JP4593502B2 - Method of reducing and firing metal oxide particles or surface oxide film of metal particles and method of forming conductive parts - Google Patents
Method of reducing and firing metal oxide particles or surface oxide film of metal particles and method of forming conductive parts Download PDFInfo
- Publication number
- JP4593502B2 JP4593502B2 JP2006085910A JP2006085910A JP4593502B2 JP 4593502 B2 JP4593502 B2 JP 4593502B2 JP 2006085910 A JP2006085910 A JP 2006085910A JP 2006085910 A JP2006085910 A JP 2006085910A JP 4593502 B2 JP4593502 B2 JP 4593502B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- firing
- particles
- metal oxide
- oxide film
- 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 - Fee Related
Links
- 238000010304 firing Methods 0.000 title claims description 85
- 238000000034 method Methods 0.000 title claims description 74
- 239000002245 particle Substances 0.000 title claims description 74
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 71
- 150000004706 metal oxides Chemical class 0.000 title claims description 71
- 239000002923 metal particle Substances 0.000 title claims description 54
- 239000000758 substrate Substances 0.000 claims description 39
- 230000001590 oxidative effect Effects 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003575 carbonaceous material Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000005751 Copper oxide Substances 0.000 claims description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims description 11
- 239000002134 carbon nanofiber Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229910003472 fullerene Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000059 patterning Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims 2
- 239000002105 nanoparticle Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 102000011632 Caseins Human genes 0.000 description 2
- 108010076119 Caseins Proteins 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 229940071162 caseinate Drugs 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- -1 polyethylene glycol Chemical compound 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080237 sodium caseinate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
Images
Description
本発明は、プリント配線基板や電子実装部品（基板等）の製造に用いる金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法及び導電部品の形成方法であって、特に導電路、バンプ、立体金属配線パターン、アンテナパターン、熱伝導路あるいは触媒電極等の導電部品の製造に用いる金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法及び導電部品の形成方法に関する。 The present invention is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles used in the manufacture of printed wiring boards and electronic mounting parts (boards, etc.) and a method for forming conductive parts, particularly conductive paths, bumps, The present invention relates to a reduction firing method of metal oxide particles or a surface oxide film of metal particles used for manufacturing a conductive component such as a three-dimensional metal wiring pattern, an antenna pattern, a heat conduction path, or a catalyst electrode, and a method of forming a conductive component.
金属（あるいは金属酸化物）微細粒子の製造技術、独立分散技術、さらには、超微量インクジェット、精密スクリーン印刷、ナノプリンティング、ナノインプリンティングによる微細配線パターニング技術が、近年著しく進展しているのに伴い、それら技術を応用した直接回路描画法が次世代の電子実装部品形成技術として大いに注目されている。 Along with the recent significant progress in metal (or metal oxide) fine particle manufacturing technology, independent dispersion technology, and micro wiring patterning technology using ultra-micro inkjet, precision screen printing, nanoprinting and nanoimprinting The direct circuit drawing method applying these technologies is attracting much attention as the next generation electronic component forming technology.
この直接回路描画法は、それまでリゾグラフィーやエッチングといった複雑な工程を経て製造されていた電子実装部品を、金属（あるいは金属酸化物）粒子の直接描画→焼成→相互融着→導電化といった工程で製造するという手法であり、その詳細については非特許文献1の第７１頁に記載されている。この手法の確立により、導電回路パターン、バンプ、パッド、ビア、アンテナパターンやその他の電子実装部品を、安価かつ簡便に製造することが可能になると期待されている。さらには、電子実装部品の熱伝導路としての利用も検討されている。 This direct circuit drawing method is a process of direct drawing of metal (or metal oxide) particles → firing → mutual fusion → electrical conduction of electronic mounting parts that have been manufactured through complicated processes such as lithography and etching. The details are described on page 71 of Non-Patent Document 1. By establishing this method, it is expected that conductive circuit patterns, bumps, pads, vias, antenna patterns and other electronic mounting parts can be manufactured inexpensively and easily. Furthermore, the use of electronic mounting parts as a heat conduction path is also being studied.
上記の直接回路描画法に使用される微細粒子として、従来は金もしくは銀からなるナノ粒子が用いられることが多かった。しかしながら、金のナノ粒子を用いる場合は、金自体の材料価格が非常に高価なため、これを用いて形成される電子部品も高価になってしまうといった問題があり、また銀のナノ粒子を用いる場合には、エレクトロマイグレーション現象に起因する断線等の問題を解決しなければならないといった課題が指摘されてきた。 Conventionally, nanoparticles made of gold or silver are often used as the fine particles used in the direct circuit drawing method. However, when gold nanoparticles are used, the material price of gold itself is very expensive, so that there is a problem that electronic parts formed using the gold nanoparticles are also expensive, and silver nanoparticles are used. In some cases, it has been pointed out that a problem such as disconnection caused by the electromigration phenomenon must be solved.
これに対し近年は、上記の金、銀に代わる微細粒子として、安価でかつエレクトロマイグレーションも少ない銅ナノ粒子の利用が検討されている。しかしながら、銅は、貴金属の金・銀と異なって酸化しやすく、室温でも空気中の酸素と容易に反応して表面に酸化被膜を形成してしまうことが知られている。特に、表面積比率の高い微粒子状の銅の場合には、空気中であってもほぼ全体が酸化銅になってしまう。 On the other hand, in recent years, the use of copper nanoparticles that are inexpensive and have low electromigration as fine particles to replace the above gold and silver has been studied. However, it is known that copper is easily oxidized unlike the noble metals gold and silver, and easily reacts with oxygen in the air even at room temperature to form an oxide film on the surface. In particular, in the case of finely divided copper having a high surface area ratio, almost the whole becomes copper oxide even in the air.
そこで、上記の直接回路描画法において、銅などの酸化されやすい金属を用いて良好な導電性を有する導電部品等を形成するためには、表面もしくは全体が酸化された金属微粒子（金属酸化物微粒子）の酸化物をまず還元する必要があり、その上で粒子同士を焼成（相互融着）する必要がある。 Therefore, in the direct circuit drawing method described above, in order to form a conductive part having good conductivity using a metal that is easily oxidized such as copper, metal fine particles (metal oxide fine particles) whose surface or the whole is oxidized are formed. ) Oxide must first be reduced, and then the particles must be fired (mutual fusion).
