JP5286846B2 - Conductive substrate and method for manufacturing the same, copper wiring substrate and method for manufacturing the same - Google Patents
Conductive substrate and method for manufacturing the same, copper wiring substrate and method for manufacturing the same Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 143
- 229910052802 copper Inorganic materials 0.000 title claims description 137
- 239000010949 copper Substances 0.000 title claims description 137
- 239000000758 substrate Substances 0.000 title claims description 89
- 238000004519 manufacturing process Methods 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 35
- 239000002245 particle Substances 0.000 claims description 139
- 239000005751 Copper oxide Substances 0.000 claims description 72
- 229910000431 copper oxide Inorganic materials 0.000 claims description 72
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 71
- 239000011248 coating agent Substances 0.000 claims description 69
- 238000000576 coating method Methods 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 57
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- 238000005245 sintering Methods 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000003223 protective agent Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 5
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- 239000004020 conductor Substances 0.000 description 18
- 239000011258 core-shell material Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 16
- -1 and specifically Substances 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
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- 239000005749 Copper compound Substances 0.000 description 8
- 150000001880 copper compounds Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000012756 surface treatment agent Substances 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 229910021642 ultra pure water Inorganic materials 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 125000006239 protecting group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 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
- 230000000052 comparative effect Effects 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
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- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 239000002798 polar solvent Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 241001424397 Paralucia pyrodiscus Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GXROCGVLAIXUAF-UHFFFAOYSA-N copper octan-1-ol Chemical compound [Cu].CCCCCCCCO GXROCGVLAIXUAF-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子、又は酸化銅からなる粒子を用いて製造される導電性基板及びその製造方法、並びに該粒子を用いて製造される銅配線基板及びその製造方法に関する。 The present invention relates to a conductive substrate manufactured using particles having a core / shell structure in which the core portion is copper and the shell portion is copper oxide, or particles made of copper oxide, a method for manufacturing the same, and the particles. The present invention relates to a copper wiring board manufactured using the same and a manufacturing method thereof.
近年、金属ナノ粒子を用いた配線パターン製造方法が検討されており、金あるいは銀ナノ粒子を用いる方法は確立されている（例えば、特許文献１、２参照。）。具体的には、金あるいは銀ナノ粒子を含む分散液を利用して極めて微細な回路パターンを描画し、その後、金属ナノ粒子相互の焼結を施すことにより、得られる焼結体型配線層において、配線幅および配線間スペースが５〜５０ｎｍ、体積平均抵抗率が１×１０−７Ω・ｍ以下の配線形成が可能となっている。
しかしながら、金や銀といった貴金属ナノ粒子を用いる際には、材料自体が高価であるため、かかる超微細印刷用分散液の作製単価も高くなり、汎用品として幅広く普及する上での大きな経済的障害となっている。さらに、銀ナノ粒子では、配線幅および配線間スペースが狭くなっていくにつれ、エレクトロマイグレーションに起因する回路間の絶縁低下という欠点や問題として浮上している。
以上のことから、微細配線形成用の金属ナノ粒子分散液としては、エレクトロマイグレーションが少なく、金や銀と比較して材料自体の単価も相当に安価な銅の利用が期待されている。銅の粒子は貴金属と比較して酸化されやすい性質を持つため、表面処理剤には分散性の向上目的以外に酸化防止の作用を持つものが用いられ、例えば、銅表面と相互作用する置換基を有する高分子や長鎖アルキル基を有する表面処理剤が用いられている（例えば、特許文献３、４参照。）。
In recent years, wiring pattern manufacturing methods using metal nanoparticles have been studied, and methods using gold or silver nanoparticles have been established (see, for example,
However, when using noble metal nanoparticles such as gold and silver, the material itself is expensive, so the production unit price of such a dispersion for ultra fine printing is also high, which is a major economic obstacle to widespread use as a general-purpose product. It has become. Furthermore, with silver nanoparticles, as the wiring width and inter-wiring space become narrower, it has emerged as a drawback and problem of reduced insulation between circuits due to electromigration.
From the above, it is expected that the metal nanoparticle dispersion for forming the fine wiring has less electromigration and the use of copper, which is considerably less expensive than gold and silver. Since copper particles are more easily oxidized than precious metals, surface treatment agents that have an anti-oxidation function other than the purpose of improving dispersibility are used, for example, substituents that interact with the copper surface. Or a surface treatment agent having a long-chain alkyl group is used (for example, see Patent Documents 3 and 4).
上記表面処理剤を有する銅粒子の導体化法は、（１）銅粒子表面における表面処理剤の保護基の脱離、（２）還元雰囲気による表面酸化層の還元及び焼結中の酸化防止、（３）粒子間接触部の融着、の３つのステップからなる。そして、（１）保護基の脱離に大きなエネルギーを必要とし、２００℃以上への加熱あるいはエネルギー線の併用が必須であり、耐熱性の高い基板が要求されることから、使用可能な基板が限られることが課題である。また、逆に言えば、低温での焼結では保護基の脱離が不十分となり、配線パターンが導通されないか、あるいは導通されても低抵抗とはならないという問題があった。 The copper particles having the surface treatment agent are made into a conductor: (1) elimination of the protective group of the surface treatment agent on the surface of the copper particles, (2) reduction of the surface oxide layer in a reducing atmosphere and oxidation prevention during sintering, (3) It consists of three steps of fusion of the interparticle contact part. And (1) a large energy is required for elimination of the protecting group, heating to 200 ° C. or higher, or combined use of energy rays is essential, and a substrate having high heat resistance is required. It is a problem to be limited. In other words, there is a problem in that the sintering of the protective group becomes insufficient in sintering at a low temperature, and the wiring pattern is not conducted or the resistance is not lowered even when conducted.
そこで本発明は、銅粒子による導体層を有する導電性基板でありながら、銅粒子の表面処理剤（分散剤、保護剤）を要せず、比較的低温にて銅粒子の焼結が可能で、基板の耐熱性の制約が少ない導電性基板及びその製造方法を提供することを目的とする。
また本発明の別の目的は、比較的低温で焼結しても、低抵抗の銅配線パターンが得られ、基板の耐熱性の制約が少ない銅配線基板及びその製造方法を提供することにある。
Therefore, the present invention does not require a surface treatment agent (dispersant, protective agent) for copper particles, and can sinter copper particles at a relatively low temperature, although it is a conductive substrate having a conductor layer of copper particles. An object of the present invention is to provide a conductive substrate with less restrictions on the heat resistance of the substrate and a method for manufacturing the same.
Another object of the present invention is to provide a copper wiring board having a low resistance even when sintered at a relatively low temperature, and having less restrictions on the heat resistance of the board, and a method for manufacturing the same. .
前記課題を解決するための手段は以下に通りである。
（１）コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子を含む塗布乾燥膜が成膜された基板を還元性液体に浸漬し、前記塗布乾燥膜中に含まれる各粒子の酸化銅を銅に還元する工程と、
前記還元性液体を加熱して、還元されて得られた銅粒子同士を焼結する工程と、
を含むことを特徴とする導電性基板の製造方法。
Means for solving the above-described problems are as follows.
(1) A substrate on which a coating / drying film containing particles having a core / shell structure in which a core part is copper and a shell part is copper oxide is immersed in a reducing liquid and included in the coating / drying film Reducing the copper oxide of each particle to copper,
Heating the reducing liquid and sintering the copper particles obtained by reduction; and
The manufacturing method of the electroconductive board | substrate characterized by the above-mentioned.
