal fine particle dispersion is applied as a coating film having a desired film thickness by a screen printing method or the like in the coating process, and therefore it is necessary to maintain a suitable liquid viscosity range. It becomes. Considering its handling characteristics, non-polar or low-polarity solvents with relatively high boiling points that do not easily evaporate near room temperature, such as terpineol, mineral spirits, xylene, toluene, ethylbenzene, mesitylene, etc. It can be suitably used, and hexane, heptane, octane, decane, dodecane, cyclohexane, cyclooctane and the like can also be used.
[0036]
The content of such an organic solvent depends on the amount of the compound, such as an organic acid anhydride or a derivative thereof or an organic acid, that is reactive with a group containing nitrogen, oxygen, or sulfur atoms to be dissolved. Selected. Further, the content ratio is selected according to the amount of the ultrafine metal particles to be dispersed and the dispersion density. In that case, it is usually preferable to select the content of the organic solvent in the range of 5 to 100 parts by mass per 100 parts by mass of the ultrafine metal particles in the dispersion medium in the paste-like fine metal particle dispersion. In addition, it is necessary to adjust the liquid viscosity of the paste-like metal fine particle dispersion according to appropriate coating performance, for example, line width accuracy, film thickness controllability, for example, by adjusting the amount of organic solvent added The final liquid viscosity is desirably selected in the range of 1 to 500 Pa · s, preferably in the range of 2 to 200 Pa · s.
[0037]
On the other hand, the ultrafine metal particles with a fine average particle diameter contained in the paste-like fine metal particle dispersion liquid may be, for example, silver depending on the use and material of the plating film substituted by the conductive metal film to be formed. Selected from the group consisting of copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum, or from two or more metals. The alloy fine particles to be selected can be appropriately selected. For normal purposes, fine particles made of a metal having excellent electrical conductivity such as gold, silver, copper and platinum are often used. In addition, when using alloy fine particles, the effect of the present invention is exhibited when using an alloy whose melting point is higher than the heat treatment temperature for sintering.
[0038]
In addition, the electronic component mounting method of the present invention has been developed by replacing the conductive metal film produced by adopting the above-described plating substitute conductive metal film formation method with an electronic material member that conventionally uses a plated film. This is a method for mounting and mounting electronic components on the mounting substrate. Various plating films are used for electronic component mounting members. Among them, unlike the normal plating method, this is a characteristic and essential step in the method of forming a plating substitute conductive metal film of the present invention. As long as the heat treatment in the low-temperature sintering process of the metal ultrafine particles does not cause any problems, the plating film can be replaced. In particular, in the method for forming a plating substitute conductive metal film of the present invention, unlike plating, a form that exhibits the advantage of not requiring a wet process using an aqueous reagent is more preferable.
[0039]
For example, it is more suitable when it is necessary to form a selective conductive metal film only in a specific region. Therefore, a series of steps for mounting electronic components on the substrate establishes electrical connection between the electronic components and the wiring circuit formed on the substrate, which is conductive through the conductive metal film. In this case, the conductive metal film formed on the substrate is selectively formed only on necessary portions by using the plating substitute conductive metal film forming method of the present invention. This is preferable.
[0040]
As an example, when a conductive metal film that conducts electricity is used as an alternative conductive metal film for a through-hole plating film between the front surface and the back surface of the substrate, or at least one of wiring circuits formed on the substrate. The case where it utilizes as an alternative electroconductive metal film of the plating film which comprises a part is mentioned. In addition, an example of a case in which a conductive metal film that conducts electricity is used as an alternative conductive metal film for a bonding plating film that connects a wiring circuit formed on a substrate to the wiring of an electronic component. As mentioned. In addition, after applying the paste-like fine metal particle dispersion of the present invention to a substrate, an electronic component such as a chip is mounted on the coating film portion, and heat sintering is performed at a low temperature of 250 ° C. or less, thereby achieving high reliability. It is also possible to join high electronic components.
[0041]
In addition, in the electronic component mounting method of the present invention, the paste-like fine metal particle dispersion to be used does not use an organic binder for electrical conduction between metal fine particles and molding / solidification. Unlike a conductive metal paste that uses an organic binder, a plurality of electronic components can be mounted on such a conductive metal film by further using a soldering agent.
[0042]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. Although this example is an example of the best mode of the present invention, the present invention is not limited by this example.