上記の酸化物粒子を還元・相互融着させる方法として、まず、水素ガス、一酸化窒素ガスをはじめとする還元性気体を用いる方法がある。例えば、特許文献１では、水素ガスまたは水素ガスと不活性ガスとの混合ガス中において、５００℃以下の温度で熱処理する方法が開示されている。また、特許文献２では、水素、アンモニア、一酸化炭素あるいはその混合気体中でプラズマを生起・反応させる方法が紹介されている。
同じく酸化物粒子を還元・相互融着させる別の方法として、各種還元剤を混合する方法がある。例えば、特許文献２の技術背景として、水素化ホウ素誘導体等の還元剤を酸化銅に添加して熱処理する方法が記載されている。また、特許文献３では、カーボン材料をはじめとする電磁波吸収性の優れた焼結助剤を混合した後、不活性雰囲気において高周波電磁波を照射する方法が紹介されている。
Similarly, as another method for reducing and mutually fusing oxide particles, there is a method of mixing various reducing agents. For example, as a technical background of Patent Document 2, a method of adding a reducing agent such as a borohydride derivative to copper oxide and performing a heat treatment is described. Patent Document 3 introduces a method of irradiating a high-frequency electromagnetic wave in an inert atmosphere after mixing a sintering aid having excellent electromagnetic wave absorption such as a carbon material.
しかしながら、上記従来の酸化物粒子の還元・相互融着方法では、以下のような問題があった。
特許文献３に記載の方法では、焼成温度を高くする必要があるため、実装部品の形成に使用できる基板材料が、耐熱温度の高い材料に限定されてしまうといった問題があった。また特許文献１に記載の方法では、高価なプラズマ発生装置を用いる必要があり、また基板上に塗布された酸化物粒子にプラズマを照射した場合、該プラズマによって基板材料が劣化してしまう恐れがあることが知られている。
However, the conventional oxide particle reduction / mutual fusion method has the following problems.
In the method described in Patent Document 3, since it is necessary to increase the firing temperature, there is a problem that the substrate material that can be used for forming the mounted component is limited to a material having a high heat resistance temperature. Further, in the method described in Patent Document 1, it is necessary to use an expensive plasma generator, and when the oxide particles applied on the substrate are irradiated with plasma, the plasma may cause deterioration of the substrate material. It is known that there is.
さらに、特許文献１に記載の水素化ホウ素誘導体を混合する方法では、４００℃以上に高温加熱する必要があり、上記と同様、使用可能な基板材料が耐熱温度の高い材料に限定されてしまうといった問題があった。また特許文献２に記載の方法では、高価な高周波電磁波発生装置が必要となるのに加えて、高周波電磁波の照射により、基板上に配置された他の電子部品が劣化損傷してしまう恐れがあることが知られている。 Furthermore, in the method of mixing the borohydride derivative described in Patent Document 1, it is necessary to heat at a high temperature of 400 ° C. or higher, and the usable substrate material is limited to a material having a high heat resistant temperature, as described above. There was a problem. Further, in the method described in Patent Document 2, in addition to the need for an expensive high-frequency electromagnetic wave generator, there is a risk that other electronic components arranged on the substrate may be deteriorated and damaged by the irradiation of the high-frequency electromagnetic wave. It is known.
そこで、本発明は上記に鑑みてなされたものであり、耐熱温度の低い基板を溶融することなく、塗布またはパターニングされた前記金属酸化物粒子を還元焼成することで、導電性の配線パターンもしくは低抵抗の実装部品を安価に形成することが可能な金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法及び導電部品の形成方法を提供することを目的とする。 Therefore, the present invention has been made in view of the above, and by reducing and firing the coated or patterned metal oxide particles without melting a substrate having a low heat-resistant temperature, a conductive wiring pattern or a low wiring pattern can be obtained. It is an object of the present invention to provide a method for reducing and firing metal oxide particles or a surface oxide film of metal particles and a method for forming a conductive component that can form a resistance-mounted component at low cost.
この発明の第１の態様は、有機物保護材で表面が被覆された金属酸化物粒子もしくは表面酸化被膜を有する金属粒子と、カーボンブラック、カーボンナノチューブ、ＶＧＣＦ（気相成長カーボンファイバー）、カーボンフラーレンの少なくともいずれか一つを含むカーボン材料との混合物を、酸素を含有した酸化性ガス中（以下では酸化性雰囲気という）で第１焼成し、さらに不活性ガス中（以下では不活性雰囲気という）で第２焼成することを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 According to a first aspect of the present invention, a metal oxide particle or a metal particle having a surface oxide film whose surface is coated with an organic material protective material, carbon black, carbon nanotube, VGCF (vapor-grown carbon fiber), carbon fullerene A mixture with a carbon material containing at least one of them is first fired in an oxidizing gas containing oxygen (hereinafter referred to as an oxidizing atmosphere), and further in an inert gas (hereinafter referred to as an inert atmosphere). The second firing method is a reduction firing method for metal oxide particles or a surface oxide film of metal particles.
第２の態様は、前記酸化性雰囲気の酸素濃度が０．１％（原子数％、以下同じ）以上５０％以下であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 In a second aspect, the oxygen concentration of the oxidizing atmosphere is 0.1% (number of atoms, the same shall apply hereinafter) or more and 50% or less, and the reduction of the metal oxide particles or the surface oxide film of the metal particles is characterized in that It is a firing method.
第３の態様は、前記酸化性雰囲気の酸素濃度が０．５％以上２５％以下であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 A third aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the oxygen concentration in the oxidizing atmosphere is 0.5% or more and 25% or less.
第４の態様は、前記不活性雰囲気に含まれる不活性ガスが、窒素、ヘリウム、ネオン、アルゴン、クリプトン、キセノンのいずれか、もしくは前記不活性ガスの混合気体であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 In a fourth aspect, the inert gas contained in the inert atmosphere is one of nitrogen, helium, neon, argon, krypton, and xenon, or a mixed gas of the inert gas. This is a reduction firing method for surface oxide coatings of product particles or metal particles.
第５の態様は、前記不活性雰囲気に含まれる不活性ガスが、窒素またはアルゴンもしくはその混合気体であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 A fifth aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the inert gas contained in the inert atmosphere is nitrogen, argon, or a mixed gas thereof.
第６の態様は、前記酸化性雰囲気での第１焼成の温度が１００℃以上５００℃以下であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 A sixth aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the temperature of the first firing in the oxidizing atmosphere is 100 ° C. or more and 500 ° C. or less.
第７の態様は、前記酸化性雰囲気での第１焼成の温度が１５０℃以上４５０℃以下であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 A seventh aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the temperature of the first firing in the oxidizing atmosphere is 150 ° C. or higher and 450 ° C. or lower.
第８の態様は、前記不活性雰囲気での第２焼成の温度が１５０℃以上であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 An eighth aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the temperature of the second firing in the inert atmosphere is 150 ° C. or higher.
第９の態様は、前記不活性雰囲気での第２焼成の温度が２００℃以上であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 A ninth aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the temperature of the second firing in the inert atmosphere is 200 ° C. or higher.
第１０の態様は、前記金属酸化物粒子が酸化銅、酸化銀粒子、酸化ニッケルのいずれかである、もしくは前記表面酸化被膜を有する金属粒子が銅、銀、ニッケルのいずれかであることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 In a tenth aspect, the metal oxide particles are any one of copper oxide, silver oxide particles, and nickel oxide, or the metal particles having the surface oxide film are any one of copper, silver, and nickel. The metal oxide particles or the surface oxide coating of metal particles is reduced and fired.
第１１の態様は、前記金属酸化物粒子もしくは前記金属粒子の平均粒径が１ｎｍ〜１００ｎｍの微粒子であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜還元焼成方法である。 An eleventh aspect is a method for reducing and firing a surface oxide film of metal oxide particles or metal particles, wherein the metal oxide particles or the metal particles are fine particles having an average particle diameter of 1 nm to 100 nm.
第１２の態様は、前記有機物保護材が、金属酸化物と化学的もしくは物理的に結合、吸着する化合物であることを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法である。 A twelfth aspect is a method for reducing and firing metal oxide particles or a surface oxide film of metal particles, wherein the organic protective material is a compound that chemically or physically binds to and adsorbs to a metal oxide. is there.
第１３の態様は、有機物保護材で表面が被覆された金属酸化物粒子もしくは表面酸化被膜を有する金属粒子と、カーボンブラック、カーボンナノチューブ、ＶＧＣＦ、カーボンフラーレンの少なくともいずれか一つを含むカーボン材料との混合物を、基板上に塗布もしくは表面パターニングした後、第１の態様から第７の態様のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法を用いて焼成することを特徴とする導電部品の形成方法である。 In a thirteenth aspect, a metal oxide particle whose surface is coated with an organic protective material or a metal particle having a surface oxide film, and a carbon material containing at least one of carbon black, carbon nanotube, VGCF, and carbon fullerene, After the mixture is applied onto the substrate or subjected to surface patterning, firing is performed using the method for reducing and firing the metal oxide particles or the surface oxide film of the metal particles according to any one of the first to seventh embodiments. And forming a conductive component.
第１４の態様は、前記基板が酸化物、ガラス、セラミックス、金属、半導体、プラスチックのいずれか一つからなることを特徴とする導電部品の形成方法である。 A fourteenth aspect is a method for forming a conductive component, wherein the substrate is made of any one of oxide, glass, ceramics, metal, semiconductor, and plastic.
以上説明したように本発明によれば、第１焼成により予め粒子表面に形成された有機被膜を除去した上で、第２焼成により金属粒子の全体あるいは表面に形成された金属酸化物を還元するようにしたことから、導電性の優れた導電部品を形成することが可能となる。 As described above, according to the present invention, after removing the organic film previously formed on the particle surface by the first baking, the metal oxide formed on the whole or the surface of the metal particles by the second baking is reduced. Since it did in this way, it becomes possible to form the electrically conductive component excellent in electroconductivity.
ガラスエポキシ等の耐熱温度の低い基板上においても、塗布またはパターニングされた前記金属酸化物粒子を、基板を溶融することなく還元焼成することで、導電性の配線パターンもしくは低抵抗の実装部品を安価に形成することが可能となる。 Even on substrates with low heat resistance, such as glass epoxy, the metal oxide particles that have been coated or patterned can be reduced and fired without melting the substrate, thereby reducing the cost of conductive wiring patterns or low-resistance mounting components. Can be formed.
図面を参照して本発明の好ましい実施の形態における金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法及び導電部品の形成方法について詳細に説明する。なお、同一機能を有する各構成部については、図示及び説明簡略化のため、同一符号を付して示す。 A method for reducing and firing metal oxide particles or a surface oxide film of metal particles and a method for forming a conductive component in a preferred embodiment of the present invention will be described in detail with reference to the drawings. In addition, about each structural part which has the same function, the same code | symbol is attached | subjected and shown for simplification of illustration and description.
図１は、本発明の実施の形態に係る金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法を示す工程図である。同図において、第一の工程１０では、有機物保護材で表面が被覆された金属酸化物粒子もしくは表面酸化被膜を有する金属粒子と、カーボンブラック、カーボンナノチューブ、ＶＧＣＦ（気相成長カーボンファイバー）、カーボンフラーレンの少なくともいずれか一つを含むカーボン材料との混合物を生成する。
FIG. 1 is a process diagram showing a method for reducing and firing metal oxide particles or a surface oxide film of metal particles according to an embodiment of the present invention. In the figure, in the
次の第二の工程２０では、第一の工程１０で生成した前記混合物６０を所定の基板５０の上に塗布する。あるいは、混合物６０で基板５０上に表面パターニングする。基板５０として、酸化物、ガラス、セラミックス、金属、半導体、プラスチックのいずれか一つを用いることができる。
In the next
第三の工程３０では、酸素を含有した酸化性ガス中（酸化性雰囲気）において、基板５０上に塗布または表面パターニングされた混合物６０を第１焼成する。本実施形態では、第三の工程３０における第１焼成により、ナノ粒子表面に形成された有機被膜を酸化分解させるのが特徴である。
In the
前記酸化性雰囲気における酸素以外の成分としては、ガス全体の酸化性を変化させないものであれば何でも良い。しかしながら、好ましくは他の不要な化合物が生成する恐れが少ない窒素、ヘリウム、ネオン、アルゴン、クリプトン、キセノン、もしくはそれらの混合気体、より好ましくは窒素、アルゴンもしくはその混合気体とするのがよい。 Any component other than oxygen in the oxidizing atmosphere may be used as long as it does not change the oxidizing property of the entire gas. However, it is preferable to use nitrogen, helium, neon, argon, krypton, xenon, or a mixed gas thereof, more preferably nitrogen, argon, or a mixed gas thereof, which is less likely to generate other unnecessary compounds.