（２）コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子を含む塗布乾燥膜が成膜された基板を、銅粒子同士が焼結し得る温度まで加熱した還元性液体に浸漬し、前記塗布乾燥膜中に含まれる各粒子の酸化銅を銅に還元し、還元されて得られた銅粒子同士を焼結する工程を含むことを特徴とする導電性基板の製造方法。 (2) Reduction in which a substrate on which a coating / drying film containing particles having a core / shell structure in which the core part is copper and the shell part is copper oxide is heated to a temperature at which the copper particles can be sintered together A step of immersing in a conductive liquid, reducing the copper oxide of each particle contained in the dried coating film to copper, and sintering the copper particles obtained by reduction. Production method.
（３）前記塗布乾燥膜が、前記粒子に対する保護剤又は分散剤を用いずに調製された塗布液を塗布して形成されてなることを特徴とする（１）または（２）に記載の導電性基板の製造方法。 (3) The conductive dry film according to (1) or (2), wherein the coating dry film is formed by coating a coating solution prepared without using a protective agent or a dispersant for the particles. Of manufacturing a conductive substrate.
（４）前記塗布乾燥膜が、高周波誘導加熱燃焼−赤外線吸収法による炭素分測定における炭素分が３ｍａｓｓ％以下であることを特徴とする（１）または（２）に記載の導電性基板の製造方法。 (4) The conductive substrate according to (1) or (2), wherein the coating dry film has a carbon content of 3 mass% or less in a carbon content measurement by a high frequency induction heating combustion-infrared absorption method. Method.
（５）前記還元性液体の加熱温度を１２０〜２００℃とすることを特徴とする請求項（１）から（４）のいずれかに記載の導電性基板の製造方法。 (5) The method for producing a conductive substrate according to any one of (1) to (4), wherein the heating temperature of the reducing liquid is 120 to 200 ° C.
（６）（１）から（５）のいずれかに記載の導電性基板の製造方法により製造されてなる導電性基板。 (6) A conductive substrate produced by the method for producing a conductive substrate according to any one of (1) to (5).
（７）基板上に、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子を含む塗布液を用いて任意の配線パターンを描画する工程と、
描画した塗布液による配線パターンを乾燥後、還元性液体に浸漬し、前記配線パターン中に含まれる各粒子の酸化銅を銅に還元する工程と、
前記還元性液体を加熱して、還元されて得られた銅粒子同士を焼結し、銅配線とする工程と、を含むことを特徴とする銅配線基板の製造方法。
(7) A step of drawing an arbitrary wiring pattern on the substrate using a coating solution containing particles having a core / shell structure in which the core part is copper and the shell part is copper oxide;
After drying the drawn wiring pattern with the coating solution, immersing in a reducing liquid, reducing the copper oxide of each particle contained in the wiring pattern to copper,
And heating the reducing liquid to sinter the copper particles obtained by reduction to form a copper wiring.
（８）基板上に、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子を含む塗布液を用いて任意の配線パターンを描画する工程と、
描画した塗布液による配線パターンを乾燥後、銅粒子同士が焼結し得る温度まで加熱した還元性液体に浸漬し、前記配線パターン中に含まれる各粒子の酸化銅を銅に還元し、還元されて得られた銅粒子同士を焼結し、銅配線とする工程と、を含むことを特徴とする銅配線基板の製造方法。
(8) A step of drawing an arbitrary wiring pattern on the substrate using a coating solution containing particles having a core / shell structure in which the core part is copper and the shell part is copper oxide;
After the wiring pattern with the drawn coating solution is dried, it is immersed in a reducing liquid heated to a temperature at which the copper particles can sinter, and the copper oxide of each particle contained in the wiring pattern is reduced to copper and reduced. And a step of sintering the copper particles obtained in this way to form a copper wiring.
（９）前記塗布液が、前記粒子に対する保護剤又は分散剤を用いずに調製されてなることを特徴とする（７）または（８）に記載の銅配線基板の製造方法。 (9) The method for producing a copper wiring board according to (7) or (8), wherein the coating liquid is prepared without using a protective agent or a dispersant for the particles.
（１０）前記塗布乾燥膜が，高周波誘導加熱燃焼−赤外線吸収法による炭素分測定における炭素分が３ｍａｓｓ％以下であることを特徴とする（７）または（８）に記載の銅配線基板の製造方法。 (10) The copper wiring substrate according to (7) or (8), wherein the coating dry film has a carbon content of 3 mass% or less in a carbon content measurement by high-frequency induction heating combustion-infrared absorption method. Method.
（１１）前記還元性液体の加熱温度を１２０〜２００℃とすることを特徴とする（７）から（１０）のいずれかに記載の銅配線基板の製造方法。 (11) The method for producing a copper wiring board according to any one of (7) to (10), wherein the heating temperature of the reducing liquid is 120 to 200 ° C.
（１２）（７）から（１１）のいずれかに記載の銅配線基板の製造方法により製造されてなる銅配線基板。 (12) A copper wiring board manufactured by the method for manufacturing a copper wiring board according to any one of (7) to (11).
本発明によれば、銅粒子による導体層を有する導電性基板でありながら、銅粒子の表面処理剤（分散剤、保護剤）を要せず、比較的低温にて銅粒子の焼結が可能で、基板の耐熱性の制約が少ない導電性基板及びその製造方法を提供することができる。
また本発明によれば、比較的低温で焼結しても、低抵抗の銅配線パターンが得られ、基板の耐熱性の制約が少ない銅配線基板及びその製造方法を提供することができる。
According to the present invention, a copper substrate can be sintered at a relatively low temperature without a copper particle surface treatment agent (dispersant, protective agent), even though it is a conductive substrate having a conductor layer of copper particles. Thus, it is possible to provide a conductive substrate with less restrictions on the heat resistance of the substrate and a manufacturing method thereof.
In addition, according to the present invention, a copper wiring board having a low resistance can be obtained even when sintered at a relatively low temperature, and a copper wiring board with less restrictions on the heat resistance of the board and a manufacturing method thereof can be provided.
＜導電性基板及びその製造方法＞
本発明の導電性基板の製造方法は、第１の態様によると、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子、又は酸化銅からなる粒子を含む塗布乾燥膜が成膜された基板を還元性液体に浸漬し、前記塗布乾燥膜中に含まれる各粒子の酸化銅を銅に還元する工程と、前記還元性液体を加熱して、還元されて得られた銅粒子同士を焼結する工程と、を含むことを特徴とする。
本発明の導電性基板の製造方法は、第２の態様によると、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子、又は酸化銅からなる粒子を含む塗布乾燥膜が成膜された基板を、銅粒子同士が焼結し得る温度まで加熱した還元性液体に浸漬し、前記塗布乾燥膜中に含まれる各粒子の酸化銅を銅に還元し、還元されて得られた銅粒子同士を焼結する工程を含むことを特徴とする。
また、本発明の導電性基板は、上記本発明の導電性基板の製造方法により製造されてなる。
<Conductive substrate and manufacturing method thereof>
According to the first aspect of the method for producing a conductive substrate of the present invention, coating drying including particles having a core / shell structure in which the core part is copper and the shell part is copper oxide, or particles made of copper oxide. A step of immersing the substrate on which the film is formed in a reducing liquid, reducing the copper oxide of each particle contained in the coating dry film to copper, and heating the reducing liquid to obtain a reduced liquid. And a step of sintering the copper particles together.
According to the second aspect of the method for producing a conductive substrate of the present invention, coating drying including particles having a core / shell structure in which the core portion is copper and the shell portion is copper oxide, or particles made of copper oxide. The substrate on which the film is formed is immersed in a reducing liquid heated to a temperature at which the copper particles can sinter, and the copper oxide of each particle contained in the coating dry film is reduced to copper and reduced. It includes a step of sintering the obtained copper particles.