[0043]
Example 1
Commercially available silver ultrafine particle dispersion (trade name: Independently dispersed ultrafine particle Perfect Silver, Vacuum Metallurgical Co., Ltd.), specifically, silver fine particles 100 parts by mass, alkylamine as dodecylamine 15 parts by mass, organic Using a dispersion of silver fine particles having an average particle diameter of 8 nm containing 75 parts by mass of terpineol as a solvent, a paste-like dispersion of silver ultrafine particles was prepared.
[0044]
The paste-like silver ultrafine particle dispersion is a methylhexahydroanhydride as an acid anhydride, which becomes a component that reacts with dodecylamine when heated per 100 parts by mass of silver fine particles in the dispersion. 10 parts by mass of phthalic acid (Me-HHPA) was added, and the mixture was sufficiently stirred with a stirring deaerator to achieve homogenization. The liquid viscosity of the prepared paste-like silver ultrafine particle dispersion is 60 Pa · s.
[0045]
The prepared paste-like silver ultrafine particle dispersion is applied onto the copper foil surface of the copper-clad laminate, and a gold wiring of a semiconductor component is placed on the coating film having a thickness of 80 μm, and 150 ° C. in an inert atmosphere. The heat treatment was performed under the temperature conditions of × 210 minutes and + 210 ° C. × 60 minutes. By this heat treatment, the silver ultrafine particles contained in the coating film are sintered, and silver formed as an alternative layer of the bonding plating film between the copper foil surface of the copper-clad laminate and the gold wiring of the semiconductor component Fixation and electrical continuity were formed through the ultrafine particle sintered body film. At that time, the connection resistance value between the bonded gold wiring and the laminate (copper foil surface) is 1.2 × 10 -6 Ω.
[0046]
(Example 2)
In the same manner as in Example 1, a paste-like silver ultrafine particle dispersion was prepared. Per 100 parts by mass of silver fine particles having an average particle diameter of 8 nm, per 100 parts by mass of silver fine particles in the dispersion using a dispersion containing 15 parts by mass of dodecylamine as an alkylamine and 75 parts by mass of terpineol as an organic solvent. Add 10 parts by mass of methylhexahydrophthalic anhydride (Me-HHPA) as an acid anhydride, which is a component that reacts with the contained dodecylamine when heated, and stir well with a stirring defoamer. I tried to change. The liquid viscosity of the prepared paste-like silver ultrafine particle dispersion is 60 Pa · s.
[0047]
The prepared paste-like silver ultrafine particle dispersion was printed on the surface of the printed wiring board by screen printing. This 50 μm-thick coating film was subjected to heat treatment under an inert atmosphere under the temperature conditions of 150 ° C. × 30 minutes and + 210 ° C. × 60 minutes. By this heat treatment, the silver ultrafine particles contained in the coating film are sintered, and a circuit wiring composed of a sintered film of silver ultrafine particles formed as an alternative layer of the plating film is formed on the surface of the printed wiring board. It was. The resistance value (surface resistivity) of the obtained circuit is 7.5 × 10 -6 It was Ω · □.
[0048]
Example 3
In the same manner as in Example 1, a paste-like silver ultrafine particle dispersion was prepared. Per 100 parts by mass of silver fine particles having an average particle diameter of 8 nm, per 100 parts by mass of silver fine particles in the dispersion using a dispersion containing 15 parts by mass of dodecylamine as an alkylamine and 75 parts by mass of terpineol as an organic solvent. Add 10 parts by mass of methylhexahydrophthalic anhydride (Me-HHPA) as an acid anhydride, which is a component that reacts with the contained dodecylamine when heated, and stir well with a stirring defoamer. I tried to change. The liquid viscosity of the prepared paste-like silver ultrafine particle dispersion is 60 Pa · s.
[0049]
The prepared paste-like silver ultrafine particle dispersion was printed by screen printing so as to embed a through hole having an inner diameter of 0.5 mm in a double-sided wiring board having a substrate thickness of 1.6 mm. The coating film having a thickness of 50 μm on the planar portion was subjected to heat treatment under an inert atmosphere under the temperature conditions of 150 ° C. × 30 minutes and + 210 ° C. × 60 minutes. By this heat treatment, the silver ultrafine particles contained in the coating film are sintered, and the silver ultrafine particles formed as an alternative layer of the through hole plating film on the inner wall surface of the through hole penetrating the double-sided wiring board. A body membrane was formed. The resistance value of the conductive path through the obtained through hole (interlayer connection resistance value) is 9.1 × 10 5 per through hole. -6 Ω.
[0050]
【The invention's effect】
In the method for forming an alternative conductive metal film for plating using the metal fine particle dispersion of the present invention, as the metal fine particles dispersed in the metal fine particle dispersion to be used, metal ultrafine particles having an average particle diameter of 1 to 100 nm are used. The surface of the ultrafine metal particles is coated by providing a dense molecular coating layer of at least one compound having a group containing nitrogen, oxygen, or sulfur atoms as a group capable of coordinative bonding with the metal element. -Until the printing, the aggregation and fusion of the ultrafine metal particles are suppressed. In addition, the dense molecular coating layer also suppresses the natural oxidation of the surface of the metal ultrafine particles, and makes it possible to store the metal fine particle dispersion for a long period of time, maintain the quality, and maintain the dispersion characteristics. On the other hand, in the organic solvent in which the metal ultrafine particles are dispersed, the surface of the metal ultrafine particles can be obtained by adding a compound reactive with a group containing nitrogen, oxygen, and sulfur atoms at the temperature at which the heat treatment is performed. It is possible to remove the coating layer of the compound having a group containing nitrogen, oxygen and sulfur atoms covering the substrate. The fine metal particles that maintain excellent compressibility and moldability and are uniformly dispersed in the organic solvent are finally densely packed in the coating film. Can be formed at a high reproducibility with a high-quality reproducibility. In addition, unlike a general conductive metal paste, the paste-like fine metal particle dispersion of the present invention essentially does not contain an organic binder component, and its shape and conductivity are improved by sintering metal ultrafine particles. Since this is achieved, it is possible to provide a uniform conductive film regardless of the surface shape of the applied portion, the gap interval, and the like.
Claims (10)
メッキ代替導電膜を形成する領域に、前記金属微粒子分散液の塗布層を形成する工程と、
形成された前記金属微粒子分散液の塗布層を２５０℃を超えない温度にて加熱処理し、含有される金属微粒子相互を焼結する工程とを有し、
利用する前記金属微粒子分散液は、本質的に有機バインダー成分を含まず、分散媒体となる有機溶剤中に平均粒子径が１〜１００ｎｍの範囲に選択される金属超微粒子が分散されており、
金属超微粒子表面は、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する化合物１種以上により被覆されており、
前記加熱処理を施す際、金属元素と配位的な結合が可能な基として、少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する前記化合物の金属超微粒子表面からの解離がなされ、
その際、該金属微粒子分散液中には、
金属超微粒子表面を被覆している、金属元素と配位的な結合が可能な基として、少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する前記化合物に対して、前記加熱処理を施す温度において、その少なくとも窒素、酸素、イオウ原子のいずれかを含む基と反応性を有する化合物が溶解されており、
金属超微粒子表面からの少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する前記化合物の解離は、かかる少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する前記化合物に対する、その少なくとも窒素、酸素、イオウ原子のいずれかを含む基と反応性を有する前記化合物との反応により促進される
ことを特徴とするメッキ代替導電性金属膜の形成方法。A method of forming a plating-substitute conductive metal film using a metal fine particle dispersion,
Forming a coating layer of the metal fine particle dispersion in a region where the plating alternative conductive film is formed;
Heat-treating the formed coating layer of the metal fine particle dispersion at a temperature not exceeding 250 ° C., and sintering the contained metal fine particles.
The metal fine particle dispersion to be used essentially does not contain an organic binder component, and an ultrafine metal particle having an average particle diameter of 1 to 100 nm is dispersed in an organic solvent serving as a dispersion medium.
The surface of the ultrafine metal particle is coated with one or more compounds having a group containing at least one of nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with the metal element contained in the ultrafine metal particle. And
When performing the heat treatment, as a group capable of coordinative bonding with a metal element, dissociation from the surface of the metal ultrafine particles of the compound having a group containing at least one of nitrogen, oxygen, and sulfur atoms is made ,
At that time, in the metal fine particle dispersion,
The heat treatment is performed on the compound having a group containing at least one of nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with a metal element that covers the surface of the ultrafine metal particles. At temperature, the compound reactive with the group containing at least one of nitrogen, oxygen and sulfur atoms is dissolved,
The dissociation of the compound having a group containing at least one of nitrogen, oxygen, and sulfur atoms from the surface of the metal ultrafine particles is at least nitrogen for the compound having a group containing at least one of nitrogen, oxygen, and sulfur atoms. A plating substitute conductive metal film forming method characterized by being promoted by a reaction between a group containing any one of oxygen, oxygen and sulfur atoms and the compound having reactivity .
前記金属微粒子分散液は、本質的に有機バインダー成分を含まず、分散媒体となる有機溶剤中に平均粒子径が１〜１００ｎｍの範囲に選択される金属超微粒子が分散されており、
金属超微粒子表面は、かかる金属超微粒子に含まれる金属元素と配位的な結合が可能な基として、少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する化合物１種以上により被覆されており、
金属元素と配位的な結合が可能な基として、少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する前記化合物は、２５０℃を超えない温度にて加熱処理により、金属超微粒子表面からの解離が可能であり、
その際、該金属微粒子分散液中には、
金属超微粒子表面を被覆している、金属元素と配位的な結合が可能な基として、少なくとも窒素、酸素、イオウ原子のいずれかを含む基を有する前記化合物に対して、前記加熱処理を施す温度において、その少なくとも窒素、酸素、イオウ原子のいずれかを含む基と反応性を有する化合物が溶解されている
ことを特徴とする金属微粒子分散液。A metal fine particle dispersion used for forming a plating alternative conductive film,
The metal fine particle dispersion essentially does not contain an organic binder component, and ultrafine metal particles having an average particle size selected in the range of 1 to 100 nm are dispersed in an organic solvent serving as a dispersion medium.
The surface of the ultrafine metal particle is coated with one or more compounds having a group containing at least one of nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with the metal element contained in the ultrafine metal particle. And
The compound having a group containing at least one of nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with a metal element is heated from a surface of the ultrafine metal particles at a temperature not exceeding 250 ° C. Dissociation is possible,
At that time, in the metal fine particle dispersion,
The heat treatment is performed on the compound having a group containing at least one of nitrogen, oxygen, and sulfur atoms as a group capable of coordinative bonding with a metal element that covers the surface of the ultrafine metal particles. A metal fine particle dispersion , wherein a compound reactive with a group containing at least one of nitrogen, oxygen and sulfur atoms is dissolved at a temperature .
前記電子部品を、前記基板上に形成されている配線回路に対して、電気的な接続をとるように搭載する工程を有し、
基板上に形成されている配線回路と前記電子部品の配線との接合部位、あるいは、基板上に形成されている配線回路相互間の接続部位のいずれかにおいて、基板上に形成されている導電性金属皮膜を介して導通が図られ、
基板上に形成されている前記導電性金属皮膜は、請求項１〜３のいずれかに記載される方法により形成されていることを特徴とする電子部品の搭載方法。A method of mounting electronic components on a substrate,
A step of mounting the electronic component so as to be electrically connected to a wiring circuit formed on the substrate;
Conductivity formed on the substrate at either the junction between the wiring circuit formed on the substrate and the wiring of the electronic component or the connection between the wiring circuits formed on the substrate Conductivity is achieved through the metal film,
The method for mounting an electronic component, wherein the conductive metal film formed on the substrate is formed by the method according to claim 1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001136077A JP3764349B2 (en) | 2001-05-07 | 2001-05-07 | Method of forming an alternative conductive metal film for plating using metal fine particle dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001136077A JP3764349B2 (en) | 2001-05-07 | 2001-05-07 | Method of forming an alternative conductive metal film for plating using metal fine particle dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002334618A JP2002334618A (en) | 2002-11-22 |
| JP3764349B2 true JP3764349B2 (en) | 2006-04-05 |
Family
ID=18983437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001136077A Expired - Lifetime JP3764349B2 (en) | 2001-05-07 | 2001-05-07 | Method of forming an alternative conductive metal film for plating using metal fine particle dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3764349B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011034019A1 (en) | 2009-09-16 | 2011-03-24 | 日立化成工業株式会社 | Printing ink, metal nanoparticles used in the same, wiring, circuit board, and semiconductor package |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4021361B2 (en) * | 2003-04-23 | 2007-12-12 | 東邦チタニウム株式会社 | Nickel powder dispersion and method for preparing the same, and method for preparing conductive paste using the powder dispersion |
| WO2004096470A1 (en) | 2003-04-28 | 2004-11-11 | Sumitomo Metal Mining Co., Ltd. | Method for preparing liquid colloidal dispersion of silver particles, liquid colloidal dispersion of silver particles, and silver conductive film |
| EP1626614B1 (en) * | 2003-05-16 | 2013-08-28 | Harima Chemicals, Inc. | Method for forming fine copper particle sintered product type of electric conductor having fine shape, method for forming fine copper wiring and thin copper film |
| ATE531669T1 (en) | 2003-06-10 | 2011-11-15 | Asahi Glass Co Ltd | PRODUCTION METHOD FOR METAL HYDRIDE FINE PARTICLES, LIQUID DISPERSION CONTAINING METAL HYDRIDE FINE PARTICLES AND METALLIC MATERIAL |
| WO2005025787A1 (en) * | 2003-09-12 | 2005-03-24 | National Institute Of Advanced Industrial Science And Technology | Metal nano particle liquid dispersion capable of being sprayed in fine particle form and being applied in laminated state |
| JP4298704B2 (en) | 2003-10-20 | 2009-07-22 | ハリマ化成株式会社 | Dry powder metal fine particles and metal oxide fine particles and their uses |
| EP1716578A4 (en) * | 2004-02-18 | 2009-11-11 | Virginia Tech Intell Prop | Nanoscale metal paste for interconnect and method of use |
| US8257795B2 (en) | 2004-02-18 | 2012-09-04 | Virginia Tech Intellectual Properties, Inc. | Nanoscale metal paste for interconnect and method of use |
| JP4973186B2 (en) | 2004-03-10 | 2012-07-11 | 旭硝子株式会社 | Metal-containing fine particles, metal-containing fine particle dispersions and conductive metal-containing materials |
| JP4535797B2 (en) * | 2004-07-21 | 2010-09-01 | ハリマ化成株式会社 | Method for forming metal fine-particle sintered body type thin film conductor layer, metal wiring using the method, and method for forming metal thin film |
| JP4812329B2 (en) * | 2004-09-29 | 2011-11-09 | 京セラ株式会社 | Electronic components, ferrite cores and inductors |
| JP4799881B2 (en) | 2004-12-27 | 2011-10-26 | 三井金属鉱業株式会社 | Conductive ink |
| JP4293181B2 (en) | 2005-03-18 | 2009-07-08 | セイコーエプソン株式会社 | Metal particle dispersion, method for producing metal particle dispersion, method for producing conductive film-formed substrate, electronic device and electronic apparatus |
| JP4748158B2 (en) * | 2005-04-06 | 2011-08-17 | 株式会社村田製作所 | Conductive resin cured product and electronic component module |
| KR101249192B1 (en) | 2005-04-12 | 2013-04-03 | 아사히 가라스 가부시키가이샤 | Ink composition and metallic material |
| JP4973830B2 (en) * | 2005-07-29 | 2012-07-11 | 戸田工業株式会社 | Conductive composition, conductive paste and conductive film |
| JP4728755B2 (en) * | 2005-09-22 | 2011-07-20 | ハリマ化成株式会社 | Method for forming conductive joint |
| EP1952918B1 (en) | 2005-10-14 | 2013-05-22 | Toyo Ink Mfg. Co., Ltd | Method for producing metal particle dispersion, conductive ink using metal particle dispersion produced by such method, and conductive coating film |
| JP2007146117A (en) | 2005-11-04 | 2007-06-14 | Mitsui Mining & Smelting Co Ltd | Nickel ink and electrically conductive film formed from the same |
| CN101312800B (en) | 2005-12-08 | 2011-05-25 | 住友金属矿山株式会社 | Liquid colloidal dispersion of silver particles, coating liquid for forming silver film, manufacturing method and silver film |
| JP5065613B2 (en) | 2006-04-10 | 2012-11-07 | 三井金属鉱業株式会社 | Nickel ink |
| JP4614101B2 (en) * | 2006-04-28 | 2011-01-19 | 戸田工業株式会社 | Silver powder, method for producing the same, and conductive paste containing the silver powder |
| JP4995491B2 (en) * | 2006-06-02 | 2012-08-08 | 株式会社日本触媒 | Method for producing copper coating |
| WO2008013002A1 (en) | 2006-07-28 | 2008-01-31 | Asahi Glass Company, Limited | Dispersion conatining metal fine particles, process for production of the dispersion, and articles having metal films |
| JP4963393B2 (en) * | 2006-10-03 | 2012-06-27 | 三ツ星ベルト株式会社 | Low temperature firing type silver paste |
| WO2009016863A1 (en) | 2007-07-31 | 2009-02-05 | Bando Chemical Industries, Ltd. | Conductive ink, conductive coating therefrom and method for producing the same |
| JP4838219B2 (en) * | 2007-10-01 | 2011-12-14 | ハリマ化成株式会社 | Method for producing metal nanoparticle sintered body |
| CN104962214A (en) * | 2008-04-30 | 2015-10-07 | 日立化成工业株式会社 | Connecting material and semiconductor device |
| JP5252344B2 (en) * | 2008-06-10 | 2013-07-31 | ハリマ化成株式会社 | Method for forming metal nanoparticle sintered body thick film layer |
| JP5651299B2 (en) * | 2008-11-11 | 2015-01-07 | Dic株式会社 | Process for producing conductive molded product, conductive molded product, and silver paste used therefor |
| JP5468885B2 (en) * | 2009-12-01 | 2014-04-09 | ハリマ化成株式会社 | Conductive aluminum paste |
| JP2012057217A (en) * | 2010-09-09 | 2012-03-22 | Honda Motor Co Ltd | Method for manufacturing sliding member, and sliding member |
| KR102158290B1 (en) * | 2010-11-22 | 2020-09-21 | 도와 일렉트로닉스 가부시키가이샤 | Binding material, binding body, and binding method |
| JP5642312B1 (en) * | 2014-05-13 | 2014-12-17 | イサハヤ電子株式会社 | Semiconductor device and manufacturing method thereof |
| CN113893701B (en) * | 2021-11-10 | 2022-06-14 | 贵州省材料产业技术研究院 | Preparation method of conductive polyether sulfone separation membrane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4362170B2 (en) * | 1999-07-22 | 2009-11-11 | アルバックマテリアル株式会社 | Silver ultrafine particle independent dispersion |
| JP4871443B2 (en) * | 2000-10-13 | 2012-02-08 | 株式会社アルバック | Method for producing metal ultrafine particle dispersion |
| CN1319075C (en) * | 2000-10-25 | 2007-05-30 | 播磨化成株式会社<Del/> | Electroconductive metal paste |
-
2001
- 2001-05-07 JP JP2001136077A patent/JP3764349B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011034019A1 (en) | 2009-09-16 | 2011-03-24 | 日立化成工業株式会社 | Printing ink, metal nanoparticles used in the same, wiring, circuit board, and semiconductor package |
| KR20120094157A (en) | 2009-09-16 | 2012-08-23 | 히다치 가세고교 가부시끼가이샤 | Printing ink, metal nanoparticles used in the same, wiring, circuit board, and semiconductor package |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002334618A (en) | 2002-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3764349B2 (en) | Method of forming an alternative conductive metal film for plating using metal fine particle dispersion | |
| JP4496216B2 (en) | Conductive metal paste | |
| JP4894266B2 (en) | Conductive powder surface treatment method, conductive powder and conductive paste | |
| CN1316509C (en) | Conductor composition and method for production thereof | |
| JP3942816B2 (en) | Brazing joining method between metals | |
| JP5505695B2 (en) | Metal paste for conductive film formation | |
| JPWO2006109410A1 (en) | Ink composition and metallic material | |
| KR20000075549A (en) | Low temperature method and compositions for producing electrical conductors | |
| TW201207055A (en) | Metal nanoparticle paste, electronic component assembly using metal nanoparticle paste, led module, and method for forming circuit for printed wiring board | |
| JP2013055193A (en) | Formation method of conductive metal film | |
| WO2013147235A1 (en) | Conductive paste, hardened material, electrode, and electronic device | |
| JP2514516B2 (en) | Solderable conductive paste | |
| JP2011119340A (en) | Conductive aluminum paste | |
| JP2004063446A (en) | Conductive paste | |
| JP2013149618A (en) | Polymer thick film solder alloy conductor composition | |
| JPH0216172A (en) | Solderable conductive paint | |
| TW201842086A (en) | Method of finishing a metallic conductive layer | |
| JP2005044798A (en) | Conductive powder and its production method | |
| JP4106447B2 (en) | Method of forming an electroless gold plating alternative conductive gold film using conductive gold paste | |
| JP5988762B2 (en) | Method for forming metal film, method for forming conductive film for through hole, and method for fixing electronic component | |
| JPS62230869A (en) | Electrically conductive coating compound to be soldered | |
| JP2005293937A (en) | Method of forming metal thin-film layer on conductive ito film or on glass substrate surface as base substrate of ito film, and metal thin-film layer on conductive ito film or on glass substrate surface as base substrate of the ito film | |
| JP2018122309A (en) | Powder for joining and paste for joining using the powder | |
| JP2005190907A (en) | Surface treatment metal powder, conductive paste using same, and printed wiring board and chip components obtained by using conductive paste | |
| JPH0619075B2 (en) | Conductive paint that can be soldered |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041101 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050629 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050829 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20050829 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051012 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051104 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060104 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060119 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3764349 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090127 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100127 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100127 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110127 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110127 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120127 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130127 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140127 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |