JP2008016360A5 - - Google Patents
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- JP2008016360A5 JP2008016360A5 JP2006187411A JP2006187411A JP2008016360A5 JP 2008016360 A5 JP2008016360 A5 JP 2008016360A5 JP 2006187411 A JP2006187411 A JP 2006187411A JP 2006187411 A JP2006187411 A JP 2006187411A JP 2008016360 A5 JP2008016360 A5 JP 2008016360A5
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- Prior art keywords
- copper
- fine particles
- particle dispersion
- dispersion
- producing
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- 239000010419 fine particle Substances 0.000 claims description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 229910052802 copper Inorganic materials 0.000 claims description 53
- 239000010949 copper Substances 0.000 claims description 53
- 239000006185 dispersion Substances 0.000 claims description 46
- -1 amine compound Chemical class 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 230000001603 reducing Effects 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N Decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 20
- 239000011521 glass Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- 238000010304 firing Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000007641 inkjet printing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;N-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N 1-Decanol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N Hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N Hexylamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecan-1-amine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (-)-propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000001706 (4R)-4-methyloctanoic acid Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentanediol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-Heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N 1-Hexanol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N 2,3-Butanediol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- SNUXYHQSKLNSJB-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpentan-1-ol Chemical compound CCCC(C)(CO)N(C)C SNUXYHQSKLNSJB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-Ethylhexanol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- RVDHMTFOOQCZBD-UHFFFAOYSA-N 2-amino-3-methylpentan-2-ol Chemical compound CCC(C)C(C)(N)O RVDHMTFOOQCZBD-UHFFFAOYSA-N 0.000 description 1
- 229940013085 2-diethylaminoethanol Drugs 0.000 description 1
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 1
- WKCYFSZDBICRKL-UHFFFAOYSA-N 3-(diethylamino)propan-1-ol Chemical compound CCN(CC)CCCO WKCYFSZDBICRKL-UHFFFAOYSA-N 0.000 description 1
- LEGGANXCVQPIAI-UHFFFAOYSA-N 4-Methyloctanoic acid Chemical compound CCCCC(C)CCC(O)=O LEGGANXCVQPIAI-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N Acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N Cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N Diethylethanolamine Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N Heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N Hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N N,N-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-Methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- SDWBRBLWPQDUQP-UHFFFAOYSA-N N-boranyl-N-methylmethanamine Chemical compound BN(C)C SDWBRBLWPQDUQP-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N N-methylhexan-1-amine Chemical compound CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N Nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229960004063 Propylene glycol Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N decan-1-amine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N heptan-1-amine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HBXNJMZWGSCKPW-UHFFFAOYSA-N octan-2-amine Chemical compound CCCCCCC(C)N HBXNJMZWGSCKPW-UHFFFAOYSA-N 0.000 description 1
- QYPUTBKHHRIDGS-UHFFFAOYSA-N octane-1,1-diol Chemical compound CCCCCCCC(O)O QYPUTBKHHRIDGS-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- YOQDYZUWIQVZSF-UHFFFAOYSA-N sodium borohydride Substances [BH4-].[Na+] YOQDYZUWIQVZSF-UHFFFAOYSA-N 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- ODGROJYWQXFQOZ-UHFFFAOYSA-N sodium;boron(1-) Chemical compound [B-].[Na+] ODGROJYWQXFQOZ-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は導電性銅被膜の製造方法に関し、詳しくはナノサイズの銅微粒子または銅酸化物微粒子の分散液を基板に塗布した後、焼成して、比抵抗値の低い導電性銅被膜を形成する方法に関する。 The present invention relates to a method for producing a conductive copper film, and more specifically, after applying a dispersion of nano-sized copper fine particles or copper oxide fine particles to a substrate, firing is performed to form a conductive copper film having a low specific resistance value. Regarding the method.
金属微粒子または金属酸化物微粒子の分散液を基板に塗布した後、焼成して導電性金属被膜を形成することは、電極、配線、電子回路などの作製に一般に用いられていることはよく知られているところである。 It is well known that a conductive metal film is formed by applying a dispersion of metal fine particles or metal oxide fine particles to a substrate and then firing to form electrodes, wirings, and electronic circuits. It is in place.
例えば、特許文献１には、平均粒子径が１〜１００ｎｍの金、銀、銅などの金属微粒子を、アミン、アルコール、チオールなどの金属微粒子と配位可能な化合物で被覆した状態で含むペーストを用いて多層配線板を製造することが記載されている。しかし、実施例に示された、上記ペーストの粘度は８０Ｐａ・ｓ程度と高く、また熱硬化物の比抵抗値も１×１０−５Ω・ｃｍ以上と高いものである。 For example, Patent Document 1 includes a paste containing metal fine particles such as gold, silver and copper having an average particle diameter of 1 to 100 nm coated with a compound capable of coordinating with metal fine particles such as amine, alcohol and thiol. It is described that a multilayer wiring board is manufactured using the same. However, the viscosity of the paste shown in the examples is as high as about 80 Pa · s, and the specific resistance value of the thermoset is as high as 1 × 10 −5 Ω · cm or more.
また、特許文献２には、金属ペーストの塗膜を真空中で仮焼した後、酸化性雰囲気として仮焼して残存する分解物残渣を酸化させて排除し、さらに還元性雰囲気下で酸化された金属を還元して本焼成することにより金属薄膜を形成することが記載されている。しかし、この方法は、真空焼却炉などの特別な装置を必要とし、またこの方法によって得られる薄膜は基板との密着性が十分でないという問題がある。 Patent Document 2 discloses that a metal paste coating is calcined in a vacuum, then calcined as an oxidizing atmosphere to oxidize and remove residual decomposition products, and further oxidized in a reducing atmosphere. It is described that a metal thin film is formed by reducing the metal and performing main firing. However, this method requires a special apparatus such as a vacuum incinerator, and there is a problem that the thin film obtained by this method has insufficient adhesion to the substrate.
また、特許文献３には、粒子径が２００ｎｍ以下の還元可能な金属酸化物を分散させた分散体を基板に塗布した後、不活性雰囲気中、次いで還元性雰囲気中で焼成して金属被膜を形成することが記載されている。しかし、この方法によって、低温で焼成して得られる金属被膜の比抵抗値は十分低いものといえない。 In Patent Document 3, a dispersion in which a reducible metal oxide having a particle size of 200 nm or less is applied to a substrate, and then fired in an inert atmosphere and then in a reducing atmosphere to form a metal film. It is described to form. However, it cannot be said that the specific resistance value of the metal coating obtained by firing at this low temperature is sufficiently low.
本発明は、粘度の低い銅微粒子分散液を用い、これを２５０℃以下の低温で焼成することにより、比抵抗値の低い銅被膜を容易に形成し得る、新規な銅被膜の形成方法を提供することを目的とする。 The present invention provides a novel method for forming a copper film, which can easily form a copper film having a low specific resistance value by firing a copper fine particle dispersion having a low viscosity at a low temperature of 250 ° C. or lower. The purpose is to do.
本発明者らの研究によれば、上記課題は、下記発明により解決できることがわかった。
（１）平均粒子径が１〜１００ｎｍの範囲にある銅微粒子または銅酸化物微粒子を分散させた微粒子分散液を基板に塗布した後、還元雰囲気中、２５０℃以下の温度で焼成することを特徴とする導電性銅被膜の製造方法。
（２）微粒子分散液が炭素数６〜１０のアミン化合物およびカルボン酸化合物から選ばれる少なくとも１種の化合物を含有する上記（１）の導電性銅被膜の製造方法。
（３）微粒子分散液中の炭素数６〜１０のアミン化合物およびカルボン酸化合物から選ばれる少なくとも１種の化合物の含有量が銅微粒子または銅酸化物微粒子１００質量部に対し３０〜１５０質量部である上記（２）の導電性銅被膜の製造方法。
（４）銅微粒子または銅酸化物微粒子の平均粒子径が１０ｎｍ以下、σ／Ｄ値（σ：標準偏差、Ｄ：平均粒子径）が０．２以下である上記（１）ないし（３）のいずれかの導電性銅被膜の製造方法。
（５）微粒子分散液の粘度が１０Ｐａ・ｓ以下である上記（１）ないし（４）のいずれかに記載の導電性銅被膜の製造方法。
According to the studies by the present inventors, it has been found that the above problem can be solved by the following invention.
(1) A fine particle dispersion in which copper fine particles or copper oxide fine particles having an average particle diameter in the range of 1 to 100 nm are applied to a substrate and then fired at a temperature of 250 ° C. or lower in a reducing atmosphere. A method for producing a conductive copper coating.
(2) The method for producing a conductive copper coating according to the above (1), wherein the fine particle dispersion contains at least one compound selected from an amine compound having 6 to 10 carbon atoms and a carboxylic acid compound.
(3) The content of at least one compound selected from an amine compound having 6 to 10 carbon atoms and a carboxylic acid compound in the fine particle dispersion is 30 to 150 parts by mass with respect to 100 parts by mass of the copper fine particles or copper oxide fine particles. A method for producing a conductive copper film according to (2) above.
(4) The average particle size of copper fine particles or copper oxide fine particles is 10 nm or less, and σ / D value (σ: standard deviation, D: average particle size) is 0.2 or less. A method for producing any one of the conductive copper coatings.
(5) The method for producing a conductive copper film according to any one of (1) to ( 4 ), wherein the viscosity of the fine particle dispersion is 10 Pa · s or less.
本発明の方法によれば、特殊な装置を使用することなく、比抵抗値の低い銅被膜を容易に形成することができる。また、本発明で使用する微粒子分散体は粘度が低く取扱いが容易であることから、本発明の方法は、電子回路用導電体の製造に好適である。 According to the method of the present invention, a copper film having a low specific resistance value can be easily formed without using a special apparatus. Further, since the fine particle dispersion used in the present invention has a low viscosity and is easy to handle, the method of the present invention is suitable for the production of a conductor for electronic circuits.
本発明で用いる「微粒子分散液」とは、平均粒子径が１〜１００ｎｍ、好ましくは１〜５０ｎｍ、より好ましくは２〜１０ｎｍの範囲にある銅微粒子または銅酸化物微粒子が有機溶媒に分散したものである。上記銅微粒子または銅酸化物微粒子のなかでも、粒子径が均一なもの、具体的には、平均粒子径をＤ、標準偏差をσとすると、σ／Ｄ値が０．０１〜０．５、好ましくは０．０５〜０．２の範囲にあるものが好適に用いられる。 The “fine particle dispersion” used in the present invention is a dispersion in which copper fine particles or copper oxide fine particles having an average particle diameter of 1 to 100 nm, preferably 1 to 50 nm, more preferably 2 to 10 nm are dispersed in an organic solvent. It is. Among the copper fine particles or copper oxide fine particles, those having a uniform particle diameter, specifically, when the average particle diameter is D and the standard deviation is σ, the σ / D value is 0.01 to 0.5, Those in the range of 0.05 to 0.2 are preferably used.
上記微粒子分散液中の微粒子の粒子径は電界放射型透過電子顕微鏡（ＦＥ−ＴＥＭ）を用いて測定し、それに基づいて平均粒子径（Ｄ）および標準偏差（σ）を求めた。 The particle diameter of the fine particles in the fine particle dispersion was measured using a field emission transmission electron microscope (FE-TEM), and the average particle diameter (D) and the standard deviation (σ) were determined based on the measurement.
上記有機溶媒としては、この種の金属微粒子の分散体の調製に一般に用いられているものであればいずれでも用いることができる。なかでも、２５０℃以下の焼成時に容易に揮散するものが好適に用いられる。具体的には、例えば、ノルマルヘキサン、シクロヘキサン、ノルマルペンタン、ノルマルヘプタン、オクタン、デカン、ドデカン、テトラデカン、ヘキサデカン、トルエン、キシレンなどの炭化水素類、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、ヘプタノール、オクタノール、デカノール、シクロヘキサノール、２−エチル−１−ヘキサノール、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，４−ブタンジオール、２，３−ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、２−ジメチルアミノエタノール、２−ジエチルアミノエタノール、２−ジメチルアミノイソプロパノール、３−ジエチルアミノ−１−プロパノール、２−ジメチルアミノ−２−プロパノール、２−メチルアミノエタノール、４−ジメチルアミノ−１−ブタノールなどのアルコール類、メチルエチルケトン、アセトン、メチルイソブチルケトン、アセチルアセトンなどのケトン類などを挙げることができる。 As the organic solvent, any organic solvent can be used as long as it is generally used for the preparation of this kind of fine metal particle dispersion. Among these, those that readily volatilize during firing at 250 ° C. or lower are preferably used. Specifically, for example, hydrocarbons such as normal hexane, cyclohexane, normal pentane, normal heptane, octane, decane, dodecane, tetradecane, hexadecane, toluene, xylene, methanol, ethanol, propanol, butanol, hexanol, heptanol, octanol , Decanol, cyclohexanol, 2-ethyl-1-hexanol, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol, 2,3-butanediol, pentanediol, hexanediol, octanediol, 2 -Dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylaminoisopropanol, 3-diethylamino-1-propanol, 2-dimethylamino-2-propyl Propanol, 2-methyl-aminoethanol, 4-alcohols such as dimethyl-amino-1-butanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, and the like ketones such as acetylacetone.
上記微粒子分散液は、微粒子の凝集を防止するために、銅と配位可能な有機化合物、例えば、アミン化合物、チオール化合物、カルボン酸化合物などを含んでいるのが好ましい。これらのなかでも、炭素数６〜１０のアミン化合物およびカルボン酸化合物が好適に用いられる。これら化合物の具体例としては、例えば、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、２−エチルヘキシルアミン、１，１，３，３−テトラメチルブチルアミン、シクロヘキシルアミン、Ｎ，Ｎ−ジエチルシクロヘキシルアミン、Ｎ−メチルヘキシルアミン、Ｎ−メチルシクロヘキシルアミン、シクロヘプチルアミン、１−メチルヘプチルアミンなどのアミン化合物、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、２−エチルヘキサン酸、２−メチルヘプタン酸、４−メチルオクタン酸、グルコン酸、サリチル酸などのカルボン酸化合物を挙げることができる。なかでも、ヘキシルアミン、オクチルアミン、２−エチルヘキシルアミン、デカン酸および２−エチルヘキサン酸が好適に用いられる。これらは単独でも、２種以上混合して使用してもよい。 The fine particle dispersion preferably contains an organic compound capable of coordinating with copper , such as an amine compound, a thiol compound, and a carboxylic acid compound, in order to prevent aggregation of the fine particles. Of these, amine compounds having 6 to 10 carbon atoms and carboxylic acid compounds are preferably used. Specific examples of these compounds include, for example, hexylamine, heptylamine, octylamine, nonylamine, decylamine, 2-ethylhexylamine, 1,1,3,3-tetramethylbutylamine, cyclohexylamine, N, N-diethylcyclohexylamine. , Amine compounds such as N-methylhexylamine, N-methylcyclohexylamine, cycloheptylamine, 1-methylheptylamine, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, 2- Examples thereof include carboxylic acid compounds such as methylheptanoic acid, 4-methyloctanoic acid, gluconic acid, and salicylic acid. Of these, hexylamine, octylamine, 2-ethylhexylamine, decanoic acid and 2-ethylhexanoic acid are preferably used. These may be used alone or in combination of two or more.
上記有機化合物の含有量については、分散液中の銅微粒子または銅酸化物微粒子の１００質量部あたり、３０〜１５０質量部、好ましくは５０〜１００質量部とするのよい。有機化合物の含有量が少なすぎると、微粒子の凝集が起こりやすくなり、また多量に用いても、それ以上の微粒子凝集防止効果は得られず、かえって粘度が高くなるなどの問題が生じる。 The content of the organic compound is 30 to 150 parts by mass, preferably 50 to 100 parts by mass, per 100 parts by mass of the copper fine particles or copper oxide fine particles in the dispersion. If the content of the organic compound is too small, aggregation of fine particles is likely to occur, and even if used in a large amount, the effect of preventing further aggregation of fine particles cannot be obtained, and problems such as an increase in viscosity occur.
上記微粒子分散液は、一般によく知られて方法により調製することができ、その調製方法は特に限定されるものではない。例えば、銅化合物とアミン化合物とを混合した後、この混合溶液に還元剤、例えば、水素、水素化ホウ素ナトリウム、ジメチルアミノボラン、アスコルビン酸、ホルムアルデヒドなどを添加して還元処理を行うことにより銅微粒子分散液が得られる。 The fine particle dispersion can be prepared by a generally well-known method, and the preparation method is not particularly limited. For example, after a copper compound and an amine compound are mixed, a reducing agent such as hydrogen, sodium borohydride, dimethylaminoborane, ascorbic acid, formaldehyde, etc. is added to the mixed solution and subjected to a reduction treatment to form copper fine particles. A dispersion is obtained.
上記微粒子分散液の粘度は、通常、１０ｍＰａ・ｓ〜１０Ｐａ・ｓであり、好ましくは１０ｍＰａ・ｓ〜１００ｍＰａ・ｓである。 The viscosity of the fine particle dispersion is usually 10 mPa · s to 10 Pa · s, preferably 10 mPa · s to 100 mPa · s.
特に、平均粒子径が１０ｎｍ以下、σ／Ｄ値が０．２以下である銅微粒子を、炭素数６〜１０のアミン化合物とともに、有機溶媒に分散してなる微粒子分散液は、上記のような低い粘度を有し、基板への塗布作業性に優れ、また焼成によって、低い比抵抗値を有する銅被膜を形成するので好適に用いられる。 In particular, a fine particle dispersion obtained by dispersing copper fine particles having an average particle size of 10 nm or less and a σ / D value of 0.2 or less together with an amine compound having 6 to 10 carbon atoms in an organic solvent is as described above. Since it has a low viscosity, is excellent in workability for application to a substrate, and forms a copper film having a low specific resistance value by firing, it is preferably used.
本発明によれば、上記微粒子分散液を基板に塗布した後、還元性雰囲気中、２５０℃以下、好ましくは１５０〜２５０℃の範囲の温度で焼成する。還元性雰囲気としては、例えば、水素と窒素との混合ガスを挙げることができる。この場合、水素の濃度は０．５〜１０容量％とすれば十分である。 According to this invention, after apply | coating the said fine particle dispersion to a board | substrate, it bakes at the temperature of 250 degrees C or less in a reducing atmosphere, Preferably it is the range of 150-250 degreeC. Examples of the reducing atmosphere include a mixed gas of hydrogen and nitrogen. In this case, it is sufficient that the hydrogen concentration is 0.5 to 10% by volume.
上記基板については、特に制限はなく、例えば、電子回路の作製に一般に用いられている基板を挙げることができる。本発明においては、２５０℃以下の温度で焼成するので、耐熱性の低いプラスチック製基板なども用いることができる。 There is no restriction | limiting in particular about the said board | substrate, For example, the board | substrate generally used for preparation of an electronic circuit can be mentioned. In the present invention, since baking is performed at a temperature of 250 ° C. or lower, a plastic substrate having low heat resistance can be used.
また、上記微粒子分散液の基板への塗布方法については、インクジェット印刷方式、スクリーン印刷法、ディップコーティング法、スプレー法、スピンコーティング法、インクジェット法などの通常の塗布手段を用いることができる。本発明の微粒子分散液はインクジェット法に特に好適に用いられる。 Moreover, about the coating method of the said fine particle dispersion to a board | substrate, normal coating means, such as an inkjet printing system, a screen printing method, a dip coating method, a spray method, a spin coating method, an inkjet method, can be used. The fine particle dispersion of the present invention is particularly preferably used in the ink jet method.
本発明の有利な実施態様を示している以下の実施例を挙げて、本発明を更に具体的に説明する。 The invention is further illustrated by the following examples, which illustrate advantageous embodiments of the invention.
（実施例１）
１Ｌのガラスビーカーに酢酸銅一水和物（和光純薬工業株式会社製）１５．７ｇとオクチルアミン（和光純薬工業株式会社製）９０．６ｇとを添加し、４０℃にて１０分間攪拌混合する。次に、前記ガラスビーカーを２０℃の恒温水槽に入れ、溶解させたジメチルアミンボラン溶液を徐々に添加することにより還元処理を実施した。
(Example 1)
15.7 g of copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 90.6 g of octylamine (manufactured by Wako Pure Chemical Industries, Ltd.) are added to a 1 L glass beaker and stirred at 40 ° C. for 10 minutes. Mix. Next, the glass beaker was placed in a constant temperature water bath at 20 ° C., and a reduced treatment was performed by gradually adding the dissolved dimethylamine borane solution.
還元処理後の溶液にアセトン１００ｇと水１０ｇを添加し、しばらく放置した後、ろ過により銅および有機物からなる沈殿物を分離回収した。回収物にデカンを添加して溶解させた後、ろ過して、銅微粒子４０質量％とオクチルアミン２０質量％とを含有するデカン分散液を得た。この分散液の粘度は３０ｍＰａ・ｓであった。また、この分散液をＦＥ−ＳＥＭで観察したところ、銅微粒子の平均粒子径は５ｎｍ、σ／Ｄ値は０．１５であることが確認された。 To the solution after the reduction treatment, 100 g of acetone and 10 g of water were added and allowed to stand for a while, and then a precipitate made of copper and organic matter was separated and collected by filtration. After the decane was added to the recovered product and dissolved, it was filtered to obtain a decane dispersion containing 40% by mass of copper fine particles and 20% by mass of octylamine. The viscosity of this dispersion was 30 mPa · s. Further, when this dispersion was observed by FE-SEM, it was confirmed that the average particle diameter of the copper fine particles was 5 nm and the σ / D value was 0.15.
次に、ガラス板上に、上記のデカン分散液（銅微粒子分散液）を用いて、インクジェット印刷方式により印刷した。印刷後、上記ガラス板を焼成炉内に設置し、水素−窒素混合ガス（水素５容量％）を流通させながら、２００℃まで３０分で上昇させ、昇温後３０分間保持することにより銅薄膜を形成した。得られた銅薄膜の平均膜厚は２μｍ、比抵抗値は４．０μΩ・ｃｍであった。また、銅薄膜表面にテープを貼って剥がしたが、剥がれは殆ど認められなかった。 Next, it printed by the inkjet printing system on said glass plate using said decane dispersion liquid (copper fine particle dispersion liquid). After printing, the above glass plate was placed in a firing furnace, and while flowing a hydrogen-nitrogen mixed gas (5% by volume of hydrogen), the temperature was raised to 200 ° C. over 30 minutes, and the temperature was maintained for 30 minutes after being heated. Formed. The obtained copper thin film had an average film thickness of 2 μm and a specific resistance value of 4.0 μΩ · cm. Moreover, although the tape was stuck and peeled off on the copper thin film surface, peeling was hardly recognized.
（実施例２）
１Ｌのガラスビーカーに酢酸銅一水和物（和光純薬工業株式会社製）１５．７ｇとドデシルアミン（和光純薬工業株式会社製）１３０．２ｇとを添加し、６０℃にて１０分間攪拌混合する。次に、前記ガラスビーカーを２０℃の恒温水槽に入れ、溶解させたジメチルアミンボラン溶液を徐々に添加することにより還元処理を実施した。
(Example 2)
15.7 g of copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 130.2 g of dodecylamine (manufactured by Wako Pure Chemical Industries, Ltd.) are added to a 1 L glass beaker and stirred at 60 ° C. for 10 minutes. Mix. Next, the glass beaker was placed in a constant temperature water bath at 20 ° C., and a reduced treatment was performed by gradually adding the dissolved dimethylamine borane solution.
還元処理後の溶液にアセトン１００ｇと水１０ｇを添加し、しばらく放置した後、ろ過により銅および有機物からなる沈殿物を分離回収した。回収物にデカンを添加して溶解させた後、ろ過して、銅微粒子４０質量％とドデシルアミン２０質量％とを含有するデカン分散液を得た。この分散液の粘度は６０ｍＰａ・ｓであった。また、この分散液をＦＥ−ＳＥＭで観察したところ、銅微粒子の平均粒子径は７ｎｍ、σ／Ｄ値は０．１５であることが確認された。 To the solution after the reduction treatment, 100 g of acetone and 10 g of water were added and allowed to stand for a while, and then a precipitate made of copper and organic matter was separated and collected by filtration. After the decane was added to the recovered product and dissolved, it was filtered to obtain a decane dispersion containing 40% by mass of copper fine particles and 20% by mass of dodecylamine. The viscosity of this dispersion was 60 mPa · s. Moreover, when this dispersion liquid was observed by FE-SEM, it was confirmed that the average particle diameter of copper fine particles was 7 nm, and (sigma) / D value was 0.15.
次に、ガラス板上に、上記のデカン分散液（銅微粒子分散液）を用いて、インクジェット印刷方式により印刷した。印刷後、上記ガラス板を焼成炉内に設置し、水素−窒素混合ガス（水素５容量％）を流通させながら、２００℃まで３０分で上昇させ、昇温後３０分間保持することにより銅薄膜を形成した。得られた銅薄膜の平均膜厚は２μｍ、比抵抗値は８．０μΩ・ｃｍであった。 Next, it printed by the inkjet printing system on said glass plate using said decane dispersion liquid (copper fine particle dispersion liquid). After printing, the above glass plate was placed in a firing furnace, and while flowing a hydrogen-nitrogen mixed gas (5% by volume of hydrogen), the temperature was raised to 200 ° C. over 30 minutes, and the temperature was maintained for 30 minutes after being heated. Formed. The obtained copper thin film had an average film thickness of 2 μm and a specific resistance value of 8.0 μΩ · cm.
（実施例３）
１Ｌのガラスビーカーに酢酸銅一水和物（和光純薬工業株式会社製）１５．７ｇと２−エチルヘキシルアミン（和光純薬工業株式会社製）１００．５ｇとを添加し、３０℃にて１０分間攪拌混合する。次に、前記ガラスビーカーを２０℃の恒温水槽に入れ、溶解させたジメチルアミンボラン溶液を徐々に添加することにより還元処理を実施した。
(Example 3)
Into a 1 L glass beaker, 15.7 g of copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 100.5 g of 2-ethylhexylamine (manufactured by Wako Pure Chemical Industries, Ltd.) are added, and 10 at 30 ° C. Stir and mix for a minute. Next, the glass beaker was placed in a constant temperature water bath at 20 ° C., and a reduced treatment was performed by gradually adding the dissolved dimethylamine borane solution.
還元処理後の溶液にアセトン１００ｇと水１０ｇを添加し、しばらく放置した後、ろ過により銅および有機物からなる沈殿物を分離回収した。回収物にテトラデカンを添加して再溶解させた後、ろ過して、銅微粒子４０質量％と２−エチルヘキシルアミン２０質量％とを含有するデカン分散液を得た。この分散液の粘度は４０ｍＰａ・ｓであった。また、この分散液をＦＥ−ＳＥＭで観察したところ、銅微粒子の平均粒子径は５ｎｍ、σ／Ｄ値は０．１５であることが確認された。 To the solution after the reduction treatment, 100 g of acetone and 10 g of water were added and allowed to stand for a while, and then a precipitate made of copper and organic matter was separated and collected by filtration. Tetradecane was added to the recovered material and redissolved, followed by filtration to obtain a decane dispersion containing 40% by mass of copper fine particles and 20% by mass of 2-ethylhexylamine. The viscosity of this dispersion was 40 mPa · s. Further, when this dispersion was observed by FE-SEM, it was confirmed that the average particle diameter of the copper fine particles was 5 nm and the σ / D value was 0.15.
次に、ガラス板上に、上記のデカン分散液（銅微粒子分散液）を用いて、インクジェット印刷方式により印刷した。印刷後、上記ガラス板を焼成炉内に設置し、水素−窒素混合ガス（水素５容量％）を流通させながら、２００℃まで３０分で上昇させ、昇温後３０分間保持することにより銅薄膜を形成した。得られた銅薄膜の平均膜厚は２μｍ、比抵抗値は６．０μΩ・ｃｍであった。また、銅薄膜表面にテープを貼って剥がしたが、剥がれは殆ど認められなかった。 Next, it printed by the inkjet printing system on said glass plate using said decane dispersion liquid (copper fine particle dispersion liquid). After printing, the above glass plate was placed in a firing furnace, and while flowing a hydrogen-nitrogen mixed gas (5% by volume of hydrogen), the temperature was raised to 200 ° C. over 30 minutes, and the temperature was maintained for 30 minutes after being heated. Formed. The obtained copper thin film had an average film thickness of 2 μm and a specific resistance value of 6.0 μΩ · cm. Moreover, although the tape was stuck and peeled off on the copper thin film surface, peeling was hardly recognized.
（実施例４）
１Ｌのガラスビーカーに酢酸銅一水和物（和光純薬工業株式会社製）１５．７ｇと１，１，３，３−テトラメチルブチルアミン（和光純薬工業株式会社製）８０．２ｇとを添加し、３０℃にて１０分間攪拌混合する。次に、前記ガラスビーカーを２０℃の恒温水槽に入れ、溶解させたジメチルアミンボラン溶液を徐々に添加することにより還元処理を実施した。
Example 4
Add 15.7 g of copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 80.2 g of 1,1,3,3-tetramethylbutylamine (manufactured by Wako Pure Chemical Industries, Ltd.) to a 1 L glass beaker. And stirring and mixing at 30 ° C. for 10 minutes. Next, the glass beaker was placed in a constant temperature water bath at 20 ° C., and a reduced treatment was performed by gradually adding the dissolved dimethylamine borane solution.
還元処理後の溶液にアセトン１００ｇと水１０ｇを添加し、しばらく放置した後、ろ過により銅および有機物からなる沈殿物を分離回収した。回収物にテトラデカンを添加して再溶解させた後、ろ過して、銅微粒子４０質量％と１，１，３，３−テトラメチルブチルアミン２０質量％とを含有するテトラデカン分散液を得た。この分散液の粘度は４０ｍＰａ・ｓであった。また、この分散液をＦＥ−ＳＥＭで観察したところ、銅微粒子の平均粒子径は５ｎｍ、σ／Ｄ値は０．１５であることが確認された。 To the solution after the reduction treatment, 100 g of acetone and 10 g of water were added and allowed to stand for a while, and then a precipitate made of copper and organic matter was separated and collected by filtration. Tetradecane was added to the recovered product and redissolved, followed by filtration to obtain a tetradecane dispersion containing 40% by mass of copper fine particles and 20% by mass of 1,1,3,3-tetramethylbutylamine. The viscosity of this dispersion was 40 mPa · s. Further, when this dispersion was observed by FE-SEM, it was confirmed that the average particle diameter of the copper fine particles was 5 nm and the σ / D value was 0.15.
次に、ガラス板上に、上記のデカン分散液（銅微粒子分散液）を用いて、インクジェット印刷方式により印刷した。印刷後、上記ガラス板を焼成炉内に設置し、水素−窒素混合ガス（水素５容量％）を流通させながら、２００℃まで３０分で上昇させ、昇温後３０分間保持することにより銅薄膜を形成した。得られた銅薄膜の平均膜厚は２μｍ、比抵抗値は７．０μΩ・ｃｍであった。 Next, it printed by the inkjet printing system on said glass plate using said decane dispersion liquid (copper fine particle dispersion liquid). After printing, the above glass plate was placed in a firing furnace, and while flowing a hydrogen-nitrogen mixed gas (5% by volume of hydrogen), the temperature was raised to 200 ° C. over 30 minutes, and the temperature was maintained for 30 minutes after being heated. Formed. The obtained copper thin film had an average film thickness of 2 μm and a specific resistance value of 7.0 μΩ · cm.
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