The conductive substrate of the present invention is manufactured by the above-described method for manufacturing a conductive substrate of the present invention.
すなわち本発明においては、酸化銅の還元から銅粒子の焼結までの工程を終始還元性液体中で行うことにより、生成する銅粒子の酸化を防止しているため、酸化防止のための保護剤や分散剤（表面処理剤）を必要としない。すなわち、保護剤などを使用しないため、銅粒子表面の保護基の脱離などに必要なエネルギーが不要であり、比較的低温で銅粒子生成から焼結までを行うことができ、ひいては耐熱性が低い基板でも使用することが可能となり、基板の耐熱性の制約が少なくなる。
以下にまず、本発明の導電性基板の製造方法のいずれの態様にも使用する粒子、還元性液体など各要素について説明する。
That is, in the present invention, since the process from the reduction of copper oxide to the sintering of copper particles is carried out in a reducing liquid throughout the process, the generated copper particles are prevented from being oxidized. And no dispersant (surface treatment agent) is required. That is, since a protective agent is not used, energy necessary for detachment of the protecting group on the surface of the copper particles is not required, and the process from copper particle generation to sintering can be performed at a relatively low temperature. Even a low substrate can be used, and the heat resistance restriction of the substrate is reduced.
Below, each element, such as particle | grains used for any aspect of the manufacturing method of the electroconductive board | substrate of this invention, a reducing liquid, is demonstrated.
［銅／酸化銅コアシェル粒子］
コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子（以下、「銅／酸化銅コアシェル粒子」と称する。）は、例えば、還元作用を示さない有機溶剤中に分散させた原料金属化合物にレーザー光を攪拌下で照射して製造されたものを用いることができる。また，不活性ガス中のプラズマ炎に銅原料を導入し，冷却用不活性ガスで急冷して製造された銅/酸化銅コアシェル粒子を用いることもできる。レーザー光を用いた銅／酸化銅コアシェル粒子の特性は、原料銅化合物の種類、原料銅化合物の粒子径、原料銅化合物の量、有機溶剤の種類、レーザー光の波長、レーザー光の出力、レーザー光の照射時間、温度、銅化合物の攪拌状態、有機溶剤中に導入する気体バブリングガスの種類、バブリングガスの量、添加物などの諸条件を適宜選択することによって制御される。
以下にレーザー光を用いた銅/酸化銅コアシェル粒子の詳細について説明する。
[Copper / copper oxide core-shell particles]
Particles having a core / shell structure in which the core portion is copper and the shell portion is copper oxide (hereinafter referred to as “copper / copper oxide core-shell particles”) are dispersed in, for example, an organic solvent that does not exhibit a reducing action. What was manufactured by irradiating the raw material metal compound with laser light under stirring can be used. It is also possible to use copper / copper oxide core-shell particles produced by introducing a copper raw material into a plasma flame in an inert gas and quenching it with an inert gas for cooling. The characteristics of copper / copper oxide core-shell particles using laser light are as follows: raw material copper compound type, raw material copper compound particle size, raw material copper compound amount, organic solvent type, laser light wavelength, laser light output, laser It is controlled by appropriately selecting various conditions such as light irradiation time, temperature, stirring state of the copper compound, the type of gas bubbling gas introduced into the organic solvent, the amount of bubbling gas, and additives.
Details of the copper / copper oxide core-shell particles using laser light will be described below.
Ａ．原料
原料は銅化合物であって、具体的には、酸化銅・亜酸化銅・硫化銅・オクチル酸銅・塩化銅などを用いることができる。
なお、原料の大きさは重要であり、同じエネルギー密度のレーザー光を照射する場合でも、原料の金属化合物粉体の粒径が小さいほど粒径の小さなコア／シェル粒子が効率よく得られる。また、形状は真球状、破砕状、板状、鱗片状、棒状など種々の形状の原料を用いることができる。
A. Raw material The raw material is a copper compound, and specifically, copper oxide, cuprous oxide, copper sulfide, copper octylate, copper chloride and the like can be used.
The size of the raw material is important. Even when the laser beam having the same energy density is irradiated, the smaller the particle size of the metal compound powder of the raw material, the more efficiently the core / shell particles having a smaller particle size can be obtained. Moreover, the raw material of various shapes, such as a spherical shape, a crushed shape, plate shape, scale shape, rod shape, can be used for a shape.
Ｂ．レーザー光
レーザー光の波長は銅化合物の吸収係数がなるべく大きくなるような波長とすることが好ましいが、ナノサイズの銅微粒子の結晶成長を抑制するためには、熱線としての効果が低い短波長のレーザー光を使用することが好ましい。
例えば、レーザー光は、Ｎｄ：ＹＡＧレーザー、エキシマレーザー、半導体レーザー、色素レーザーなどを用いることができる。また、高エネルギーのレーザーを同じ条件で多くの銅化合物に照射するためにはパルス照射が好ましい。
B. Laser light The wavelength of the laser light is preferably such that the absorption coefficient of the copper compound is as large as possible. However, in order to suppress the crystal growth of nano-sized copper fine particles, the wavelength of the short wavelength has a low effect as a heat ray. It is preferable to use laser light.
For example, an Nd: YAG laser, an excimer laser, a semiconductor laser, a dye laser, or the like can be used as the laser light. Moreover, pulse irradiation is preferable in order to irradiate many copper compounds with a high energy laser under the same conditions.
Ｃ．有機溶剤（粒子生成時の分散媒）
粒子生成の際の銅化合物の分散媒に用いる有機溶剤としては、アセトン、メチルエチルケトン、γ−ブチロラクトン、シクロヘキサノンなどのケトン系溶剤を使用することがナノサイズの粒子を得る際には好ましいが、ジメチルアセトアミド、Ｎ−メチルピロリドン、プロピレングリコールモノエチルエーテルなどの極性溶剤やトルエン、テトラデカンなどの炭化水素系溶剤を用いることもできる。また、１種を単独で又は２種以上を組合わせて使用してもよい。なお、還元性を示す有機溶剤を用いると、銅粒子のシェルを形成する酸化皮膜を還元し、金属が露出することにより、凝集体を形成するために、粒子の分散安定性を損なうことになる。従って、還元作用を示さない有機溶剤を用いることが好ましい。
なお、以上の銅／酸化銅コアシェル粒子の作製手法は一例であり、本発明はそれに限定されることはない。また、例えば、市販のものがあればそれを用いてもよい。
C. Organic solvent (dispersion medium during particle generation)
As the organic solvent used for the dispersion medium of the copper compound during particle formation, it is preferable to use a ketone solvent such as acetone, methyl ethyl ketone, γ-butyrolactone, cyclohexanone, etc., in order to obtain nano-sized particles, but dimethylacetamide Also, polar solvents such as N-methylpyrrolidone and propylene glycol monoethyl ether, and hydrocarbon solvents such as toluene and tetradecane can be used. Moreover, you may use 1 type individually or in combination of 2 or more types. When an organic solvent exhibiting reducibility is used, the oxide film that forms the shell of the copper particles is reduced, and the metal is exposed to form aggregates, thereby impairing the dispersion stability of the particles. . Therefore, it is preferable to use an organic solvent that does not exhibit a reducing action.
In addition, the preparation methods of the above copper / copper oxide core-shell particle | grains are an example, and this invention is not limited to it. For example, if there is a commercially available product, it may be used.
本発明において使用される銅／酸化銅コアシェル粒子は、粒子間の融着温度の低減という観点から、一次粒子の数平均粒子径が１０，０００〜５ｎｍであることが好ましく、１，０００〜１０ｎｍであることがより好ましく、１００〜１０ｎｍであることがさらに好ましい。 The copper / copper oxide core-shell particles used in the present invention preferably have a number average particle size of primary particles of 10,000 to 5 nm, and 1,000 to 10 nm, from the viewpoint of reducing the fusion temperature between the particles. It is more preferable that the thickness is 100 to 10 nm.
［分散媒］
本発明の製造方法において、前記粒子を含む塗布乾燥膜は、前記粒子を含有する分散液を塗布液として基板などに塗布し、形成された塗膜を乾燥して形成することができる。ここで、前記粒子を含有する分散液を調製する際に用いる分散媒としては、例えば、アセトン、メチルエチルケトン、γ−ブチロラクトン、シクロヘキサノンなどのケトン系溶剤、ジメチルアセトアミド、Ｎ−メチルピロリドン、プロピレングリコールモノエチルエーテルなどの極性溶剤やトルエン、テトラデカンなどの炭化水素系溶剤を用いることができる。
[Dispersion medium]
In the production method of the present invention, the coating and drying film containing the particles can be formed by applying a dispersion containing the particles to a substrate or the like as a coating liquid, and drying the formed coating film. Here, examples of the dispersion medium used in preparing the dispersion containing the particles include ketone solvents such as acetone, methyl ethyl ketone, γ-butyrolactone, and cyclohexanone, dimethylacetamide, N-methylpyrrolidone, and propylene glycol monoethyl. Polar solvents such as ether and hydrocarbon solvents such as toluene and tetradecane can be used.
本発明においては、銅酸化物皮膜により酸化が抑えられるため前記分散液の調製に際し、分散剤や保護剤（表面処理剤）を使用しなくても導体層の形成に際し生成した銅粒子が酸化されることはない。従って、酸化防止のための分散剤や保護剤は必要としないが、本発明の効果を損なわない範囲で、分散安定性の向上などのために使用するのは差し支えない。 In the present invention, since the oxidation is suppressed by the copper oxide film, the copper particles generated during the formation of the conductor layer are oxidized without using a dispersant or a protective agent (surface treatment agent) when preparing the dispersion. Never happen. Therefore, a dispersant and a protective agent for preventing oxidation are not required, but they can be used for improving dispersion stability and the like within a range not impairing the effects of the present invention.
前記粒子の分散は、超音波分散機、ビーズミルなどのメディア分散機，ホモミキサーやシルバーソン攪拌機などのキャビテーション攪拌装置，アルテマイザーなどの対向衝突法，クレアSS5などの超薄膜高速回転式分散機，自転公転式ミキサなどを用いて行うことができる。 Dispersion of the particles includes ultrasonic dispersers, media dispersers such as bead mills, cavitation stirrers such as homomixers and silverson stirrers, opposed collision methods such as artemizers, ultrathin high-speed rotary dispersers such as Claire SS5, This can be done using a rotating / revolving mixer.
前記分散液中の前記粒子の濃度は、１〜７０重量％とすることが好ましく、５〜６０重量％とすることがより好ましく、１０〜５０重量％とすることがさらに好ましい。 The concentration of the particles in the dispersion is preferably 1 to 70% by weight, more preferably 5 to 60% by weight, and still more preferably 10 to 50% by weight.
［基板］
本発明の導電性基板の製造方法において使用される基板として、具体的には、ポリイミド、ポリエチレンナフレタート、ポリエーテルスルホン、ポリエチレンテレフタレート、ポリアミドイミド、ポリエーテルエーテルケトン、ポリカーボネート、液晶ポリマー、エポキシ樹脂、フェノール樹脂、シアネートエステル樹脂、繊維強化樹脂、無機粒子充填樹脂，ポリオレフィン、ポリアミド、ポリフェニレンスルフィド、ポリプロピレン，架橋ポリビニル樹脂、ガラス、セラミックス等からなるフィルム、シート、板が挙げられる。
なお、本発明においては、比較的低温での焼結を可能としているため、耐熱性が低い基板を使用することができるなど、使用する基板の制約が少ない。
[substrate]
Specifically, as a substrate used in the method for producing a conductive substrate of the present invention, polyimide, polyethylene naphthalate, polyethersulfone, polyethylene terephthalate, polyamideimide, polyetheretherketone, polycarbonate, liquid crystal polymer, epoxy resin, Examples thereof include films, sheets, and plates made of phenol resin, cyanate ester resin, fiber reinforced resin, inorganic particle filling resin, polyolefin, polyamide, polyphenylene sulfide, polypropylene, cross-linked polyvinyl resin, glass, ceramics, and the like.
In the present invention, since sintering at a relatively low temperature is possible, there are few restrictions on the substrate to be used, for example, a substrate having low heat resistance can be used.
［還元性液体］
本発明に用いられる還元性液体としては、酸化銅を還元し得る液体で、かつ銅の焼結温度よりも沸点が高い液体であればよく、例えば、一級あるいは二級水酸基を有する有機化合物、フェノール基を有する化合物、水素化珪素基を有する液状の有機化合物、１級あるいは２級アミノ基を有する有機化合物、亜リン酸化合物、ヒドラジン化合物があげられる。また、これらの化合物あるいは固体の還元性物質を混ぜた高沸点溶媒でもよい。水酸基を有する有機溶媒としては、グリセリン、エチレングリコール、プロパンジオール，ブタノール，ブタンジオールなどが好ましい。また，還元性物質としては，アスコルビン酸、クエン酸、亜リン酸塩、スズ(II)化合物、水素化ホウ素化合物、水素化珪素化合物、水素化アルミニウム化合物、有機アルミニウムがあげられる。
[Reducing liquid]
The reducing liquid used in the present invention may be any liquid capable of reducing copper oxide and having a boiling point higher than the sintering temperature of copper. For example, an organic compound having a primary or secondary hydroxyl group, phenol A compound having a group, a liquid organic compound having a silicon hydride group, an organic compound having a primary or secondary amino group, a phosphorous acid compound, and a hydrazine compound. Further, a high boiling point solvent in which these compounds or a solid reducing substance is mixed may be used. As the organic solvent having a hydroxyl group, glycerin, ethylene glycol, propanediol, butanol, butanediol and the like are preferable. Examples of the reducing substance include ascorbic acid, citric acid, phosphite, tin (II) compound, borohydride compound, silicon hydride compound, aluminum hydride compound, and organic aluminum.
次に、本発明の導電性基板の製造方法の手順、及び各工程における操作の詳細について順次説明する。 Next, the procedure of the method for manufacturing the conductive substrate of the present invention and the details of the operation in each step will be described in order.
〈塗布乾燥膜の成膜〉
塗布乾燥膜の成膜は、銅／酸化銅コアシェル粒子又は酸化銅粒子を含む既述の分散液を塗布液として基板表面に塗布し、得られた塗布膜を乾燥することにより行うことができる。塗布液の塗布は、バーコーター、カンマコータ、ダイコータ、スリットコータ、グラビアコータ，インクジェットコータなどを用いて行うことができる。塗布膜厚は、０．０１〜１００μｍとすることが好ましく、０．１〜５０μｍとすることがより好ましく、０．１〜１０μｍとすることがさらに好ましい。塗布膜の乾燥は、用いた分散媒や塗布膜厚に依存するが，例えば、塗布膜が形成された基板をホットプレート上にて、８０〜１５０℃で、５〜３０分間載置することにより行うことができる。その他、周知の乾燥手段を採用することができる。この際、銅／酸化銅コアシェル粒子及び酸化銅粒子のいずれも、表面が酸化銅であるため金属銅粒子のように酸素を除いた雰囲気で乾燥する必要はない。
<Deposition of coated and dried film>
The coating / drying film can be formed by applying the above-described dispersion containing copper / copper oxide core-shell particles or copper oxide particles as a coating liquid to the substrate surface and drying the obtained coating film. The coating liquid can be applied using a bar coater, a comma coater, a die coater, a slit coater, a gravure coater, an ink jet coater, or the like. The coating thickness is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and still more preferably 0.1 to 10 μm. The drying of the coating film depends on the dispersion medium used and the coating film thickness. For example, the substrate on which the coating film is formed is placed on a hot plate at 80 to 150 ° C. for 5 to 30 minutes. It can be carried out. In addition, a known drying means can be employed. At this time, both the copper / copper oxide core-shell particles and the copper oxide particles need not be dried in an atmosphere excluding oxygen as in the case of metal copper particles because the surface is copper oxide.
以上のようにして成膜された塗布乾燥膜は、高周波誘導加熱燃焼−赤外線吸収法による炭素分測定における炭素分が３ｍａｓｓ％以下であることが好ましい。つまり、当該塗布乾燥膜に炭素分が含まれるとすれば、それは分散剤や保護剤由来の炭素分であるが、塗布液調製において分散剤や保護剤を必要以上に使用しないという観点から塗布乾燥膜中の炭素分はその程度の含有量であることが好ましい。 The coated and dried film formed as described above preferably has a carbon content of 3 mass% or less in the carbon content measurement by high-frequency induction heating combustion-infrared absorption method. In other words, if carbon content is included in the coating and drying film, it is carbon content derived from the dispersant and the protective agent, but coating and drying from the viewpoint that the dispersant and the protective agent are not used more than necessary in the preparation of the coating liquid. The carbon content in the film is preferably such a content.
塗布乾燥膜を成膜後は、第１の態様と第２の態様とで工程が異なる。具体的には、第１の態様と第２の態様とでは、還元性液体を加熱するタイミングが異なり、第１の態様では焼結する工程の直前から加熱するのに対し、第２の態様では塗布乾燥膜を浸漬する前に焼結温度まで加熱する。以下にまず、第１の態様について説明する。 After the coating and drying film is formed, the process differs between the first aspect and the second aspect. Specifically, the timing at which the reducing liquid is heated is different between the first aspect and the second aspect. In the first aspect, the heating is performed immediately before the sintering step, whereas in the second aspect, Heat to the sintering temperature before dipping the coated dry film. First, the first aspect will be described.
〈塗布乾燥膜の還元性液体への浸漬〉
第１の態様では、上述の工程により塗布乾燥膜が成膜された基板を還元性液体に浸漬する。還元性液体への浸漬により、塗布乾燥膜中の銅／酸化銅コアシェル粒子又は酸化銅粒子の酸化銅が還元されて銅粒子となる。上述のように、この状態での還元性液体は非加熱であるが、還元反応の進行を促進させる目的で適宜加熱してもよい。この場合の還元性液体の温度は、室温〜２００℃とすることが好ましく、その温度の保持時間は、処理する粒子層の厚さや基板の熱容量，還元剤，温度により異なるが，１０秒〜６０分とすることが好ましい。
<Immersion of coated dry film in reducing liquid>
In the first aspect, the substrate on which the coating dry film has been formed by the above-described process is immersed in a reducing liquid. By immersion in the reducing liquid, the copper / copper oxide core-shell particles or the copper oxide particles of the copper oxide particles in the dried coating film are reduced to copper particles. As described above, the reducing liquid in this state is not heated, but may be appropriately heated for the purpose of promoting the progress of the reduction reaction. In this case, the temperature of the reducing liquid is preferably room temperature to 200 ° C., and the holding time of the temperature varies depending on the thickness of the particle layer to be processed, the heat capacity of the substrate, the reducing agent, and the temperature, but is 10 seconds to 60 seconds. Minutes are preferred.
〈焼結〉
一定時間経過し、還元反応がある程度進行したものと認められたら、前記基板を還元性液体に浸漬させたままの状態で、還元性液体を銅粒子同士が焼結し得る温度（以下、「焼結温度」と称する。）まで加熱し、この焼結温度を一定時間維持する。このように、塗布乾燥膜を焼結温度まで加熱・維持することにより生成した銅粒子同士が焼結し導体化し全体として導体層をなす。
焼結温度としては、１２０〜３００℃とすることが好ましく、１３０〜２５０℃とすることがより好ましく、１４０〜２００℃とすることがさらに好ましい。また、焼結時間は、処理する粒子層の厚さや基板の熱容量，温度により異なるが、例えば０．５〜６０分とすることが好ましく、２〜２０分とすることがより好ましい。
<Sintering>
When it is recognized that the reduction reaction has progressed to some extent after a certain period of time, the temperature at which the reducing particles can sinter the copper particles with the substrate immersed in the reducing liquid (hereinafter referred to as “firing”). The sintering temperature is referred to as "condensation temperature") and this sintering temperature is maintained for a certain period of time. Thus, the copper particles produced | generated by heating and maintaining an application | coating dry film to sintering temperature sinter, make it into a conductor, and make a conductor layer as a whole.
The sintering temperature is preferably 120 to 300 ° C, more preferably 130 to 250 ° C, and further preferably 140 to 200 ° C. Moreover, although sintering time changes with the thickness of the particle layer to process, the heat capacity of a board | substrate, and temperature, it is preferable to set it as 0.5 to 60 minutes, for example, and it is more preferable to set it as 2 to 20 minutes.
一方、第２の態様では、上述のように、予め焼結温度まで加熱した還元性液体に塗布乾燥膜が形成された基板を浸漬する。ここでの焼結温度は第１の態様で説明した温度と同様である。また、浸漬時間は維持する温度によっても異なるが、例えば、１〜６０分とすることが好ましく、２〜２０分とすることがより好ましい。 On the other hand, in the second aspect, as described above, the substrate on which the dried coating film is formed is immersed in a reducing liquid that has been heated to a sintering temperature in advance. The sintering temperature here is the same as the temperature described in the first embodiment. Moreover, although immersion time changes also with the temperature to maintain, it is preferable to set it as 1 to 60 minutes, for example, and it is more preferable to set it as 2 to 20 minutes.
焼結後、導体層が形成された基板は、第１の態様及び第２の態様のいずれにおいても、超純水等にさらした後、アセトン等をかけて乾燥することができる。
以上のようにして、いずれの態様においても低抵抗の銅の導体層を有する導電性基板を製造することができる。
After sintering, the substrate on which the conductor layer is formed can be dried by applying acetone or the like after being exposed to ultrapure water or the like in both the first and second embodiments.
As described above, a conductive substrate having a low-resistance copper conductor layer can be manufactured in any aspect.
＜銅配線基板の製造方法＞
次に、本発明の銅配線基板の製造方法について説明する。
本発明の銅配線基板の製造方法は、第１の態様によると、基板上に、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子、又は酸化銅粒子を含む塗布液を用いて任意の配線パターンを描画する工程と、描画した塗布液による配線パターンを乾燥後、還元性液体に浸漬し、前記配線パターン中に含まれる各粒子の酸化銅を銅に還元する工程と、前記還元性液体を加熱して、還元されて得られた銅粒子同士を焼結し、銅配線とする工程と、を含むことを特徴とする。
<Copper wiring board manufacturing method>
Next, the manufacturing method of the copper wiring board of this invention is demonstrated.
According to the first aspect of the method for manufacturing a copper wiring board of the present invention, the substrate includes particles having a core / shell structure in which the core part is copper and the shell part is copper oxide, or copper oxide particles. A step of drawing an arbitrary wiring pattern using a coating solution, and a wiring pattern formed by the drawn coating solution is dried and then immersed in a reducing liquid to reduce the copper oxide of each particle contained in the wiring pattern to copper. And a step of heating the reducing liquid to sinter the copper particles obtained by reduction to form a copper wiring.
本発明の銅配線基板の製造方法は、第２の態様によると、基板上に、コア部が銅であり、シェル部が酸化銅であるコア／シェル構造を有する粒子、又は酸化銅粒子を含む塗布液を用いて任意の配線パターンを描画する工程と、描画した塗布液による配線パターンを乾燥後、銅粒子同士が焼結し得る温度まで加熱した還元性液体に浸漬し、前記配線パターン中に含まれる各粒子の酸化銅を銅に還元し、還元されて得られた銅粒子同士を焼結し、銅配線とする工程と、を含むことを特徴とする。 According to the second aspect, the method for producing a copper wiring board of the present invention includes particles having a core / shell structure in which the core portion is copper and the shell portion is copper oxide, or copper oxide particles on the substrate. A process of drawing an arbitrary wiring pattern using a coating liquid, and after drying the wiring pattern with the drawn coating liquid, it is immersed in a reducing liquid heated to a temperature at which copper particles can be sintered together, A step of reducing the copper oxide of each particle contained therein to copper and sintering the resulting copper particles to form a copper wiring.
本発明の銅配線基板の製造方法において、第１の態様と第２の態様とで、銅／酸化銅コアシェル粒子、又は酸化銅粒子を含む塗布液を用いて任意の配線パターンを描画する工程は共通する。以下にまず、当該工程について説明する。 In the method for producing a copper wiring board according to the present invention, in the first aspect and the second aspect, a step of drawing an arbitrary wiring pattern using a coating solution containing copper / copper oxide core-shell particles or copper oxide particles is provided. Common. First, the process will be described below.
［塗布液］
銅／酸化銅コアシェル粒子、又は酸化銅粒子を含む塗布液は、これらの粒子を既述の分散媒に分散させることにより得ることができる。当該粒子は、既述の本発明の導電性基板の製造方法において使用する銅／酸化銅コアシェル粒子、又は酸化銅粒子と同様であるが、一次粒子の数平均粒子径は、配線の微細化や後述する各塗布装置への適用を考慮し、１００ｎｍ以下のものを用いることが好ましい。
また、前記塗布液中の前記粒子の濃度は、１〜７０重量％とすることが好ましく、５〜６０重量％とすることがより好ましく、１０〜５０重量％とすることがさらに好ましい。
[Coating solution]
The coating liquid containing copper / copper oxide core-shell particles or copper oxide particles can be obtained by dispersing these particles in the aforementioned dispersion medium. The particles are the same as the copper / copper oxide core-shell particles or the copper oxide particles used in the above-described method for producing a conductive substrate of the present invention. In consideration of application to each coating apparatus described later, it is preferable to use one having a thickness of 100 nm or less.
The concentration of the particles in the coating solution is preferably 1 to 70% by weight, more preferably 5 to 60% by weight, and still more preferably 10 to 50% by weight.
〈配線パターンの描画〉
前記塗布液を基板上に任意の配線パターンを描画する手法としては、従来からインクを塗布するのに用いられている印刷あるいは塗工を利用することができる。配線パターンを描画するには、前記塗布液を用い、スクリーン印刷、ジェットプリンティング法、インクジェット印刷、転写印刷、オフセット印刷、ディスペンサを用いることができる。
<Drawing of wiring pattern>
As a method for drawing an arbitrary wiring pattern on the substrate using the coating solution, printing or coating conventionally used for applying ink can be used. In order to draw the wiring pattern, the coating liquid can be used, and screen printing, jet printing, ink jet printing, transfer printing, offset printing, and dispenser can be used.
前記塗布液を用い、配線パターンの描画を終えた後、分散媒の揮発性にあわせた温度で乾燥を行う。この際、銅／酸化銅コアシェル粒子及び酸化銅粒子のいずれも、表面が酸化銅であるため金属銅粒子のように酸素を除いた雰囲気で乾燥する必要はない。 After drawing the wiring pattern using the coating solution, drying is performed at a temperature that matches the volatility of the dispersion medium. At this time, both the copper / copper oxide core-shell particles and the copper oxide particles need not be dried in an atmosphere excluding oxygen as in the case of metal copper particles because the surface is copper oxide.
以上のようにして配線パターンの描画後は、第１の態様においては、既述の本発明の導電性基板の製造方法の第１の態様と同様にして、塗布液による配線パターンが描画された基板（乾燥後）を還元性液体に浸漬し、加熱し、焼結することにより、銅／酸化銅コアシェル粒子又は酸化銅粒子を含む配線パターン中の酸化銅が金属銅に変化し導体化して、銅配線パターンが形成される。
一方、第２の態様においては、既述の本発明の導電性基板の製造方法の第２の態様と同様にして、塗布液による配線パターンが描画された基板（乾燥後）を、予め加熱された還元性液体に浸漬し、還元、焼結することにより、銅／酸化銅コアシェル粒子及び酸化銅粒子を含む配線パターン中の酸化銅が金属銅に変化し導体化し、銅配線パターンが形成される。
なお、配線パターン描画後の工程は、第１の態様、第２の態様のそれぞれにおいて、既述の本発明の導電性基板の製造方法の第１の態様、第２の態様と実質的に同様であるため詳細な説明は省略する。既述の本発明の導電性基板の製造方法の説明において、「塗布乾燥膜が成膜された基板」は、本発明の銅配線基板の製造方法において「配線パターンが描画された基板」に相当し、「塗布乾燥膜」は「配線パターン」に相当する。
After the wiring pattern is drawn as described above, in the first mode, the wiring pattern by the coating liquid is drawn in the same manner as the first mode of the method for manufacturing the conductive substrate of the present invention described above. By immersing the substrate (after drying) in a reducing liquid, heating, and sintering, the copper oxide in the wiring pattern including the copper / copper oxide core-shell particles or the copper oxide particles is converted into metal copper to be a conductor, A copper wiring pattern is formed.
On the other hand, in the second aspect, the substrate (after drying) on which the wiring pattern by the coating liquid is drawn is heated in advance in the same manner as the second aspect of the conductive substrate manufacturing method of the present invention described above. The copper oxide in the wiring pattern containing copper / copper oxide core-shell particles and copper oxide particles is converted to metal copper to become a conductor by dipping in a reducing liquid, reducing, and sintering to form a copper wiring pattern. .
In addition, the process after drawing the wiring pattern is substantially the same as the first aspect and the second aspect of the manufacturing method of the conductive substrate of the present invention described above in each of the first aspect and the second aspect. Therefore, detailed description is omitted. In the description of the method for manufacturing a conductive substrate of the present invention described above, “the substrate on which the coating dry film is formed” corresponds to “the substrate on which the wiring pattern is drawn” in the method for manufacturing the copper wiring substrate of the present invention. The “coating dry film” corresponds to a “wiring pattern”.
本発明の銅配線基板の製造方法において使用される基板の材質として、具体的には、ポリイミド、ポリエチレンナフタレート、ポリエーテルスルホン、ポリエチレンテレフタレート、ポリアミドイミド、ポリエーテルエーテルケトン、ポリカーボネート、液晶ポリマー、エポキシ樹脂、フェノール樹脂、シアネートエステル樹脂、繊維強化樹脂、粒子充填樹脂、ポリオレフィン、ポリアミド、ポリフェニレンスルフィド、架橋ポリビニル樹脂、ガラス、セラミックス等が挙げられる。
なお、本発明においては、比較的低温での焼結を可能としているため、耐熱性が低い基板を使用することができるなど、使用する基板の制約が少ない。
Specifically, as a substrate material used in the method for producing a copper wiring board of the present invention, polyimide, polyethylene naphthalate, polyethersulfone, polyethylene terephthalate, polyamideimide, polyetheretherketone, polycarbonate, liquid crystal polymer, epoxy Resins, phenol resins, cyanate ester resins, fiber reinforced resins, particle-filled resins, polyolefins, polyamides, polyphenylene sulfide, cross-linked polyvinyl resins, glass, ceramics, and the like.
In the present invention, since sintering at a relatively low temperature is possible, there are few restrictions on the substrate to be used, for example, a substrate having low heat resistance can be used.
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
［実施例１］
（銅ナノ粒子塗布基板の作製）
保護剤を用いず、銅／酸化銅コアシェル粒子（数平均粒径４１ｎｍ、日清エンジニアリング製）をγ−ブチロラクトンに３０重量％となるように混合し、超音波洗浄機にかけて分散し分散液を得た。この分散液を図１の銅箔パターン（図１においてハッチング部分）を有するポリイミド基板（日立化成工業（株）製、ＭＣＦ−５０００ｌ）１０上にバーコーターを用いて塗布し、ホットプレート上で空気中、１００℃１０分の条件で塗布膜を乾燥して塗布乾燥膜とし、銅ナノ粒子塗布基板を作製した。
[Example 1]
(Preparation of copper nanoparticle coated substrate)
Without using a protective agent, copper / copper oxide core-shell particles (number average particle size 41 nm, manufactured by Nissin Engineering Co., Ltd.) were mixed with γ-butyrolactone so as to be 30% by weight, and dispersed with an ultrasonic cleaner to obtain a dispersion. It was. This dispersion was applied on a polyimide substrate (manufactured by Hitachi Chemical Co., Ltd., MCF-5000l) 10 having a copper foil pattern (hatched portion in FIG. 1) using a bar coater, and air on a hot plate. Inside, the coating film was dried at 100 ° C. for 10 minutes to form a coating dry film, and a copper nanoparticle coated substrate was produced.
（導体層の形成）
次に、あらかじめホットプレート上で加熱した、グリセリン（還元性液体）が満たされた容器の中に、銅ナノ粒子塗布基板を沈めて３０分処理を行った。処理温度は処理中のグリセリン温度を熱電対式温度計（ＴＸ１００３、横河メータ＆インスツルメント製）にて測定した。その後、超純水に５分さらした後、アセトンをかけて乾燥した。この処理の結果、１２０℃以上の温度で赤銅色への変色が生じ、特に１４０℃以上で処理した場合には全体が明るい銅色になった。この処理により銅粒子層は導体層となった。図１の１ｍｍ、５ｍｍそれぞれのギャップを有する電極間における抵抗を４探針法微小抵抗測定装置（Ｌｏｒｅｓｔａ ＭＣＰ−Ｔ６１０、三菱化学（株）製）にて測定し、ＦＩＢ／ＳＩＭ断面観察で求めた層厚を用いて体積抵抗率を求めた。処理前には導通はなかったが、グリセリン中で加熱処理したサンプルすべてで導通が見られ、特に、１４０℃で処理した銅粒子層の体積抵抗率は５．３×１０−７Ω・ｍに達した。１４０℃以上で処理した場合には、１０−７Ω・ｍ以下の体積抵抗率になった。
グリセリン中で加熱処理した銅粒子層（導体層）をＦＩＢにて加工し断面のＳＩＭ観察を行った。その結果を図３に示す。１４０℃で処理した場合（図３（ｂ））、焼結前の粒子（図２）の高次構造が１００ｎｍ程度の構造からなっているのに対し、５００ｎｍ近い構造からなっており、さらにその構造が連続体となっていることが分かった。
図４には、図１に示す２ｍｍギャップの銅箔パターンにおける銅粒子層を１２０℃、１４０℃、１６０℃、１８０℃の各焼結温度にて焼結させた場合のそれぞれの体積抵抗率をグラフで示す。図４より、１４０℃以上の焼結温度で焼結させた場合に、低抵抗の導体層が得られたことが分かる。
(Formation of conductor layer)
Next, the copper nanoparticle-coated substrate was submerged in a container filled with glycerin (reducing liquid) that had been heated on a hot plate in advance, and the treatment was performed for 30 minutes. The treatment temperature was determined by measuring the glycerin temperature during treatment with a thermocouple thermometer (TX1003, manufactured by Yokogawa Meter & Instruments). Thereafter, it was exposed to ultrapure water for 5 minutes and then dried with acetone. As a result of this treatment, discoloration to a bronze color occurred at a temperature of 120 ° C. or higher, and in particular when treated at 140 ° C. or higher, the whole became a bright copper color. By this treatment, the copper particle layer became a conductor layer. The resistance between electrodes having gaps of 1 mm and 5 mm in FIG. 1 was measured with a 4-probe microresistance measuring device (Loresta MCP-T610, manufactured by Mitsubishi Chemical Corporation), and obtained by FIB / SIM cross-sectional observation. The volume resistivity was determined using the layer thickness. There was no conduction before treatment, but conduction was observed in all the samples heat-treated in glycerin, and in particular, the volume resistivity of the copper particle layer treated at 140 ° C. was 5.3 × 10 −7 Ω · m. Reached. When treated at 140 ° C. or higher, the volume resistivity was 10 −7 Ω · m or lower.
The copper particle layer (conductor layer) heat-treated in glycerin was processed with FIB, and SIM observation of the cross section was performed. The result is shown in FIG. When treated at 140 ° C. (FIG. 3B), the higher order structure of the particles before sintering (FIG. 2) is about 100 nm, whereas the structure is close to 500 nm. It was found that the structure was a continuum.
FIG. 4 shows the respective volume resistivity when the copper particle layer in the copper foil pattern of 2 mm gap shown in FIG. 1 is sintered at each sintering temperature of 120 ° C., 140 ° C., 160 ° C., and 180 ° C. Shown in the graph. FIG. 4 shows that a low-resistance conductor layer was obtained when sintered at a sintering temperature of 140 ° C. or higher.
［実施例２］
実施例１において作製した銅ナノ粒子塗布基板を予めホットプレート上で加熱した、エチレングリコール（還元性液体）が満たされた容器の中に沈めて３０分処理を行った。処理温度は処理中のエチレングリコールの温度を熱電対式温度計にて測定した。その後、超純水に５分さらした後、アセトンをかけて乾燥した。この処理により、銅粒子層は銅色になった。図１の１ｍｍ、２ｍｍ、５ｍｍそれぞれのギャップを有する電極間における抵抗は０Ω、０Ω、０Ωとなり導通が認められた。
[Example 2]
The copper nanoparticle-coated substrate prepared in Example 1 was submerged in a container filled with ethylene glycol (reducing liquid) heated in advance on a hot plate for 30 minutes. The treatment temperature was determined by measuring the temperature of ethylene glycol during treatment with a thermocouple thermometer. Thereafter, it was exposed to ultrapure water for 5 minutes and then dried with acetone. By this treatment, the copper particle layer became copper color. Resistance between electrodes having gaps of 1 mm, 2 mm, and 5 mm in FIG. 1 was 0Ω, 0Ω, and 0Ω, and conduction was recognized.
［実施例３］
酸化銅ナノ粒子（数平均粒径５０ｎｍ、シーアイ化成製）をγ−ブチロラクトンに２０重量％混合し、超音波洗浄機にかけて分散して分散液を得た。この分散液を図１の銅箔パターンを有するポリイミド基板（ＭＣＦ−５０００ｌ）上にバーコーターを用いて塗布し、ホットプレート上に１００℃１０分乾燥して、酸化銅粒子塗布基板を作製した。
[Example 3]
Copper oxide nanoparticles (number average particle size 50 nm, manufactured by C.I. Kasei Co., Ltd.) were mixed with γ-butyrolactone in an amount of 20% by weight and dispersed with an ultrasonic cleaner to obtain a dispersion. This dispersion was applied on a polyimide substrate (MCF-5000 l) having a copper foil pattern of FIG. 1 using a bar coater, and dried on a hot plate at 100 ° C. for 10 minutes to prepare a copper oxide particle-coated substrate.
次に、あらかじめホットプレート上で１６０℃に加熱した、グリセリン（還元性液体）が満たされた容器の中に酸化銅粒子塗布基板を沈めて３０分処理を行った。処理温度は処理中のグリセリン温度を熱電対式温度計（ＴＸ１００３、横河メータ＆インスツルメント製）にて測定した。その後、超純水に５分さらした後、アセトンをかけて乾燥した。ただし、洗浄操作において粒子の一部の流失が見られた。この処理により、銅粒子層は銅色になった。図１の１ｍｍ、２ｍｍ、５ｍｍそれぞれのギャップを有する電極間における抵抗は、１０ＭΩ、２５ＭΩ、２８ＭΩとなり導通が認められた。 Next, the copper oxide particle-coated substrate was submerged in a container filled with glycerin (reducing liquid), which had been heated to 160 ° C. on a hot plate in advance, and then treated for 30 minutes. The treatment temperature was determined by measuring the glycerin temperature during treatment with a thermocouple thermometer (TX1003, manufactured by Yokogawa Meter & Instruments). Thereafter, it was exposed to ultrapure water for 5 minutes and then dried with acetone. However, some particles were washed away in the washing operation. By this treatment, the copper particle layer became copper color. Resistance between electrodes having 1 mm, 2 mm, and 5 mm gaps in FIG. 1 was 10 MΩ, 25 MΩ, and 28 MΩ, and conduction was recognized.
［比較例１］
保護剤を有する銅ナノ粒子として、銅ナノ粒子の３０質量％トルエン分散液（Ｃｕ１Ｔ，アルバック製）を図１の銅箔パターンを有するポリイミド基板（ＭＣＦ−５０００））上にバーコーターを用いて塗布し、ホットプレート上で、窒素気流下１００℃１０分乾燥して、銅粒子の堆積膜を有する基板を作製した。あらかじめホットプレート上で１６０℃に加熱した、グリセリン（還元性液体）が満たされた容器の中に該基板を沈めて３０分間処理を行った。処理温度は処理中のグリセリン温度を熱電対式温度計にて測定した。その後、超純水に５分さらした後、アセトンをかけて乾燥した。該処理により銅粒子層は光沢のない銅色に変色したが、図１に示す電極いずれにおいても抵抗はテスターの測定限界以上、すなわち導通はなかった。
[Comparative Example 1]
As copper nanoparticles having a protective agent, a 30% by mass toluene dispersion of copper nanoparticles (Cu1T, manufactured by ULVAC) is applied on a polyimide substrate (MCF-5000) having the copper foil pattern of FIG. 1 using a bar coater. Then, the substrate was dried at 100 ° C. for 10 minutes under a nitrogen stream on a hot plate to prepare a substrate having a deposited film of copper particles. The substrate was submerged in a container filled with glycerin (reducing liquid), which had been heated to 160 ° C. in advance on a hot plate, and was treated for 30 minutes. The treatment temperature was determined by measuring the glycerin temperature during the treatment with a thermocouple thermometer. Thereafter, it was exposed to ultrapure water for 5 minutes and then dried with acetone. Although the copper particle layer was discolored to a dull copper color by this treatment, the resistance was not less than the tester's measurement limit in any of the electrodes shown in FIG.
以上の実施例１〜３、及び比較例１の結果を表１、表２に示す。 The results of Examples 1 to 3 and Comparative Example 1 are shown in Tables 1 and 2.
表１より、焼結温度が１４０℃以上で低抵抗の導体層となったことが分かる。
また表２より、銅／酸化銅コアシェル粒子を用いて導体層を形成した実施例２、酸化銅粒子を用いて導体層を形成した実施例３のいずれの場合でも低抵抗の導体層が得られたのに対し、保護剤とともに銅ナノ粒子を用いて層を形成した比較例１は導通すら認められなかった。
It can be seen from Table 1 that a low resistance conductor layer was obtained at a sintering temperature of 140 ° C. or higher.
Further, from Table 2, a low resistance conductor layer can be obtained in any of Example 2 in which a conductor layer was formed using copper / copper oxide core-shell particles and Example 3 in which a conductor layer was formed using copper oxide particles. In contrast, Comparative Example 1 in which the layer was formed using copper nanoparticles together with the protective agent was not even conducted.
１０ 基板 10 Substrate
Claims (12)
前記還元性液体を加熱して、還元されて得られた銅粒子同士を焼結する工程と、
を含むことを特徴とする導電性基板の製造方法。 Each of the particles contained in the coating / drying film is obtained by immersing a substrate on which a coating / drying film containing particles having a core / shell structure in which the core part is copper and the shell part is copper oxide in a reducing liquid. Reducing the copper oxide to copper,
Heating the reducing liquid and sintering the copper particles obtained by reduction; and
The manufacturing method of the electroconductive board | substrate characterized by the above-mentioned.
描画した塗布液による配線パターンを乾燥後、還元性液体に浸漬し、前記配線パターン中に含まれる各粒子の酸化銅を銅に還元する工程と、
前記還元性液体を加熱して、還元されて得られた銅粒子同士を焼結し、銅配線とする工程と、を含むことを特徴とする銅配線基板の製造方法。 A step of drawing an arbitrary wiring pattern on the substrate using a coating liquid containing particles having a core / shell structure in which the core part is copper and the shell part is copper oxide;
After drying the drawn wiring pattern with the coating solution, immersing in a reducing liquid, reducing the copper oxide of each particle contained in the wiring pattern to copper,
And heating the reducing liquid to sinter the copper particles obtained by reduction to form a copper wiring.
描画した塗布液による配線パターンを乾燥後、銅粒子同士が焼結し得る温度まで加熱した還元性液体に浸漬し、前記配線パターン中に含まれる各粒子の酸化銅を銅に還元し、還元されて得られた銅粒子同士を焼結し、銅配線とする工程と、を含むことを特徴とする銅配線基板の製造方法。 A step of drawing an arbitrary wiring pattern on the substrate using a coating liquid containing particles having a core / shell structure in which the core part is copper and the shell part is copper oxide;
After the wiring pattern with the drawn coating solution is dried, it is immersed in a reducing liquid heated to a temperature at which the copper particles can sinter, and the copper oxide of each particle contained in the wiring pattern is reduced to copper and reduced. And a step of sintering the copper particles obtained in this way to form a copper wiring.
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