第四の工程４０では、第三の工程３０で第１焼成された基板５０上の混合物６０を、さらに不活性ガス中で第２焼成する。
上記説明の本実施形態の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法によれば、第三の工程３０の第１焼成により予め粒子表面に形成された有機被膜を除去した上で、第四の工程４０の第２焼成により金属粒子の全体あるいは表面に形成された金属酸化物を還元するようにしたことから、導電性の優れた導電部品を形成することが可能となる。
In the
According to the reduction firing method of the metal oxide particles or the surface oxide coating of the metal particles of the present embodiment described above, the organic coating previously formed on the particle surface by the first firing of the
混合物６０に用いるカーボン材料として、カーボンブラック、カーボンナノチューブ、ＶＧＣＦ、カーボンフラーレンの少なくともいずれか一つを用いるのがよい。特に、絶縁性のカーボンフラーレンより、カーボンブラック、カーボンナノチューブ、ＶＧＣＦなどの導電性カーボンの方が、金属酸化物に対する還元効果がより顕著なことから、混合物６０に用いるカーボン材料としてより好ましい。
As a carbon material used for the
本発明の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法による効果を、実施例を用いて以下に説明する。ここでは、酸化されやすい金属として銅を選択し、金属微粒子の一例として表面酸化被膜を有する銅ナノ粒子（独立分散型Ｃｕナノメタルインク、平均粒径１０ｎｍ）を用いる。また、カーボン材料としてカーボンブラック粉末（活性炭）を用い、前記銅ナノ粒子との混合割合を重量比で、前記銅ナノ粒子：前記カーボンブラック粉末＝２４：１としている。 The effect of the reduction firing method of the metal oxide particles or the surface oxide film of the metal particles of the present invention will be described below using examples. Here, copper is selected as a metal that is easily oxidized, and copper nanoparticles having a surface oxide film (independently dispersed Cu nanometal ink, average particle size of 10 nm) are used as an example of metal fine particles. Further, carbon black powder (activated carbon) is used as a carbon material, and the mixing ratio with the copper nanoparticles is set to the copper nanoparticles: carbon black powder = 24: 1 by weight ratio.
まず、上記実施形態の第三の工程３０で行われる第１焼成の効果を確認した結果について、以下に説明する。第三の工程３０では、酸化性雰囲気の中で第１焼成を行っている。そこで、第三の工程３０の第１焼成を行う本実施形態と、これを行わない従来例との比較結果を以下に示す。
First, the result of confirming the effect of the first firing performed in the
前記銅ナノ粒子と前記カーボンブラック粉末との混合物を石英硝子基板上に塗布したものを２枚用意し、下記の通り、２種類の熱処理を行った。すなわち、一方の前記基板には第１焼成と第２焼成の２段階の熱処理を行い、他方の前記基板には第２焼成のみの１段階の熱処理を行った。 Two sheets of a mixture of the copper nanoparticles and the carbon black powder coated on a quartz glass substrate were prepared, and two types of heat treatment were performed as follows. That is, one of the substrates was subjected to a two-step heat treatment of the first firing and the second firing, and the other substrate was subjected to a one-step heat treatment of only the second firing.
前記一方の基板は、雰囲気が窒素ガス比率９５％、酸素ガス比率５％となるよう調整された電気炉内に入れられ、内部温度を３００℃にして３０分間保持された（第１焼成）。その後、雰囲気が窒素ガス比率１００％に調整された別の電気炉に入れられ、内部温度を３００℃にしてさらに３０分間保持された（第２焼成）後、炉冷された。 The one substrate was placed in an electric furnace whose atmosphere was adjusted to a nitrogen gas ratio of 95% and an oxygen gas ratio of 5%, and the internal temperature was kept at 300 ° C. for 30 minutes (first firing). Then, the atmosphere was put into another electric furnace adjusted to a nitrogen gas ratio of 100%, the internal temperature was set to 300 ° C. and held for another 30 minutes (second firing), and then the furnace was cooled.
これに対し前記他方の基板は、雰囲気を窒素ガス比率１００％に調整された前記別の電気炉に入れられ、内部温度を３００℃にして３０分間保持された後、さらに同じ窒素ガス比率１００％の雰囲気中に３００℃で３０分間保持され、その後炉冷された。すなわち、前記他方の基板は、前記別の電気炉内で合計１時間の第２焼成のみが行われた。 On the other hand, the other substrate is placed in the other electric furnace whose atmosphere is adjusted to a nitrogen gas ratio of 100%, held at an internal temperature of 300 ° C. for 30 minutes, and then the same nitrogen gas ratio of 100%. Was kept at 300 ° C. for 30 minutes in the atmosphere, and then cooled in the furnace. That is, the second substrate was only subjected to second baking for a total of 1 hour in the separate electric furnace.
上記のように熱処理された前記２枚の基板に対し、各々の前記混合物が塗布された部分を粉末Ｘ線回折装置（ＸＲＤ）を用いて測定し、それぞれの結晶構造を同定した。同定した結果を表１に示す。
上記同定結果より、第１焼成と第２焼成の２段階の熱処理を行った場合には、銅酸化物が効率的に還元されていることが確認できた。これにより、カーボン材料を用いた本発明の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法は、酸化性雰囲気における第１焼成を行うようにしたことにより、金属酸化物粒子の還元を効果よく行うことができることが確認できた。 From the above identification results, it was confirmed that the copper oxide was efficiently reduced when the two-step heat treatment of the first firing and the second firing was performed. As a result, the reduction firing method of the metal oxide particles or the surface oxide coating of the metal particles according to the present invention using the carbon material reduces the metal oxide particles by performing the first firing in an oxidizing atmosphere. It was confirmed that it can be performed effectively.
なお、熱処理後の前記基板上には、未反応のカーボン材料が残留していると考えられるが、上記の粉末Ｘ線回折による測定結果には、前記カーボン材料の存在を示す顕著なピークは確認されなかった。これは、前記カーボン材料に用いたカーボンブラックの結晶構造が、非晶質状態であったことに起因するものと考えられる。 In addition, although it is thought that the unreacted carbon material remains on the substrate after the heat treatment, a remarkable peak indicating the presence of the carbon material is confirmed in the measurement result by the powder X-ray diffraction. Was not. This is considered due to the fact that the crystal structure of carbon black used for the carbon material was in an amorphous state.
次に、前記カーボン材料の有無により、金属酸化物の還元性にどのような影響を与えるかを確認した結果を以下に説明する。ここでは、前記銅ナノ粒子と前記カーボンブラック粉末との混合物を石英硝子基板上に塗布したものと、前記銅ナノ粒子のみを石英硝子基板に塗布した２種類のサンプルを用意し、それぞれに対し前記第１焼成と第２焼成の２段階の熱処理を行っている。 Next, the result of confirming how the presence or absence of the carbon material affects the reducibility of the metal oxide will be described below. Here, two types of samples prepared by applying a mixture of the copper nanoparticles and the carbon black powder on a quartz glass substrate and two samples obtained by applying only the copper nanoparticles to the quartz glass substrate are prepared. Two-stage heat treatment is performed, ie, first firing and second firing.
前記２段階の熱処理を行った後、前記混合物あるいは前記銅ナノ粒子が塗布された部分を粉末Ｘ線回折装置（ＸＲＤ）を用いて測定し、それぞれの結晶構造を同定した。該測定による同定結果を表２に示す。
上記同定結果より、カーボン材料を用いずに熱処理を行った場合には銅酸化物が残留しているのに対し、カーボン材料を用いて熱処理を行った場合には、銅酸化物が効率的に還元されていることが確認できた。これにより、カーボン材料を用いた本発明の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法は、金属酸化物粒子の還元を効果よく行えることが確認できた。 From the above identification results, when heat treatment was performed without using a carbon material, copper oxide remained, whereas when heat treatment was performed using a carbon material, copper oxide was efficiently It was confirmed that the product was reduced. Thus, it was confirmed that the metal oxide particles of the present invention using the carbon material or the method for reducing and firing the metal oxide surface oxide film can effectively reduce the metal oxide particles.
次に、前記第１焼成を行う前記電気炉内の酸化性雰囲気として、好ましい酸素分圧を検討した。ここでは、前記石英硝子基板を８枚用意し、それぞれに表面酸化皮膜を有する銅ナノ粒子とカーボンブラックからなる前記混合物を部分的に塗布した。そして、前記電気炉内の酸素分圧を０．１％、０．５％、１．０％、１０．０％、２５．０％、５０．０％、７５．０％、１００．０％とし、それぞれの酸化性雰囲気の中に前記石英硝子基板を１枚ずつ入れて第１焼成を行った。なお、酸素分圧１００．０％以外のケースでは、酸素以外は窒素のみが含まれる酸化性雰囲気とした。 Next, a preferable oxygen partial pressure was examined as an oxidizing atmosphere in the electric furnace for performing the first firing. Here, eight quartz glass substrates were prepared, and the mixture composed of copper nanoparticles having a surface oxide film and carbon black was partially applied thereto. And the oxygen partial pressure in the electric furnace is 0.1%, 0.5%, 1.0%, 10.0%, 25.0%, 50.0%, 75.0%, 100.0% Then, the quartz glass substrates were put one by one in each oxidizing atmosphere, and the first firing was performed. In cases other than oxygen partial pressure of 100.0%, an oxidizing atmosphere containing only nitrogen other than oxygen was used.
前記第１焼成後に前記第２焼成を行い、さらにその後に前記混合物が塗布された部分を粉末Ｘ線回折装置（ＸＲＤ）を用いて測定した。前記酸素分圧毎に同定された結晶構造の結果を表３に示す。
上記同定結果より、前記第１焼成を行う酸化性雰囲気として、酸素分圧が０．１％以上５０％以下とするのがよく、より好ましくは０．５％以上２５％以下とするのがよい。酸化性雰囲気を上記のようにすることにより、銅酸化物が効率的に還元されることが確認できた。 From the above identification result, the oxygen partial pressure is preferably 0.1% or more and 50% or less, more preferably 0.5% or more and 25% or less as the oxidizing atmosphere for performing the first firing. . It was confirmed that the copper oxide was efficiently reduced by making the oxidizing atmosphere as described above.
次に、前記第１焼成を行う前記電気炉内の内部温度が金属酸化物の還元性にどのような影響を与えるかを確認した。ここでは、前記石英硝子基板を１０枚用意し、それぞれに表面酸化皮膜を有する銅ナノ粒子とカーボンブラックからなる前記混合物を部分的に塗布した。 Next, it was confirmed how the internal temperature in the electric furnace where the first firing is performed affects the reducibility of the metal oxide. Here, ten quartz glass substrates were prepared, and the mixture of copper nanoparticles having a surface oxide film and carbon black was partially applied thereto.
そして、前記電気炉内の内部温度を１００℃、１５０℃、２００℃、２５０℃、３００℃、３５０℃、４００℃、４５０℃、５００℃、６００℃とし、それぞれの内部温度で第１焼成を行った。なお、前記電気炉内の酸化性雰囲気は、酸素ガス比率５％、窒素ガス比率９５％としている。 And the internal temperature in the said electric furnace is 100 degreeC, 150 degreeC, 200 degreeC, 250 degreeC, 300 degreeC, 350 degreeC, 400 degreeC, 450 degreeC, 500 degreeC, 600 degreeC, and 1st baking is carried out at each internal temperature. went. The oxidizing atmosphere in the electric furnace has an oxygen gas ratio of 5% and a nitrogen gas ratio of 95%.
上記各内部温度で前記第１焼成を行い、続いて前記第２焼成を行った後に、前記混合物が塗布された部分を粉末Ｘ線回折装置（ＸＲＤ）を用いて測定し、それぞれの結晶構造を同定した。前記測定により得られた同定結果を表４に示す。
上記同定結果より、前記第１焼成を行うときの前記電気炉内の内部温度として、１００℃以上５００℃以下とするのがよく、より好ましくは１５０℃以上４５０℃以下とするのがよい。前記第１焼成時の温度を上記のように設定することにより、銅酸化物が効率的に還元されることが確認できた。 From the above identification result, the internal temperature in the electric furnace when performing the first firing is preferably 100 ° C. or more and 500 ° C. or less, more preferably 150 ° C. or more and 450 ° C. or less. It was confirmed that the copper oxide was efficiently reduced by setting the temperature during the first firing as described above.
前記第１焼成時の温度が、例えば１００℃以下と低すぎる場合には、有機被膜の酸化分解反応が進行せず好ましくない。逆に、前記第１焼成時の温度が例えば５００℃以上と高すぎる場合には、金属粒子自体がその内部まで強固に酸化され、その後の第２焼成による還元が困難になってしまうため好ましくない。 If the temperature during the first baking is too low, for example, 100 ° C. or less, the oxidative decomposition reaction of the organic coating does not proceed, which is not preferable. On the contrary, when the temperature at the first firing is too high, for example, 500 ° C. or higher, the metal particles themselves are strongly oxidized to the inside, and subsequent reduction by the second firing becomes difficult, which is not preferable. .
最後に、前記第２焼成を行う前記別の電気炉内の内部温度が金属酸化物の還元性にどのような影響を与えるかを確認した。ここでも、前記石英硝子基板を１０枚用意し、それぞれに表面酸化皮膜を有する銅ナノ粒子とカーボンブラックからなる前記混合物を部分的に塗布した。そして、前記電気炉内の酸化性雰囲気を窒素ガス比率９５％、酸素ガス比率５％とし、内部温度２００℃で３０分間保持して前記各石英硝子基板を第１焼成した。 Finally, it was confirmed how the internal temperature in the second electric furnace where the second firing is performed affects the reducibility of the metal oxide. Also here, ten quartz glass substrates were prepared, and the mixture composed of copper nanoparticles and carbon black each having a surface oxide film was partially applied. Then, the quartz glass substrate was first fired by maintaining the oxidizing atmosphere in the electric furnace at a nitrogen gas ratio of 95% and an oxygen gas ratio of 5% and holding at an internal temperature of 200 ° C. for 30 minutes.
その後、窒素ガス比率１００％の前記別の電気炉内に前記各石英硝子基板を入れ、前記別の電気炉内の内部温度を１００℃、１５０℃、２００℃、２５０℃、３００℃、３５０℃、４００℃、４５０℃、５００℃、６００℃とした各ケースについて、それぞれ３０分間保持して第２焼成を行い、その後炉冷した。 Thereafter, each quartz glass substrate is placed in another electric furnace having a nitrogen gas ratio of 100%, and the internal temperature in the other electric furnace is 100 ° C., 150 ° C., 200 ° C., 250 ° C., 300 ° C., 350 ° C. , 400 ° C., 450 ° C., 500 ° C., and 600 ° C., each case was held for 30 minutes for second firing, and then cooled in the furnace.
上記炉冷後に、前記混合物が塗布された部分を粉末Ｘ線回折装置（ＸＲＤ）を用いて測定し、それぞれの結晶構造を同定した。前記測定により得られた結果を表５に示す。
上記同定結果より、前記第２焼成を行うときの前記別の電気炉内の内部温度として、１５０℃以上とするのがよく、より好ましくは２００℃以上とするのがよい。前記第２焼成時の温度を上記のようにすることにより、銅酸化物が効率的に還元されることが確認できた。 From the above identification result, the internal temperature in the separate electric furnace when performing the second firing is preferably 150 ° C. or higher, more preferably 200 ° C. or higher. It was confirmed that the copper oxide was efficiently reduced by setting the temperature during the second firing as described above.
前記第２焼成の温度が、例えば１５０℃以下と低すぎる場合には、酸化物の還元反応（２ＭＯ＋Ｃ→２Ｍ＋ＣＯ２、ここで、Ｃはカーボン、Ｍは金属元素を表す）が進行しないため好ましくない。なお、金属酸化物の還元方法という観点からは、焼成温度の上限は特に存在しない。但し、金属酸化物を塗布する基板からの制約が考えられ、該基板の耐熱温度以下にする必要があると考えられる。 When the temperature of the second baking is too low, for example, 150 ° C. or lower, the oxide reduction reaction (2MO + C → 2M + CO 2 , where C represents carbon and M represents a metal element) is not preferable. . From the viewpoint of the method for reducing the metal oxide, there is no particular upper limit for the firing temperature. However, there may be restrictions from the substrate to which the metal oxide is applied, and it is considered necessary to set the temperature to be equal to or lower than the heat resistant temperature of the substrate.
上記実施形態及び実施例では金属酸化物粒子として酸化銅を対象に説明したが、このほか酸化銀粒子あるいは酸化ニッケルナノ粒子であっても同様である。もしくは、表面酸化被膜を有する銅、銀あるいはニッケルからなる金属粒子であってもよい。上記いずれの金属酸化物粒子もしくは金属粒子の表面酸化被膜に対しても、本発明の還元焼成方法により効率的に還元することが可能となる。 Although the said embodiment and Example demonstrated copper oxide as object as a metal oxide particle, it is the same even if it is a silver oxide particle or nickel oxide nanoparticle. Or the metal particle which consists of copper, silver, or nickel which has a surface oxide film may be sufficient. Any of the above metal oxide particles or the surface oxide film of the metal particles can be efficiently reduced by the reduction firing method of the present invention.
また、前記金属酸化物粒子もしくは前記金属粒子の平均粒径は、１ｎｍ〜１００ｎｍの微粒子とするのがよく、より好ましくは1ｎｍ〜１０ｎｍとするのがよい。前記平均粒径を1ｎｍ〜１０ｎｍとした場合には、焼成後の粒子融着性が向上するといった効果が得られる。 Moreover, the average particle diameter of the metal oxide particles or the metal particles is preferably 1 nm to 100 nm, and more preferably 1 nm to 10 nm. When the average particle diameter is 1 nm to 10 nm, the effect of improving the particle fusion property after firing can be obtained.
さらに、前記有機物保護材には、金属酸化物と化学的もしくは物理的に結合、吸着する化合物を用いるのが好ましい。具体的には、ゼラチン、アラビアゴム、カゼイン、カゼイン酸ソーダ、カゼイン酸アンモニウム等のタンパク質系、デンプン、デキストリン、寒天、アルギン酸ソーダ等の天然高分子や、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、エチルセルロース等のセルロース系、ポリビニルアルコール、ポリビニルピロリドン等のビニル系、ポリアクリル酸ソーダ、ポリアクリル酸アンモニウム等のアクリル酸系、ステアリン酸等の高級脂肪酸、ポリエチレングリコール等の合成高分子、クエン酸等の多価カルボン酸、アニリンまたはそれらの誘導体等が挙げられる。特に、ゼラチン、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコールを用いるのがよい。 Furthermore, it is preferable to use a compound that is chemically or physically bonded to and adsorbed to the metal oxide as the organic protective material. Specifically, protein systems such as gelatin, gum arabic, casein, sodium caseinate, ammonium caseinate, natural polymers such as starch, dextrin, agar, sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, etc. Cellulose, vinyl alcohol such as polyvinyl alcohol, polyvinyl pyrrolidone, acrylic acid such as sodium polyacrylate, ammonium polyacrylate, higher fatty acid such as stearic acid, synthetic polymer such as polyethylene glycol, polyvalent carboxylic acid such as citric acid Examples include acids, anilines or derivatives thereof. In particular, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, or polyethylene glycol is preferably used.
上記説明の本発明の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法を用いることで、導電性の優れた導電部品を形成することができる。すなわち、本発明の導電部品の形成方法によれば、前記金属酸化物粒子もしくは表面酸化被膜を有する前記金属粒子と前記カーボン材料との混合物を、基板上に塗布もしくは表面パターニングした後、前記第１焼成と前記第２焼成を行うことで、導電性の優れた導電部品を形成することができる。 By using the above-described method for reducing and firing the metal oxide particles or the surface oxide film of the metal particles according to the present invention, a conductive component having excellent conductivity can be formed. That is, according to the method for forming a conductive component of the present invention, after applying or surface patterning a mixture of the metal oxide particles or the metal particles having a surface oxide film and the carbon material onto the substrate, the first By performing the firing and the second firing, a conductive component having excellent conductivity can be formed.
前記導電部品として、例えば導電路、バンプ、ビア、アンテナパターン、熱伝導路及び触媒電極等が挙げられる。また、前記基板は前記導電部品の形成に使用されるものであり、例えば、酸化物、ガラス、セラミックス、金属、半導体、プラスチックのいずれかを用いることができる。特に、本発明の導電部品の形成方法によれば、耐熱性の低い汎用樹脂基板（ガラエポやポリイミド等）を用いることも可能となる。 Examples of the conductive component include conductive paths, bumps, vias, antenna patterns, thermal conductive paths, and catalyst electrodes. The substrate is used for forming the conductive component. For example, any of oxide, glass, ceramics, metal, semiconductor, and plastic can be used. In particular, according to the method for forming a conductive component of the present invention, it is possible to use a general-purpose resin substrate (eg, glass epoxy or polyimide) having low heat resistance.
なお、本実施の形態における記述は、本発明に係る金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法及び導電部品の形成方法の一例を示すものであり、これに限定されるものではない。本実施の形態における細部構成及び詳細な動作等に関しては、本発明の趣旨を逸脱しない範囲で適宜変更可能である。 Note that the description in the present embodiment shows an example of the method for reducing and firing the metal oxide particles or the surface oxide film of the metal particles and the method for forming the conductive component according to the present invention, and is not limited to this. Absent. The detailed configuration, detailed operation, and the like in the present embodiment can be changed as appropriate without departing from the spirit of the present invention.
１０〜４０・・・工程
５０・・・基板
６０・・・混合物
10-40 ...
Claims (14)
さらに不活性ガス中（以下では不活性雰囲気という）で第２焼成する
ことを特徴とする金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 Carbon material including metal oxide particles whose surface is coated with an organic protective material or metal particles having a surface oxide film, and at least one of carbon black, carbon nanotube, VGCF (vapor-grown carbon fiber), and carbon fullerene And a first firing in an oxidizing gas containing oxygen (hereinafter referred to as an oxidizing atmosphere),
Further, the second firing is performed in an inert gas (hereinafter referred to as an inert atmosphere), and the method for reducing and firing the metal oxide particles or the surface oxide film of the metal particles.
ことを特徴とする請求項１に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 2. The reduction of the metal oxide particles or the surface oxide film of the metal particles according to claim 1, wherein the oxygen concentration in the oxidizing atmosphere is 0.1% (number of atoms, hereinafter the same) to 50%. Firing method.
ことを特徴とする請求項１に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 2. The method for reducing and firing metal oxide particles or a surface oxide film of metal particles according to claim 1, wherein the oxygen concentration in the oxidizing atmosphere is 0.5% or more and 25% or less.
ことを特徴とする請求項１から請求項３のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The inert gas contained in the inert atmosphere is any one of nitrogen, helium, neon, argon, krypton, and xenon, or a mixed gas of the inert gas. The reduction firing method of the metal oxide particle of any one, or the surface oxide film of a metal particle.
ことを特徴とする請求項１から請求項３のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The surface of the metal oxide particle or metal particle according to any one of claims 1 to 3, wherein the inert gas contained in the inert atmosphere is nitrogen, argon, or a mixed gas thereof. A method for reducing and firing an oxide film.
ことを特徴とする請求項１から請求項５のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The surface oxidation of the metal oxide particles or metal particles according to any one of claims 1 to 5, wherein the temperature of the first firing in the oxidizing atmosphere is 100 ° C or higher and 500 ° C or lower. A method for reducing and firing the coating.
ことを特徴とする請求項１から請求項３のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 4. The surface oxidation of metal oxide particles or metal particles according to claim 1, wherein the temperature of the first firing in the oxidizing atmosphere is 150 ° C. or higher and 450 ° C. or lower. 5. A method for reducing and firing the coating.
ことを特徴とする請求項１から請求項７のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The reduction of the metal oxide particles or the surface oxide film of the metal particles according to any one of claims 1 to 7, wherein a temperature of the second baking in the inert atmosphere is 150 ° C or higher. Firing method.
ことを特徴とする請求項１から請求項７のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The reduction of the metal oxide particles or the surface oxide film of the metal particles according to any one of claims 1 to 7, wherein a temperature of the second baking in the inert atmosphere is 200 ° C or higher. Firing method.
ことを特徴とする、請求項１から請求項９のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The metal oxide particles are any one of copper oxide, silver oxide particles, and nickel oxide, or the metal particles having the surface oxide film are any one of copper, silver, and nickel. The method for reducing and firing the metal oxide particles or the surface oxide film of the metal particles according to claim 9.
ことを特徴とする請求項１から請求項１０のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜還元焼成方法。 The surface of the metal oxide particle or metal particle according to any one of claims 1 to 10, wherein the metal oxide particle or the metal particle is a fine particle having an average particle diameter of 1 nm to 100 nm. Oxide film reduction firing method.
ことを特徴とする請求項１から請求項１１のいずれか１項に記載の金属酸化物粒子もしくは金属粒子の表面酸化被膜の還元焼成方法。 The metal oxide particles or metal particles according to any one of claims 1 to 11, wherein the organic protective material is a compound that chemically or physically binds and adsorbs to a metal oxide. A method for reducing and firing the surface oxide film.
ことを特徴とする導電部品の形成方法。 A mixture of a metal oxide particle having a surface coated with an organic protective material or a metal particle having a surface oxide film and a carbon material containing at least one of carbon black, carbon nanotube, VGCF, and carbon fullerene is formed on a substrate. An electrically conductive component comprising: applying metal oxide particles or applying surface patterning to the surface, followed by firing using the reduction firing method for metal oxide particles or metal particle surface oxide coating according to any one of claims 1 to 7. Forming method.
ことを特徴とする請求項１３に記載の導電部品の形成方法。 The method for forming a conductive component according to claim 13, wherein the substrate is made of any one of oxide, glass, ceramics, metal, semiconductor, and plastic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006085910A JP4593502B2 (en) | 2006-03-27 | 2006-03-27 | Method of reducing and firing metal oxide particles or surface oxide film of metal particles and method of forming conductive parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006085910A JP4593502B2 (en) | 2006-03-27 | 2006-03-27 | Method of reducing and firing metal oxide particles or surface oxide film of metal particles and method of forming conductive parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007262446A JP2007262446A (en) | 2007-10-11 |
| JP4593502B2 true JP4593502B2 (en) | 2010-12-08 |
Family
ID=38635712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006085910A Expired - Fee Related JP4593502B2 (en) | 2006-03-27 | 2006-03-27 | Method of reducing and firing metal oxide particles or surface oxide film of metal particles and method of forming conductive parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4593502B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5338235B2 (en) * | 2008-09-30 | 2013-11-13 | 大日本印刷株式会社 | Manufacturing method of conductive substrate and conductive substrate obtained by the method |
| DE102008053027A1 (en) | 2008-10-24 | 2010-04-29 | Kme Germany Ag & Co. Kg | Method for producing a coating comprising carbon nanotubes, fullerenes and / or graphene |
| KR101038784B1 (en) * | 2009-02-03 | 2011-06-03 | 삼성전기주식회사 | Method for forming metal wiring and metal wiring using the same |
| JP2013135070A (en) * | 2011-12-26 | 2013-07-08 | Jsr Corp | Pattern forming method and metal pattern |
| EP3363561A1 (en) * | 2017-02-16 | 2018-08-22 | Höganäs AB | Particles having a sinterable core and a polymeric coating, use thereof, and additive manufacturing method using the same |
| CN108788132B (en) * | 2018-07-09 | 2020-04-28 | 中南大学 | In-situ reaction preparation method of copper-carbon composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103043A1 (en) * | 2003-05-16 | 2004-11-25 | 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 using said method |
| JP2006269119A (en) * | 2005-03-22 | 2006-10-05 | Furukawa Electric Co Ltd:The | Reduction/thermolysis mutual fusion method by high frequency electromagnetic wave irradiation for metal oxide particle or the like to which sintering aid is added, and calcination material for various electronic parts and metal oxide particle or like using it |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3599950B2 (en) * | 1997-04-16 | 2004-12-08 | 株式会社アルバック | Method of firing metal paste |
| JP3630920B2 (en) * | 1997-05-02 | 2005-03-23 | 株式会社アルバック | Metal paste firing method |
-
2006
- 2006-03-27 JP JP2006085910A patent/JP4593502B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103043A1 (en) * | 2003-05-16 | 2004-11-25 | 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 using said method |
| JP2006269119A (en) * | 2005-03-22 | 2006-10-05 | Furukawa Electric Co Ltd:The | Reduction/thermolysis mutual fusion method by high frequency electromagnetic wave irradiation for metal oxide particle or the like to which sintering aid is added, and calcination material for various electronic parts and metal oxide particle or like using it |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007262446A (en) | 2007-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4593502B2 (en) | Method of reducing and firing metal oxide particles or surface oxide film of metal particles and method of forming conductive parts | |
| Yang et al. | Printed electrically conductive composites: conductive filler designs and surface engineering | |
| EP2906027B1 (en) | Lead solder-free electronics | |
| JP4157468B2 (en) | Wiring board | |
| KR101020844B1 (en) | Reducing agent for low temperature reducing and sintering of copper nanoparticels, and method for low temperature sintering using the same | |
| JP2014225338A (en) | Copper fine particle dispersion liquid, conductive film forming method, and circuit board | |
| TWI665332B (en) | Dispersion,method for manufacturing structure with conductive pattern using the same,and structure with conductive pattern | |
| JP2015164896A (en) | Method for applying carbon/tin mixtures to metal or alloy coatings | |
| JP6165063B2 (en) | Conductive particles and method for producing the same | |
| Gysling | Nanoinks in inkjet metallization—Evolution of simple additive-type metal patterning | |
| Dai et al. | Self-reducible Cu nanoparticles for conductive inks | |
| JP5582498B2 (en) | Electrical conductor and method for forming the same | |
| JP4762582B2 (en) | Reduction / mutual fusion method of high-frequency electromagnetic wave irradiation such as metal oxide particles with sintering aid added, and various electronic parts using the same and firing materials such as metal oxide particles | |
| KR101235510B1 (en) | Methods of forming high density metal wiring for fine line and space packaging applications and structures formed thereby | |
| JP2005135982A (en) | Circuit board and manufacturing method therefor | |
| JP2009278045A (en) | Workpiece and method for producing the same | |
| KR100599053B1 (en) | Conductive ink, method for forming conductive wiring, and conductive substrate | |
| WO2014059798A1 (en) | Nano-copper ink and copper conductive film preparation method | |
| JP2008121043A (en) | Fine particle, fine particle dispersion, method for producing fine particle and method for producing fine particle dispersion | |
| KR100902037B1 (en) | Foramtion method for wiring pattern using nano ink comprising metals with low melting point | |
| JP4761110B2 (en) | Metal coating and method for forming the same | |
| JP2009076568A (en) | Electronic device | |
| JP2016086013A (en) | Film-like printed circuit board and method for manufacturing the same | |
| US11254156B2 (en) | Magnetic field patterning of nickel nanofibers using precursor ink | |
| JP2007154231A (en) | Spherical molybdenum metal particle and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081104 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100826 |
|
| 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: 20100903 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100915 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130924 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130924 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |