JP4762582B2 - 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 - Google Patents
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 Download PDFInfo
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- JP4762582B2 JP4762582B2 JP2005082082A JP2005082082A JP4762582B2 JP 4762582 B2 JP4762582 B2 JP 4762582B2 JP 2005082082 A JP2005082082 A JP 2005082082A JP 2005082082 A JP2005082082 A JP 2005082082A JP 4762582 B2 JP4762582 B2 JP 4762582B2
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Description
本発明はプリント配線基板や基板等の電子実装部品製造における、導電部品（導電路、バンプ等）立体金属配線パターン、アンテナパターン、熱伝導路及び触媒電極及びその形成方法、及び前記製品を製造する時に用いる金属酸化物粒子還元・相互融着するための金属酸化物粒子の焼成用材料に関する。 The present invention manufactures conductive parts (conductive paths, bumps, etc.) three-dimensional metal wiring patterns, antenna patterns, heat conduction paths and catalyst electrodes, methods for forming the same, and the products in the manufacture of electronic mounting parts such as printed wiring boards and substrates. The present invention relates to a material for firing metal oxide particles used for reduction and mutual fusion of metal oxide particles.
金属（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の近年の著しい発展に伴い、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。 With the recent remarkable development of fine wiring patterning technology by metal (metal oxide) fine particle manufacturing technology, independent dispersion technology, ultra-micro inkjet, precision screen printing, nanoprinting and nanoimprinting, these technologies are applied. The direct circuit drawing method has attracted a great deal of attention as a next-generation electronic packaging 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（金属酸化物）粒子の直接描画→焼成→相互融着→導電化によって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となると期待される。さらに、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。
In this direct circuit drawing method, an electronic packaging component that has been manufactured through complicated processes such as lithography and etching is manufactured by direct drawing of metal (metal oxide) particles → firing → mutual fusion → conducting. The details are described on page 71 of Non-Patent
この直接回路描画法の重要な工程の一つに、金属（金属酸化物）粒子をパターニングした回路基板を熱処理し、金属粒子を相互融着（金属酸化物粒子を還元後に相互融着）させ、それら粒子によって構成された回路パターンを導電化する工程がある。 One of the important steps of this direct circuit drawing method is to heat-treat the circuit board patterned with metal (metal oxide) particles, to bond the metal particles together (mutual fusion after reducing the metal oxide particles), There is a step of making a circuit pattern constituted by these particles conductive.
これまでに提案されている直接回路描画法においては、この粒子を相互融着させる熱処理工程に、熱風やスチームもしくは電熱線を用いた抵抗加熱炉によって、金属（金属酸化物）粒子によって構成された回路パターン部分と下地基板部分の実装部品全体を、１５０℃から２１０℃で加熱処理することが特許文献１に、また同じく実装部品全体を１５０℃で加熱処理することが特許文献２に記載されている。
In the direct circuit drawing method that has been proposed so far, the heat treatment step for mutual fusion of the particles is composed of metal (metal oxide) particles by a resistance heating furnace using hot air, steam, or heating wire.
しかしながら、この従来提案されていた熱処理方法では、粒子によって構成された回路パターンと共に下地基板部分も同等に等しく加熱されるため、使用可能な下地基板がこの熱処理時の保持温度よりも耐熱温度の高い材料に限定されるという問題があった。特に次世代の超高速電子デバイスにおいて不可欠な低抵抗の電子実装部品を作成する場合、この熱処理条件を高温・長時間に設定する必要があり、その意味で使用可能な基板材料は大きく限定されるものであった。
さらに、この従来提案されていた熱処理方法では、加熱に少なくとも数十分の時間を要し、生産性も低いことなどが特許文献１の実施例に記載されている。
However, in this conventionally proposed heat treatment method, since the base substrate portion is heated equally and together with the circuit pattern constituted by the particles, the usable base substrate has a heat resistant temperature higher than the holding temperature during this heat treatment. There was a problem that it was limited to materials. Especially when creating electronic components with low resistance, which are indispensable for next-generation ultra-high-speed electronic devices, it is necessary to set the heat treatment conditions at high temperature and long time. In this sense, usable substrate materials are greatly limited. It was a thing.
Furthermore, in the example of
また特に酸化物粒子の還元・相互融着方法に関しては、特許文献４に還元性気体中でプラズマ照射する方法等が記載されているが、この場合には、高価なプラズマ発生装置が必要であり、また基板上に塗布した酸化物粒子に対して使用した場合には、そのプラズマによって基板材料が劣化する恐れがあることが分かっている。
In particular, with respect to the reduction / mutual fusion method of oxide particles,
また同じく酸化物粒子の還元・相互融着方法としては、特許文献３の技術背景に水素化ホウ素誘導体等の還元剤を酸化銅に添加し熱処理する方法が紹介されているが、この方法で良好な導電性を示す焼結体を構成するためには、４００℃以上の高温加熱が必要であることが言及されている。
Similarly, as a method for reducing and mutually fusing oxide particles, a method of adding a reducing agent such as a borohydride derivative to copper oxide and heat-treating is introduced in the technical background of
さらに特許文献４には、酸化クロム含有酸化物の還元方法等が記載され、酸化クロムにカーボンを添加しマイクロ波照射することで１４００℃以上の高温に加熱し、酸化クロムを還元する方法が記載されている。
Further,
従来、金属酸化物粒子もしくは表面酸化金属粒子又は両者の混合物を含む粒子を用いた直接回路描画法においては、使用可能な下地基板が耐熱温度の高い材料に限定されるとともに、基板の加熱処理に時間がかかり生産性が低いという問題があった。本発明は上記に鑑みてなされたものであり、ガラスエポキシ等の耐熱温度の低い基板上においても、基板を溶融することなくパターンニングされた前記粒子や前記粒子の混合物を還元焼成し、導電性の配線パターンもしくは低抵抗の実装部品を形成することが可能な新しい技術手法を提供するものである。さらに、前記粒子や前記粒子の混合物の還元焼成温度をより低温化する技術をも提供するものである。 Conventionally, in a direct circuit drawing method using metal oxide particles, surface oxide metal particles, or particles containing a mixture of both, usable base substrates are limited to materials having a high heat-resistant temperature, and can be used for substrate heat treatment. There was a problem that it took time and productivity was low. The present invention has been made in view of the above, and even on a substrate having a low heat-resistant temperature such as glass epoxy, the particles and the mixture of the particles that have been patterned without melting the substrate are reduced and fired to obtain a conductive property. A new technical method capable of forming a wiring pattern or a low-resistance mounting component is provided. Furthermore, the present invention also provides a technique for lowering the reduction firing temperature of the particles and the mixture of the particles.
本発明によれば以下の手段が提供される。 According to the present invention, the following means are provided.
（１）金属酸化物粒子及び表面酸化金属粒子の少なくとも一方と電磁波吸収性の優れた焼結助剤との混合物を、基板上に塗布もしくは表面パターンニングした後、不活性雰囲気にて高周波電磁波を照射することで前記粒子を選択的に加熱還元する還元焼成方法であって、(1) After applying or surface patterning a mixture of at least one of metal oxide particles and surface oxidized metal particles and a sintering aid having excellent electromagnetic wave absorbability on a substrate, high-frequency electromagnetic waves are generated in an inert atmosphere. A reduction firing method for selectively heating and reducing the particles by irradiation,
電磁波吸収性の優れた焼結助剤が、カーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）、Ｃｒ Sintering aids with excellent electromagnetic wave absorption are carbon black, carbon nanotubes, carbon fullerene, VGCF (vapor-grown carbon fiber), Cr
２2
ＯO
３3
、ＴｉＯTiO
２2
、ＣｕＯ、ＮｉＯ、Ｃｏ, CuO, NiO, Co
３3
ＯO
４4
、ＭｎＯ, MnO
２2
、α―Ｆｅ, Α-Fe
２2
ＯO
３3
、Ｖ, V
２2
ＯO
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、ＳｎＯ, SnO
２2
、Ｉｎ, In
２2
ＯO
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、ＧｅＯ, GeO
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、ＺｎＯ、ＭｇＯ、及びＳｉＯ, ZnO, MgO, and SiO
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からなる群から選らばれる少なくとも１つであることを特徴とする還元焼成方法。A reduction firing method, wherein the reduction firing method is at least one selected from the group consisting of:
（２）（１）に記載の還元焼成方法を利用することを特徴とした、金属配線パターンの形成方法。(2) A method for forming a metal wiring pattern, wherein the reduction firing method according to (1) is used.
（３）前記高周波電磁波の周波数が１ＭＨｚ＜ｆ＜３００ＧＨｚであることを特徴とする、（２）に記載の金属配線パターンの形成方法。(3) The method for forming a metal wiring pattern according to (2), wherein the frequency of the high-frequency electromagnetic wave is 1 MHz <f <300 GHz.
（４）前記高周波電磁波の周波数が１０ＧＨｚ＜ｆ＜３００ＧＨｚであることを特徴とする、（２）又は（３）に記載の金属配線パターンの形成方法。(4) The method for forming a metal wiring pattern according to (2) or (3), wherein the frequency of the high-frequency electromagnetic wave is 10 GHz <f <300 GHz.
（５）前記金属酸化物粒子が酸化銅、酸化銀粒子、又は酸化ニッケルであることを特徴とする、（２）〜（４）のいずれかに記載の金属配線パターンの形成方法。(5) The method for forming a metal wiring pattern according to any one of (2) to (4), wherein the metal oxide particles are copper oxide, silver oxide particles, or nickel oxide.
（６）前記表面酸化金属粒子が、銅、銀、又はニッケルであることを特徴とする、（２）〜（５）のいずれかに記載の金属配線パターンの形成方法。(6) The method for forming a metal wiring pattern according to any one of (2) to (5), wherein the surface oxidized metal particles are copper, silver, or nickel.
（７）前記金属酸化物粒子もしくは表面酸化金属粒子の平均粒径が１ｎｍ〜１００ｎｍのナノ粒子であることを特徴とする（２）〜（６）のいずれかに記載の金属配線パターンの形成方法。(7) The method for forming a metal wiring pattern according to any one of (2) to (6), wherein the metal oxide particles or the surface oxidized metal particles are nanoparticles having an average particle diameter of 1 nm to 100 nm. .
（８）前記焼結助剤の高周波電磁波吸収性が、前記基板の高周波電磁波吸収性よりも高いことを特徴とする（２）〜（７）のいずれかに記載の金属配線パターンの形成方法。(8) The method for forming a metal wiring pattern according to any one of (2) to (7), wherein the sintering aid has higher radio frequency electromagnetic wave absorbability than the substrate.
（９）前記基板が酸化物、ガラス、セラミックス、金属、半導体、及びプラスチックのいずれかからなることを特徴とする（２）〜（８）のいずれかに記載の金属配線パターンの形成方法。(9) The method for forming a metal wiring pattern according to any one of (2) to (8), wherein the substrate is made of any one of oxide, glass, ceramics, metal, semiconductor, and plastic.
（１０）（２）〜（９）のいずれかに記載の方法によって各種基板上に作成されたことを特徴とする金属配線パターン。(10) A metal wiring pattern produced on various substrates by the method according to any one of (2) to (9).
（１１）（１０）に記載の金属配線パターンを利用し形成した導電路、導電路と導電路を接続する接続部および導電路を形成した基板を多数積層した多層配線基板。(11) A multilayer wiring board in which a plurality of conductive paths formed using the metal wiring pattern according to (10), a connection portion connecting the conductive paths and the conductive paths, and a substrate on which the conductive paths are formed are stacked.
（１２）（１０）に記載の金属配線パターンを利用し形成したバンプ。(12) A bump formed using the metal wiring pattern according to (10).
（１３）（１０）に記載の金属配線パターンを利用し形成したパッド。(13) A pad formed using the metal wiring pattern according to (10).
（１４）（１０）に記載の金属配線パターンを利用し形成したビア。(14) A via formed using the metal wiring pattern according to (10).
（１５）（１０）に記載の金属配線パターンを利用し形成した熱伝導路。(15) A heat conduction path formed using the metal wiring pattern according to (10).
（１６）（１０）に記載の金属配線パターンを利用し形成したアンテナ。(16) An antenna formed using the metal wiring pattern according to (10).
（１７）（１０）に記載の金属配線パターンを利用し形成した電磁シールド材。(17) An electromagnetic shielding material formed using the metal wiring pattern according to (10).
（１８）（１０）に記載の金属配線パターンと、基板の両者を含む電子実装部品。(18) An electronic mounting component including both the metal wiring pattern according to (10) and a substrate.
（１９）（１０）に記載の金属配線パターンを利用し形成した触媒電極。(19) A catalyst electrode formed using the metal wiring pattern according to (10).
（２０）スズ、鉛、ビスマス、亜鉛、もしくはこれら金属からなる合金を主成分とするハンダ材料をはんだ接合部に使用した（１０）に記載の金属配線パターン。(20) The metal wiring pattern according to (10), wherein a solder material mainly composed of tin, lead, bismuth, zinc, or an alloy made of these metals is used for a solder joint.
（２１）導電路、導電路と導電路を結ぶ接続部、多層配線基板、アンテナ、熱伝導路、電磁シールド材、バンプ、パッド、ビア、電子実装部品、触媒電極、又はハンダ接合部に用いることを特徴とする（１０）に記載の金属配線パターン。(21) Use for conductive paths, connecting sections connecting conductive paths, multilayer wiring boards, antennas, thermal conductive paths, electromagnetic shielding materials, bumps, pads, vias, electronic mounting parts, catalyst electrodes, or solder joints The metal wiring pattern as described in (10) characterized by these.
（２２）前記焼結助剤としてカーボンブラック、カーボンナノチューブ、カーボンフラーレン、及びＶＧＣＦ（気相成長カーボンファイバー）からなる群から選ばれるカーボン材料を用いた高周波電磁波照射による還元焼成方法で、その加熱温度の下限値が抵抗炉を用いた還元焼成方法における加熱温度の下限値より低温であることを特徴とする、（１）に記載の還元焼成方法。(22) A reduction firing method by high-frequency electromagnetic wave irradiation using a carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon fullerene, and VGCF (vapor-grown carbon fiber) as the sintering aid, and its heating temperature The lower limit of the temperature is lower than the lower limit of the heating temperature in the reduction firing method using a resistance furnace, the reduction firing method according to (1).
（２３）前記焼結助剤としてカーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）からなる群から選ばれるカーボン材料を用いた高周波電磁波照射による酸化銅粒子もしくは表面酸化銅粒子の還元焼成方法で、酸化銅粒子もしくは表面酸化銅粒子の加熱温度の下限値が３００℃であることを特徴とする（１）に記載の還元焼成方法。(23) Copper oxide particles or surface copper oxide particles produced by high-frequency electromagnetic wave irradiation using a carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon fullerene, and VGCF (vapor-grown carbon fiber) as the sintering aid. The reduction firing method according to (1), wherein the lower limit of the heating temperature of the copper oxide particles or the surface copper oxide particles is 300 ° C. in the reduction firing method.
（２４）前記焼結助剤としてカーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）からなる群から選ばれるカーボン材料を用いた高周波電磁波照射による酸化銀粒子もしくは表面酸化銀粒子の還元焼成方法で、酸化銀粒子もしくは表面酸化銀粒子の加熱温度の下限値が１８０℃であることを特徴とする（１）に記載の還元焼成方法。(24) Silver oxide particles or surface oxidized oxide particles by high-frequency electromagnetic wave irradiation using a carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon fullerene, and VGCF (vapor grown carbon fiber) as the sintering aid. The reduction firing method according to (1), wherein the lower limit of the heating temperature of the silver oxide particles or the surface silver oxide particles is 180 ° C. in the reduction firing method.
（２５）前記焼結助剤としてカーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）からなる群から選ばれるカーボン材料と、酸化銅粒子、表面酸化銅粒子、酸化銀もしくは表面酸化銀粒子とを混合した混合物を、ポリイミド、ポリアミドイミド、ポリアミド、ガラスエポキシ、ポリフッ化エチレン、又はガラスエポキシを主成分とするプラスチック基板上で還元焼成することを特徴とする（２３）又は（２４）に記載の還元焼成方法。(25) A carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon fullerene, and VGCF (vapor grown carbon fiber) as the sintering aid, and copper oxide particles, surface copper oxide particles, silver oxide, or surface oxidation (23) or (24), wherein the mixture obtained by mixing silver particles is reduced and fired on a plastic substrate mainly composed of polyimide, polyamideimide, polyamide, glass epoxy, polyfluorinated ethylene, or glass epoxy. The reduction firing method described in 1.
（２６）金属酸化物粒子及び表面酸化金属粒子の少なくとも一方と電磁波吸収性の優れた焼結助剤との混合物を含み、不活性雰囲気にて高周波電磁波を照射することで前記粒子を選択的に加熱還元する加熱還元焼成用材料であって、(26) A mixture of at least one of metal oxide particles and surface oxidized metal particles and a sintering aid having excellent electromagnetic wave absorbability, and selectively irradiating the particles with high-frequency electromagnetic waves in an inert atmosphere. A heat reduction baking material for heat reduction,
電磁波吸収性の優れた焼結助剤が、カーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）、Ｃｒ Sintering aids with excellent electromagnetic wave absorption are carbon black, carbon nanotubes, carbon fullerene, VGCF (vapor-grown carbon fiber), Cr
２2
ＯO
３3
、ＴｉＯTiO
２2
、ＣｕＯ、ＮｉＯ、Ｃｏ, CuO, NiO, Co
３3
ＯO
４4
、ＭｎＯ, MnO
２2
、α―Ｆｅ, Α-Fe
２2
ＯO
３3
、Ｖ, V
２2
ＯO
３3
、ＳｎＯ, SnO
２2
、Ｉｎ, In
２2
ＯO
３3
、ＧｅＯ, GeO
２2
、ＺｎＯ、ＭｇＯ、及びＳｉＯ, ZnO, MgO, and SiO
２2
からなる群から選らばれる少なくとも１つであることを特徴とする還元焼成用材料。A material for reduction firing, which is at least one selected from the group consisting of:
（２７）さらに有機系分散媒及び／又は有機系バインダーとして機能する樹脂成分、もしくは必要に応じて有機溶媒を加えたことを特徴とする（２６）に記載の加熱還元焼成用材料。(27) The heat-reduction baking material as described in (26), further comprising a resin component that functions as an organic dispersion medium and / or an organic binder, or an organic solvent as necessary.
（２８）前記金属酸化物粒子が、銀酸化物、銅酸化物、又は酸化ニッケルからなる粒子である、あるいは、前記表面酸化金属粒子が、銀、銅、又はニッケルからなる粒子であることを特徴とする（２６）又は（２７）に記載の加熱還元焼成用材料。(28) The metal oxide particles are particles made of silver oxide, copper oxide, or nickel oxide, or the surface metal oxide particles are particles made of silver, copper, or nickel. (26) or the material for heat reduction baking according to (27).
（２９）前記金属酸化物粒子もしくは表面酸化金属粒子が、粒径１ｎｍ以上、１００ｎｍ以下のナノ粒子であることを特徴とする（２６）〜（２８）のいずれかに記載の加熱還元焼成用材料。(29) The heat-reduction baking material according to any one of (26) to (28), wherein the metal oxide particles or the surface metal oxide particles are nanoparticles having a particle diameter of 1 nm or more and 100 nm or less. .
（３０）前記有機系分散媒が金属酸化物の金属成分と配位可能なアミン、アルコール、及びチオールからなる群から選ばれた少なくとも１種を含み、さらに有機バインダー樹脂がブチラール樹脂、エポキシ樹脂、フェノール樹脂、及びポリイミド樹脂からなる群から選ばれた少なくとも１種以上を含むことを特徴とする（２７）〜（２９）のいずれか１項に記載の加熱還元焼成用材料。(30) The organic dispersion medium includes at least one selected from the group consisting of amine, alcohol, and thiol capable of coordinating with the metal component of the metal oxide, and the organic binder resin is a butyral resin, an epoxy resin, The heat-reduction baking material according to any one of (27) to (29), including at least one selected from the group consisting of a phenol resin and a polyimide resin.
本発明の方法を用いて、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子を、基板上に表面塗布又はパターニング後所定の周波数の高周波電磁波を照射して選択加熱することにより、還元・相互融着させて、複雑な電子実装部品を形成することができる。またこの方法を用いることにより、各種基板上に導電路、導電路と導電路の接続部、導電路を形成した基板を多数積層した配線基板、バンプ、パッド、ビア、熱伝導路、アンテナ、電磁シールド材やその他の電子実装部品、触媒電極等を形成した電子基板やアンテナを形成した電子筐体等を形成することができる。このとき、電子部品形成部を選択的に加熱することから、電子部品実装基板には耐熱性を有する基板のみでなく、耐熱性の低い樹脂基板等を用いることが可能となる。尚、本発明における基板とは、必ずしも平板上のもののみではなく、その形状が段差を有するものや曲面を有するものを含むものとすることから、電子筐体なども基板に含むものとする。 Using the method of the present invention, metal oxide particles mixed with a sintering aid with excellent electromagnetic wave absorption, or surface oxidized metal particles mixed with a sintering auxiliary with excellent electromagnetic wave absorption, or electromagnetic wave absorbing By selectively heating a particle containing a mixture of the metal oxide particles and the surface oxidized metal particles mixed with an excellent sintering aid by irradiating the substrate with a high frequency electromagnetic wave having a predetermined frequency after surface coating or patterning. Then, reduction and mutual fusion can be performed to form a complicated electronic mounting component. In addition, by using this method, wiring boards, bumps, pads, vias, heat conduction paths, antennas, electromagnetics, which are formed by laminating a number of conductive paths, connection sections between conductive paths, and conductive paths on various substrates An electronic substrate on which a shield material, other electronic mounting parts, a catalyst electrode, and the like are formed, an electronic housing on which an antenna is formed, and the like can be formed. At this time, since the electronic component forming portion is selectively heated, not only a substrate having heat resistance but also a resin substrate having low heat resistance can be used as the electronic component mounting substrate. In addition, the board | substrate in this invention does not necessarily need to be a thing on a flat plate, but since the shape includes what has a level | step difference and what has a curved surface, an electronic housing | casing etc. shall also be included in a board | substrate.
以下に本発明の高周波電磁波照射を利用した、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子の還元・相互融着方法の詳細について説明する。 Metal oxide particles mixed with a sintering aid excellent in electromagnetic wave absorption using the high frequency electromagnetic wave irradiation of the present invention, or surface oxidized metal particles mixed with a sintering aid excellent in electromagnetic wave absorption, or The details of the reduction and mutual fusion method of the particles containing the mixture of the metal oxide particles and the surface oxidized metal particles mixed with the sintering aid having excellent electromagnetic wave absorbability will be described.
導電路もしくはバンプ等の実装部品を構成する粒子材料として、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子を各種基板上に表面塗布もしくは表面パターニングする。基板上の表面塗布又はパターンニング法としては、インクジェット法、ナノプリンティング法、ナノインプリンティング法等の各種回路パターニング方法がある。
ここで、導電路とは、そこに電流が流れるもの、電磁誘導により電流が誘起されるもの等も含むものとし、電磁誘導により電流が誘起されるものとしては電磁シールド用の回路、アンテナなどがある。導電路には、閉回路も開回路も含み、さらに回路の形状やパターニングによる制約を受けないものとする。本願における回路も同様の意味で使用しているので、必ずしも閉回路に限らない。パターニングした回路を電気導電路に限らず、熱伝導路として用いることも可能である。さらには、触媒電極として使用することも可能である。
Metal oxide particles mixed with a sintering aid with excellent electromagnetic wave absorption or surface oxidized metal mixed with a sintering auxiliary with excellent electromagnetic wave absorption as a particle material that constitutes mounting parts such as conductive paths or bumps Particles or particles containing a mixture of the metal oxide particles mixed with a sintering aid having excellent electromagnetic wave absorbability and the surface oxidized metal particles are surface coated or surface patterned on various substrates. Examples of surface coating or patterning methods on a substrate include various circuit patterning methods such as an ink jet method, a nanoprinting method, and a nanoimprinting method.
Here, the conductive path includes those in which current flows, those in which current is induced by electromagnetic induction, etc., and those in which current is induced by electromagnetic induction include circuits for electromagnetic shielding, antennas, and the like . The conductive path includes both a closed circuit and an open circuit, and is not restricted by the shape or patterning of the circuit. Since the circuit in this application is also used in the same meaning, it is not necessarily limited to a closed circuit. The patterned circuit can be used not only as an electric conduction path but also as a heat conduction path. Furthermore, it can be used as a catalyst electrode.
基板上に表面塗布もしくは表面パターニングを行う電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは同じく電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子は、少なくとも基板よりも高周波電磁波吸収性の優れたものを選択する。ただし、金属酸化物粒子自体もしくは表面酸化金属粒子自体の高周波電磁波吸収性が基板の高周波電磁波吸収性よりも低い場合でも、電磁波吸収性の優れた焼結助剤の混合により高周波電磁波吸収性が基板の高周波電磁波吸収性よりも高くなれば、そのような混合物も使用することができる。 Metal oxide particles mixed with a sintering aid with excellent electromagnetic wave absorption for surface coating or surface patterning on a substrate, or surface oxidized metal particles mixed with a sintering auxiliary with excellent electromagnetic wave absorption, or electromagnetic waves As the particles containing a mixture of the metal oxide particles and the surface oxidized metal particles mixed with a sintering aid having excellent absorbability, those having at least high frequency electromagnetic wave absorbability than the substrate are selected. However, even when the metal oxide particles themselves or the surface oxidized metal particles themselves have a lower high frequency electromagnetic wave absorbency than the high frequency electromagnetic wave absorbability of the substrate, the high frequency electromagnetic wave absorbability can be increased by mixing the sintering aid with excellent electromagnetic wave absorbability. Such a mixture can also be used if it becomes higher than the high frequency electromagnetic wave absorptivity.
また、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子をペースト状にして塗布する時には、目的とする電子部品や導電路の形成部に応じて、ペーストの組成を選択できる。ペーストには、少なくとも電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子が含まれることを必須要件とするが、この他に導電性樹脂又は有機溶媒、導電性樹脂及び有機溶媒などを必要に応じて混合してもよい。混合する目的は、上記粒子の分散状態の改善や基板との密着性の改善などのためである。 Also, metal oxide particles mixed with a sintering aid with excellent electromagnetic wave absorption, surface oxidized metal particles mixed with a sintering auxiliary with excellent electromagnetic wave absorption, or sintering auxiliary with excellent electromagnetic wave absorption When the particles containing the mixture of the metal oxide particles mixed with the surface oxidized metal particles are applied in the form of a paste, the composition of the paste can be selected according to the target electronic component and the conductive path forming part. The paste includes metal oxide particles mixed with at least a sintering aid having excellent electromagnetic wave absorption properties, surface oxidized metal particles mixed with a sintering aid having excellent electromagnetic wave absorption properties, or firing with excellent electromagnetic wave absorption properties. Although it is an essential requirement that particles containing a mixture of the metal oxide particles mixed with a binder and the surface oxidized metal particles are included, a conductive resin or an organic solvent, a conductive resin, an organic solvent, etc. May be mixed as necessary. The purpose of mixing is to improve the dispersion state of the particles and improve the adhesion to the substrate.
高周波電磁波を吸収する金属酸化物粒子としては、金属−酸素結合を持つ無機及び有機金属化合物ならばいずれの化合物でも用いることができる。ただし、導電性の高い金属配線パターンを形成するためには、酸化銀、酸化銅などの高導電性金属の酸化物を用いることが望ましく、また、触媒活性の高い金属配線パターンを形成するためには、酸化ニッケルなどの触媒活性の高い金属の酸化物を用いることが望ましい。 As the metal oxide particles that absorb high-frequency electromagnetic waves, any compound can be used as long as it is an inorganic or organic metal compound having a metal-oxygen bond. However, in order to form a highly conductive metal wiring pattern, it is desirable to use an oxide of a highly conductive metal such as silver oxide or copper oxide, and to form a metal wiring pattern with high catalytic activity. It is desirable to use a metal oxide having a high catalytic activity such as nickel oxide.
また、金属酸化物粒子もしくは表面酸化金属もしくは両者の混合物に混合する、電磁波吸収性の優れた焼結助剤としては、高周波電磁波吸収性を高めると同時に、酸化物の還元剤として、作用する第１群の材料として、カーボンブラック、カーボーンチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）等のカーボン材料等があり、酸化物の還元剤としては作用しないが高周波電磁波吸収性を高める第２群の材料として、Ｃｒ２Ｏ３、ＴｉＯ２、ＣｕＯ、ＮｉＯ、Ｃｏ３Ｏ４、ＭｎＯ２、α―Ｆｅ２Ｏ３、Ｖ２Ｏ３等の遷移金属酸化物、ｎ型半導性を示すＳｎＯ２、Ｉｎ２Ｏ３、ＧｅＯ２、ＺｎＯ、ＭｇＯ、ＳｉＯ２等の典型金属酸化物、ＩＴＯ（インジウム-スズ酸化物）などがある。 In addition, as a sintering aid having excellent electromagnetic wave absorbability, mixed with metal oxide particles or surface oxidized metal or a mixture of both, the high-frequency electromagnetic wave absorbability is enhanced, and at the same time, it acts as an oxide reducing agent. As a group of materials, there are carbon materials such as carbon black, carbon tube, carbon fullerene, VGCF (vapor-grown carbon fiber), and the like. Second group that does not act as an oxide reducing agent but enhances high frequency electromagnetic wave absorption As a material, transition metal oxides such as Cr 2 O 3 , TiO 2 , CuO, NiO, Co 3 O 4 , MnO 2 , α-Fe 2 O 3 , V 2 O 3 , SnO exhibiting n-type semiconductivity 2 , In 2 O 3 , GeO 2 , ZnO, MgO, SiO 2 and other typical metal oxides, ITO (indium-tin oxide), and the like.
これらの焼結助剤のなかで、高周波電磁波吸収性を高めると同時に酸化物の還元剤として作用する第１群の材料であるカーボンブラック、カーボーンチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）等のカーボン材料は、電磁波吸収剤としてのみならず、酸化物の還元剤としての機能を有することから、上記金属酸化物粒子もしくは表面酸化金属もしくは両者の混合物の加熱還元反応を促進する焼結助剤として特に望ましい。 Among these sintering aids, carbon black, carbon tube, carbon fullerene, and VGCF (vapor-grown carbon fiber) are the first group of materials that act as oxide reducing agents while improving high-frequency electromagnetic wave absorption. Since carbon materials such as these have functions not only as electromagnetic wave absorbers but also as oxide reducing agents, sintering aids that promote the heat reduction reaction of the above metal oxide particles or surface metal oxides or a mixture of both are preferred. Particularly desirable as an agent.
また同じく焼結助剤として挙げられる第２群の材料であるＣｒ２Ｏ３、ＴｉＯ２、ＣｕＯ、ＮｉＯ、Ｃｏ３Ｏ４、ＭｎＯ２、α―Ｆｅ２Ｏ３、Ｖ２Ｏ３等の遷移金属酸化物、ｎ型半導性を示すＳｎＯ２、Ｉｎ２Ｏ３、ＧｅＯ２、ＺｎＯ、ＭｇＯ、ＳｉＯ２等の典型金属酸化物、ＩＴＯ（インジウム-スズ酸化物）などの物質は、酸化物の還元剤としては機能しないが、電磁波の吸収剤として機能し金属酸化物粒子もしくは表面酸化金属もしくは両者の混合物の選択的な加熱を大いに促進することから、焼結助剤としてこれらの材料も有効である。 Similarly, transitions of Cr 2 O 3 , TiO 2 , CuO, NiO, Co 3 O 4 , MnO 2 , α-Fe 2 O 3 , V 2 O 3, etc., which are the second group of materials cited as sintering aids. Substances such as metal oxides, typical metal oxides such as SnO 2 , In 2 O 3 , GeO 2 , ZnO, MgO, and SiO 2 exhibiting n-type semiconductivity, ITO (indium-tin oxide) are oxides These materials are also effective as sintering aids because they do not function as reducing agents, but they function as electromagnetic wave absorbers and greatly promote selective heating of metal oxide particles or surface metal oxides or a mixture of both. It is.
次に、上記方法により、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子を、塗布もしくは回路パターニングした実装基板に対し、不活性雰囲気中で高周波電磁波の照射を行うことで、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子を選択的に加熱し、これら金属酸化物粒子もしくは表面酸化金属粒子を還元・相互融着させる。これにより各種基板上に導電性部品を形成する。 Next, by the above method, metal oxide particles mixed with a sintering aid excellent in electromagnetic wave absorption, surface oxidized metal particles mixed with a sintering auxiliary excellent in electromagnetic wave absorption, or excellent electromagnetic wave absorption By applying high frequency electromagnetic waves in an inert atmosphere to the mounting substrate on which the metal oxide particles mixed with the sintering aid and the mixture of the surface oxidized metal particles are coated or circuit patterned, Mixing metal oxide particles mixed with sintering aid with excellent electromagnetic wave absorption, surface oxidized metal particles mixed with sintering auxiliary with excellent electromagnetic wave absorption, or sintering auxiliary with excellent electromagnetic wave absorption The particles containing the mixture of the metal oxide particles and the surface oxidized metal particles are selectively heated, and the metal oxide particles or the surface oxidized metal particles are reduced and mutually fused. As a result, conductive parts are formed on various substrates.
上記方法により形成された導電性部品は、完全に還元された金属粒子のみからなる焼成体によって構成されている場合もあれば、未還元の酸化物成分もしくは未反応の焼結助剤を少量含有している場合もある。この差異は、金属酸化物もしくは表面酸化金属酸化物の還元反応の進行度合い、酸化物の還元剤として機能する焼結助剤との化学当量バランス等によって生じるものである。しかしながら、これら未還元の酸化物成分もしくは未反応の焼結助剤が少量残留した場合でも、全体に占める導電性の金属粒子の割合が、３次元パーコレーション閾値である２０％を上回っていれば、焼成体全体として導電性を示し、導電性部品として使用することが可能であると考えられる。 The conductive part formed by the above method may be composed of a fired body made of completely reduced metal particles, or may contain a small amount of an unreduced oxide component or an unreacted sintering aid. Sometimes it is. This difference is caused by the degree of progress of the reduction reaction of the metal oxide or the surface oxidized metal oxide, the chemical equivalent balance with the sintering aid functioning as the oxide reducing agent, and the like. However, even if a small amount of these unreduced oxide components or unreacted sintering aids remain, if the proportion of conductive metal particles in the total exceeds 20%, which is the three-dimensional percolation threshold, It is considered that the fired body as a whole exhibits conductivity and can be used as a conductive part.
本発明の最も特記すべき特徴は次の二つである。一つは、金属酸化物微細粒子を用いた直接回路描画法において、その熱処理（還元・相互融着）工程に、抵抗炉ではなく、高周波電磁波照射装置を用いた点であり、もう一つは、それに使用する粒子として、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子を用いた点である。 The most notable features of the present invention are the following two. One is the direct circuit drawing method using metal oxide fine particles, and the heat treatment (reduction / mutual fusion) process uses a high-frequency electromagnetic wave irradiation device instead of a resistance furnace. , Metal oxide particles mixed with sintering aids excellent in electromagnetic wave absorption, or surface oxidized metal particles mixed with sintering auxiliary agents excellent in electromagnetic wave absorption, or excellent electromagnetic wave absorption In other words, particles containing a mixture of the metal oxide particles mixed with the sintering aid and the surface oxidized metal particles are used.
高周波電磁波照射による物質加熱は、高周波電磁波の物質内部での誘電現象に起因する。すなわち、誘電損失の大きい（高周波電磁波吸収性の優れた）材料に照射された高周波電磁波は、材料を構成する分子を回転・衝突・振動・摩擦させ、エネルギーを失いながら物質内部を伝搬する。この時生じた分子の運動により材料が加熱される。ここで、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した表面酸化金属粒子、もしくは電磁波吸収性の優れた焼結助剤を混合した前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子は、加熱により熱分解もしくは共存する還元剤によって還元されて非酸化状態の金属粒子が表出し、その後それら非酸化状態の金属粒子が相互融着する。 Material heating by high-frequency electromagnetic wave irradiation is caused by a dielectric phenomenon inside the substance of high-frequency electromagnetic wave. That is, the high-frequency electromagnetic wave irradiated to a material having a large dielectric loss (excellent in high-frequency electromagnetic wave absorbability) rotates, collides, vibrates, and frictions the molecules constituting the material, and propagates inside the substance while losing energy. The material is heated by the movement of molecules generated at this time. Here, metal oxide particles mixed with a sintering aid excellent in electromagnetic wave absorption, surface oxidized metal particles mixed with a sintering auxiliary excellent in electromagnetic wave absorption, or sintering aid excellent in electromagnetic wave absorption Particles containing a mixture of the metal oxide particles and the surface oxidized metal particles mixed with an agent are thermally decomposed by heating or reduced by a coexisting reducing agent to display non-oxidized metal particles, and then those non-oxidized states The metal particles are mutually fused.
従来提案されていた熱風やスチームもしくは電熱線を用いた抵抗炉による熱処理とこの高周波電磁波加熱との最も大きな相違点は、前者では外部から熱伝導によって材料によらず均一に熱が伝えられるのに対し、後者では、目的とする物質が直接かつ選択的に加熱されるということである。 The biggest difference between the conventionally proposed heat treatment by a resistance furnace using hot air, steam, or heating wire and this high-frequency electromagnetic wave heating is that heat is transmitted uniformly from the outside by heat conduction regardless of the material. In contrast, the latter means that the target substance is directly and selectively heated.
ここで高周波電磁波による加熱特性の物質による相違について説明する。高周波電磁波が誘電性物質の中で単位面積あたり熱となって消費されるエネルギー（Ｐ）は次式で表される。 Here, the difference between the heating characteristics due to the high-frequency electromagnetic wave due to the substance will be described. Energy (P) consumed by the high frequency electromagnetic wave as heat per unit area in the dielectric material is expressed by the following equation.
従って、高周波電磁波による物質の加熱され易さは、それぞれ物質固有の誘電率と誘電損失角の積（誘電損失係数）によって決まる。つまり、誘電損失係数が高い物質では、高周波電磁波によって物質が高効率に加熱されるのに対し、誘電損失係数が低い物質では、ほとんど加熱されない。この誘電損失係数の値は、温度、周波数によって変化するが、一般に誘電損失係数の高い材料としては、水、エチレングリコール、カーボン、遷移金属酸化物、n型半導性を示す典型金属酸化物などが知られ、また誘電損失係数の低い材料としては、石英ガラス、ポリスチレン、ポリカーボネート、ポリイミド、ポリフッ化エチレンなどが知られている。酸化物の還元剤として機能する材料としては、カーボンブラック、カーボンナノチューブ、カーボンフラーレンを始めとするカーボン材料などが用いられるが、これらカーボン材料は、一般に誘電損失係数も高く、混合物粒子の選択加熱性を高めるという観点からも適当であると言える。 Therefore, the ease with which a substance is heated by high-frequency electromagnetic waves is determined by the product (dielectric loss coefficient) of the dielectric constant and dielectric loss angle inherent to the substance. That is, a substance with a high dielectric loss coefficient is heated with high efficiency by high-frequency electromagnetic waves, whereas a substance with a low dielectric loss coefficient is hardly heated. The value of this dielectric loss coefficient varies depending on the temperature and frequency. In general, materials having a high dielectric loss coefficient include water, ethylene glycol, carbon, transition metal oxides, typical metal oxides exhibiting n-type semiconductivity, etc. In addition, quartz glass, polystyrene, polycarbonate, polyimide, polyfluorinated ethylene, and the like are known as materials having a low dielectric loss coefficient. Carbon materials such as carbon black, carbon nanotubes, and carbon fullerene are used as materials that function as oxide reducing agents, but these carbon materials generally have a high dielectric loss coefficient and are capable of selectively heating mixed particles. It can be said that it is appropriate from the viewpoint of enhancing the image quality.
本発明では、使用する粒子材料として、金属酸化物もしくは表面が酸化された金属酸化物もしくは前記両者の混合物と、誘電損失係数の高いカーボンや遷移金属酸化物などの焼結助剤との混合物を用いることで粒子材料全体としての誘電損失係数を高め、さらに下地基板として誘電損失係数の低いポリイミドなどの材料を選択することで、粒子材料に対する選択的加熱を実現している。 In the present invention, as a particulate material to be used, a mixture of a metal oxide or a metal oxide whose surface is oxidized or a mixture of the two and a sintering aid such as carbon or transition metal oxide having a high dielectric loss coefficient is used. By using it, the dielectric loss coefficient of the whole particle material is increased, and a material such as polyimide having a low dielectric loss coefficient is selected as the base substrate, thereby realizing selective heating of the particle material.
次に、本発明に使用する高周波電磁波の周波数ｆの影響について説明する。本発明で使用する高周波電磁波としては、周波数が１ＭＨｚ≦ｆ≦３００ＧＨｚの範囲の高周波電磁波を用いる。これは電磁波照射により物質内部に誘電損失現象が顕著に生じると考えられる範囲である。適用周波数を１ＭＨｚ≦ｆ≦３００ＧＨｚとするのは、周波数１ＭＨｚ以下では、誘電損失効果自体がほとんど生じないからであり、また周波数３００GHz以上では、照射された電磁波は極表面で減衰し、物質内部まで侵入しないためである。なお、この周波数範囲の高周波電磁波の中で、周波数範囲が１０ＧＨｚ≦ｆ≦３００ＧＨｚの範囲のものは、電界の均一性が得られ易く、電場不均一により発生する放電現象が起こりにくいという観点から、使用する電磁波としてより適していると考えられる。 Next, the influence of the frequency f of the high frequency electromagnetic wave used in the present invention will be described. As the high frequency electromagnetic wave used in the present invention, a high frequency electromagnetic wave having a frequency in the range of 1 MHz ≦ f ≦ 300 GHz is used. This is a range in which the dielectric loss phenomenon is conspicuously generated inside the substance by the electromagnetic wave irradiation. The reason why the applied frequency is 1 MHz ≦ f ≦ 300 GHz is that the dielectric loss effect itself hardly occurs at a frequency of 1 MHz or less, and at a frequency of 300 GHz or more, the irradiated electromagnetic wave attenuates on the pole surface and reaches the inside of the substance. This is to prevent intrusion. Among the high frequency electromagnetic waves in this frequency range, those having a frequency range of 10 GHz ≦ f ≦ 300 GHz are easy to obtain the uniformity of the electric field, and from the viewpoint that the discharge phenomenon caused by the nonuniformity of the electric field hardly occurs. It is thought that it is more suitable as an electromagnetic wave to be used.
さらに式（１）より、高周波電磁波が誘電性物質の中で単位面積あたり熱となって消費されるエネルギー（Ｐ）は、照射する周波数（ｆ）に比例することが分かる。その意味からは、周波数が高いほど、物質表面の急速加熱には適していると言える。しかしながら、その一方で、高周波電磁波は物質内部では減衰する。入射電磁波が物質内で半減する深さ（D）は次式で表される。 Furthermore, it can be seen from the formula (1) that the energy (P) consumed by the high frequency electromagnetic wave as heat per unit area in the dielectric substance is proportional to the frequency (f) to be irradiated. In that sense, it can be said that the higher the frequency, the more suitable for rapid heating of the material surface. However, on the other hand, high-frequency electromagnetic waves are attenuated inside the substance. The depth (D) at which the incident electromagnetic wave is halved in the substance is expressed by the following equation.
この式から、照射電磁波の周波数が高くなるにつれて、物質内部への高周波電磁波の減衰距離は短くなることが分かる。従って、本発明では、作成する実装部品のサイズ（厚み）に応じて、照射する電磁波の周波数を調整すればよい。 From this equation, it can be seen that the attenuation distance of the high frequency electromagnetic wave into the substance becomes shorter as the frequency of the irradiated electromagnetic wave becomes higher. Therefore, in the present invention, the frequency of the electromagnetic wave to be irradiated may be adjusted according to the size (thickness) of the mounted component to be created.
次に、本発明に用いる粒子材料について説明する。本発明に使用する粒子の必要要件は、高周波電磁波吸収特性があり、且つ加熱分解もしくは還元剤との共存下での加熱還元性を持つことであり、その要件を満たすものであれば、粒子の種類を問わない。具体的には、酸化銀、酸化銅、酸化ニッケル等を用いることができる。 Next, the particulate material used in the present invention will be described. The necessary requirement of the particles used in the present invention is that they have high-frequency electromagnetic wave absorption characteristics and have heat reducibility in the presence of heat decomposition or a reducing agent. Any type. Specifically, silver oxide, copper oxide, nickel oxide, or the like can be used.
ここで、熱分解特性を有する粒子のサイズに関しては特に制限は設けない。本発明の目的とする電子実装部品の作成、特に次世代高密度電子デバイスに対応した微細実装部品の作成という観点からは、粒子径が大きいと粒子充点率が低下し、その結果抵抗率が増加する。さらに、粒子の界面エネルギー、粒径減少による融点の低下、さらには高周波電磁波の浸透深さを考慮すると、粒子サイズはより小さい方が好ましく、例えば、平均粒径１ｎｍ〜１００ｎｍが好ましいと考えられる。 Here, no particular limitation is imposed on the size of the particles having thermal decomposition characteristics. From the viewpoint of the creation of electronic mounting components that are the object of the present invention, in particular, the creation of fine mounting components that are compatible with next-generation high-density electronic devices, the particle filling rate decreases as the particle size increases, and as a result, the resistivity is reduced. To increase. Furthermore, considering the interfacial energy of the particles, the lowering of the melting point due to particle size reduction, and the penetration depth of the high-frequency electromagnetic wave, the particle size is preferably smaller, for example, it is considered that the average particle size is preferably 1 nm to 100 nm.
次に、本発明において高周波電磁波の照射を行う場合の雰囲気について説明する。本発明において高周波電磁波照射は不活性雰囲気で行うが、その理由は、一度加熱還元され導電性の金属となった粒子が、再び酸化されることを防止するためである。具体的な不活性雰囲気の例としては、減圧大気中、真空中、希ガス（窒素、アルゴン等）中などが挙げられる。 Next, the atmosphere in the present invention when high frequency electromagnetic wave irradiation is performed will be described. In the present invention, high-frequency electromagnetic wave irradiation is performed in an inert atmosphere because the particles once heated and reduced to become conductive metal are prevented from being oxidized again. Specific examples of the inert atmosphere include reduced-pressure air, vacuum, and rare gases (nitrogen, argon, etc.).
以下に本発明の実施例について説明する。各種基板上に塗布した電磁波吸収性の優れた焼結助剤を添加した金属酸化物粒子の選択加熱性について以下の実験により確認した。まず加熱分解もしくは還元剤との共存下での加熱還元性を示す物質の一例として酸化銅ナノ粒子（Ｃｕ２Ｏ、平均粒径５０ｎｍ、福田金属箔工業株式会社製）を選択し、それに酸化物の還元剤として機能する焼結助剤である気相成長カーボンファイバー（ＶＧＣＦ）を混合したものを準備した。ただし、酸化銅ナノ粒子と気相成長カーボンファイバーの混合割合は、次の還元反応、
２Ｃｕ２Ｏ ＋ Ｃ → ２Ｃｕ ＋ ＣＯ２
が過不足なく進行するよう、モル比でＣｕ２Ｏ：ＶＧＣＦ = ２：１とした。次にこの混合物を石英基板、ポリイミド、ガラスエポキシの各基板上に部分的に塗布した（図１参照）。なお塗布部分の膜厚は約５０μｍであった。
Examples of the present invention will be described below. The selective heating property of the metal oxide particles to which a sintering aid having excellent electromagnetic wave absorption applied on various substrates was added was confirmed by the following experiment. First, copper oxide nanoparticles (Cu 2 O, average particle diameter of 50 nm, manufactured by Fukuda Metal Foil Industry Co., Ltd.) are selected as an example of a substance that exhibits thermal reducibility in the presence of thermal decomposition or a reducing agent. A mixture of vapor grown carbon fiber (VGCF), which is a sintering aid functioning as a reducing agent, was prepared. However, the mixing ratio of copper oxide nanoparticles and vapor-grown carbon fiber depends on the following reduction reaction:
2Cu 2 O + C → 2Cu + CO 2
Was made to be Cu 2 O: VGCF = 2: 1 in terms of molar ratio so as to proceed without excess or deficiency. Next, this mixture was partially applied on each of a quartz substrate, a polyimide, and a glass epoxy substrate (see FIG. 1). The coating thickness was about 50 μm.
次に、このＶＧＣＦ混合Cu２Oナノ粒子を部分的に塗布した各種基板に対し、図２に示す低周波電磁波照射装置により、出力５００Ｗ、周波数（ｆ）＝１ｋＨｚの低周波電磁波の照射を行った。またこれとは別に、同じくＶＧＣＦ混合Cu２Oナノ粒子を部分的に塗布した各種基板に対し、図３に示す高周波電磁波照射装置により、出力５００Ｗ、周波数（ｆ）＝２８ＧＨｚの高周波電磁波の照射も行った。なおこれら電磁波照射実験はすべて不活性アルゴン雰囲気中で行った。それぞれの電磁波照射において、VGCF混合Cu２Oナノ粒子を塗布した部分と塗布していない基板部分の温度変化を、熱電対を用いて測定した結果を、低周波（f = 1ｋＨｚ）照射について表１に、高周波（f = ２８G Hz）照射について表２に示す。但し、ここでＶＧＣＦ混合Cu２Oナノ粒子を塗布した部分の温度変化は、特に石英基板上に塗布したものに関する測定結果であるが、この塗布部分の温度変化は基板の種類にほとんど影響されなかった。 Next, low-frequency electromagnetic waves having an output of 500 W and a frequency (f) = 1 kHz are applied to various substrates partially coated with the VGCF mixed Cu 2 O nanoparticles by a low-frequency electromagnetic wave irradiation apparatus shown in FIG. It was. Separately, irradiation of high-frequency electromagnetic waves with an output of 500 W and a frequency (f) = 28 GHz is also performed on various substrates partially coated with VGCF-mixed Cu 2 O nanoparticles by the high-frequency electromagnetic wave irradiation apparatus shown in FIG. went. All these electromagnetic wave irradiation experiments were performed in an inert argon atmosphere. Table 1 shows the results of measuring the temperature change of the part where VGCF mixed Cu 2 O nanoparticles were applied and the part where the substrate was not applied using a thermocouple in each electromagnetic wave irradiation. Table 2 shows high-frequency (f = 28 GHz) irradiation. However, the temperature change of the portion where the VGCF mixed Cu 2 O nanoparticles are applied here is a measurement result particularly on the substrate coated on the quartz substrate, but the temperature change of the coated portion is hardly influenced by the type of the substrate. It was.
先ず、表１から、周波数（ｆ）＝１ｋＨｚの電磁波を照射した場合、１２０ｓｅｃ照射後においても、ＶＧＣＦ混合Cu２Oナノ粒子塗布部分の温度上昇は２℃以下であり、この周波数の電磁波照射においてＶＧＣＦ混合Cu２Oナノ粒子がほとんど加熱されないことが確認された。この結果は、低周波の電磁波照射は、本発明の目的とする金属酸化物粒子もしくは表面酸化金属粒子もしくは両者の化合物の選択加熱および還元相互融着には不適であることを示唆するものである。 First, from Table 1, when an electromagnetic wave with a frequency (f) = 1 kHz is irradiated, the temperature rise of the VGCF mixed Cu 2 O nanoparticle applied portion is 2 ° C. or less even after 120 sec irradiation. It was confirmed that the VGCF mixed Cu 2 O nanoparticles were hardly heated. This result suggests that low frequency electromagnetic wave irradiation is unsuitable for selective heating and reductive mutual fusion of metal oxide particles or surface metal oxide particles or a compound of both, which is the object of the present invention. .
一方で、表２より、周波数（ｆ）＝２８ＧＨｚの高周波電磁波を照射した場合、ＶＧＣＦ混合Cu２Oナノ粒子塗布部分の顕著な温度上昇が確認された。一方で、この混合ナノ粒子の塗布を行っていない基板部分では、基板の種類によらずその温度上昇はわずかであった。この結果は、ＶＧＣＦ混合Cu２Oナノ粒子の顕著な選択的加熱性を示唆するものである。 On the other hand, from Table 2, when irradiated with high-frequency electromagnetic wave of a frequency (f) = 28 GHz, significant temperature rise of the VGCF mixed Cu 2 O nanoparticles coated portion was confirmed. On the other hand, in the substrate portion where the mixed nanoparticles were not applied, the temperature rise was slight regardless of the type of substrate. This result suggests a remarkable selective heating property of the VGCF mixed Cu 2 O nanoparticles.
このように、この塗布もしくは表面パターニングする粒子として、ＶＧＣＦ混合Cu２Oナノ粒子をはじめとする、電磁波吸収性の優れた焼結助剤を混合した金属酸化物粒子を用い、さらに基板材料として石英基板、ポリイミド、ガラスエポキシをはじめとする電磁波吸収性の低い基板を用いることにより、粒子塗布部分のみを選択的に加熱できることを確認した。 Thus, as the particles for coating or surface patterning, metal oxide particles mixed with a sintering aid with excellent electromagnetic wave absorption, such as VGCF mixed Cu 2 O nanoparticles, are used, and quartz is used as a substrate material. It was confirmed that only the particle-coated portion can be selectively heated by using a substrate with low electromagnetic wave absorption such as a substrate, polyimide, and glass epoxy.
高周波電磁波の照射による金属酸化物粒子（Cu２０）の還元・焼成に関する、焼結助剤混合の効果について調べることを目的に、焼結助剤としてＶＧＣＦを混合した酸化銅ナノ粒子（モル混合比、Ｃu２Ｏ：ＶＧＣＦ=２：１）と、焼結助剤を混合していない酸化銅ナノ粒子のそれぞれに対する高周波電磁波照射時の還元・焼成効果の比較実験を次のように行った。 About reduction and sintering of the metal oxide particles by irradiation of high-frequency electromagnetic waves (Cu 2 0), with the purpose to investigate the effect of sintering aid mixture, copper oxide nanoparticles were mixed VGCF as a sintering aid (molar mixing The ratio, Cu 2 O: VGCF = 2: 1) and the reduction / firing effect during high-frequency electromagnetic wave irradiation with respect to each of the copper oxide nanoparticles not mixed with the sintering aid were compared as follows.
まず、ＶＧＣＦを混合した酸化銅ナノ粒子と、ＶＧＣＦを未混合の酸化銅ナノ粒子を、それぞれ石英基板上に塗布した後に、周波数（ｆ）＝２８ＧＨｚの高周波電磁波を照射した。この時、高周波電磁波の出力値は、５０℃／ｍｉｎで３００℃まで昇温して、その後３００℃で５分間保持するようにＰＩＤ制御により調節した。また高周波電磁波の照射は不活性アルゴン雰囲気中で行い、照射終了後、サンプルの温度が室温まで冷却した後、大気中に取り出した。最後に、取り出したサンプルの粒子塗布部分について、粉末Ｘ線回折装置（ＸＲＤ、株式会社リガク製）を用いてその結晶構造を同定した。その同定結果を表３に示す。 First, copper oxide nanoparticles mixed with VGCF and copper oxide nanoparticles not mixed with VGCF were applied onto a quartz substrate, respectively, and then irradiated with a high frequency electromagnetic wave having a frequency (f) = 28 GHz. At this time, the output value of the high frequency electromagnetic wave was adjusted by PID control so that the temperature was raised to 300 ° C. at 50 ° C./min and then held at 300 ° C. for 5 minutes. Further, the irradiation with the high frequency electromagnetic wave was performed in an inert argon atmosphere, and after the irradiation was completed, the sample was cooled to room temperature and then taken out into the atmosphere. Finally, the crystal structure of the particle-coated portion of the sample taken out was identified using a powder X-ray diffractometer (XRD, manufactured by Rigaku Corporation). The identification results are shown in Table 3.
この同定結果から、焼結助剤としてＶＧＣＦを混合した酸化銅ナノ粒子は、高周波電磁波照射後、完全にＣｕに還元されているのに対し、焼結助剤を混合していない酸化銅粒子は、高周波電磁波照射後もＣｕ２Ｏのままであることが分かった。以上から、本発明において、金属酸化物粒子、もしくは表面酸化金属粒子、もしくは前記金属酸化物粒子と前記表面酸化金属粒子の混合物を含む粒子を、高周波電磁波照射により各種基板上で選択的に加熱還元する場合には、ＶＧＣＦをはじめとする各種焼結助剤を前記粒子に混合することが重要な要件であることが確認された。 From this identification result, copper oxide nanoparticles mixed with VGCF as a sintering aid are completely reduced to Cu after high frequency electromagnetic wave irradiation, whereas copper oxide particles not mixed with a sintering aid are It was found that Cu 2 O remained after high frequency electromagnetic wave irradiation. From the above, in the present invention, metal oxide particles, surface oxidized metal particles, or particles containing a mixture of the metal oxide particles and the surface oxidized metal particles are selectively heated and reduced on various substrates by high-frequency electromagnetic wave irradiation. In this case, it was confirmed that mixing various sintering aids including VGCF into the particles is an important requirement.
ただし、前記照射実験後サンプルの粒子塗布部分の構成元素について、エネルギー分散型蛍光Ｘ線分析装置（ＥＤＸ、株式会社島津製作所製）を用いて調べたところ、焼結助剤としてＶＧＣＦを添加したサンプルについては、Ｃｕ以外に微量のカーボンが検出された。この結果は、高周波電磁波照射後も未反応のＶＧＣＦがサンプル中に少量残存していることを示唆するものである。 However, when the constituent elements of the particle-coated portion of the sample after the irradiation experiment were examined using an energy dispersive X-ray fluorescence spectrometer (EDX, manufactured by Shimadzu Corporation), a sample added with VGCF as a sintering aid In addition to Cu, a trace amount of carbon was detected in addition to Cu. This result suggests that a small amount of unreacted VGCF remains in the sample even after high frequency electromagnetic wave irradiation.
次に、焼結助剤を添加した金属酸化物粒子の還元・焼成効果に関して、熱処理方法の影響を調べることを目的に、高周波電磁波照射と抵抗炉加熱のそれぞれについて、酸化銅ナノ粒子（Ｃｕ２Ｏ）に対する熱処理温度と還元・焼成効果の関係について調べた。 Next, for the purpose of investigating the influence of the heat treatment method on the reduction and firing effects of the metal oxide particles to which the sintering aid has been added, copper oxide nanoparticles (Cu 2) are used for each of high-frequency electromagnetic wave irradiation and resistance furnace heating. The relationship between the heat treatment temperature for O) and the reduction / firing effect was investigated.
ただし抵抗炉加熱については、焼結助剤としてＶＧＣＦを混合したサンプルと焼結助剤未混合のサンプルを準備し、それぞれ熱処理実験を行った。ここで、高周波電磁波の照射は、上記実験と同様、設定熱処理温度まで５０℃／ｍｉｎで昇温し、その設定温度で５分間保持するように、ＰＩＤ制御で出力を調整した。また抵抗炉加熱の熱処理条件は、昇温速度：５０℃／ｍｉｎ、設定温度保持時間：６０ｍｉｎとした。上記熱処理はすべて不活性アルゴン雰囲気中で行い、熱処理終了後、サンプルの温度が室温まで冷却した後、大気中に取り出した。最後に、取り出したサンプルの粒子塗布部分について、粉末Ｘ線回折装置（ＸＲＤ、株式会社リガク製）を用いてその結晶構造を同定した。この結晶構造の同定結果を表４に示す。 However, for resistance furnace heating, a sample in which VGCF was mixed as a sintering aid and a sample in which the sintering aid was not mixed were prepared, and a heat treatment experiment was performed. Here, in the irradiation with high-frequency electromagnetic waves, the output was adjusted by PID control so that the temperature was raised to a set heat treatment temperature at 50 ° C./min and held at the set temperature for 5 minutes, as in the above experiment. The heat treatment conditions for resistance furnace heating were set to a temperature rising rate of 50 ° C./min and a set temperature holding time of 60 min. All the heat treatments were performed in an inert argon atmosphere, and after the heat treatment was completed, the sample was cooled to room temperature and then taken out into the atmosphere. Finally, the crystal structure of the particle-coated portion of the sample taken out was identified using a powder X-ray diffractometer (XRD, manufactured by Rigaku Corporation). The identification results of this crystal structure are shown in Table 4.
表４より、抵抗炉加熱では、酸化銅ナノ粒子を還元するためには、焼結助剤としてＶＧＣＦを添加した場合でも、少なくとも４５０℃以上の温度で熱処理しなければならないのに対し、２８ＧＨｚ高周波電磁波照射では、３００℃の熱処理温度で還元反応が進行することが分かる。この結果から、高周波電磁波照射では、従来の抵抗加熱と比べて遙かに低温でかつ短時間に酸化銅の還元反応が進行することが確認された。さらに同様の２８ＧＨｚ高周波電磁波照射実験を酸化銀（Ａｇ２Ｏ）ナノ粒子について行ったところ、焼結助剤としてＶＧＣＦを添加した酸化銀ナノ粒子では、１８０℃の熱処理温度で還元反応が進行することが分かった。 From Table 4, in resistance furnace heating, in order to reduce copper oxide nanoparticles, even when VGCF is added as a sintering aid, heat treatment must be performed at a temperature of at least 450 ° C. It can be seen that in the electromagnetic wave irradiation, the reduction reaction proceeds at a heat treatment temperature of 300 ° C. From this result, it was confirmed that the reduction reaction of copper oxide proceeds at a much lower temperature and in a shorter time in high-frequency electromagnetic wave irradiation than in conventional resistance heating. Furthermore, when the same 28 GHz high frequency electromagnetic wave irradiation experiment was conducted on silver oxide (Ag 2 O) nanoparticles, the reduction reaction proceeds at a heat treatment temperature of 180 ° C. with silver oxide nanoparticles to which VGCF is added as a sintering aid. I understood.
さらに、還元剤添加酸化物粒子に対する高周波電磁波照射にともなう粒子焼成効果を確認することを目的に、周波数（ｆ）＝２８ＧＨｚの高周波電磁波を照射したサンプル（５０℃／ｍｉｎで３００℃まで昇温、３００℃で５分間保持するように高周波電磁波出力を制御）の電気抵抗測定を行った。測定は、デジタルマルチメータ（Keithley社製、型式：DMM２０００）、直流安定化電源（ケンウッド社製、形式：ＰＡＲ２０−４Ｈ）を用いて、直流四端子法によって行った。 Furthermore, for the purpose of confirming the particle firing effect accompanying high-frequency electromagnetic wave irradiation on the reducing agent-added oxide particles, a sample irradiated with high-frequency electromagnetic wave of frequency (f) = 28 GHz (temperature rising to 300 ° C. at 50 ° C./min, The electrical resistance was measured by controlling the high frequency electromagnetic wave output so as to be held at 300 ° C. for 5 minutes. The measurement was performed by a DC four-terminal method using a digital multimeter (Keithley, model: DMM2000) and a DC stabilized power supply (Kenwood, model: PAR20-4H).
その結果、この周波数（ｆ）＝２８ＧＨｚの電磁波を１０ｍｉｎ照射したサンプルに対しては、ρ=８．０μΩ・ｃｍという高い導電性が確認された。この結果は、高周波電磁波の照射によりＣｕ２Ｏ粒子がＣｕへ還元し、さらにその還元されたＣｕ粒子が相互融着して、低抵抗の銅導電膜が形成されるという事実を示唆するものである。 As a result, high conductivity of ρ = 8.0 μΩ · cm was confirmed for the sample irradiated with the electromagnetic wave having the frequency (f) = 28 GHz for 10 minutes. This result suggests the fact that Cu 2 O particles are reduced to Cu by irradiation with high-frequency electromagnetic waves, and the reduced Cu particles are fused together to form a low resistance copper conductive film. is there.
なお、同様の効果は同じくポリイミド基板上にバンプ状に形成した円柱突起（円柱状、高さ約１ｍｍ、直径２ｍｍ）においても確認され、形状によらず本方法が適用出来ることが分かった。 The same effect was also confirmed in a cylindrical protrusion (cylindrical shape, height of about 1 mm, diameter of 2 mm) formed in a bump shape on the polyimide substrate, and it was found that this method can be applied regardless of the shape.
さらに、このCu２０ナノ粒子をペースト上にしてポリイミド基板上に塗布することで形成したパッド、ビア等においても同様の効果が確認され、ペースト化した還元剤添加金属酸化物粒子においても、本方法が適用出来ることが分かった。 Furthermore, the same effect was confirmed in pads, vias, and the like formed by applying these Cu 20 nanoparticles on a paste onto a polyimide substrate. It turns out that the method is applicable.
１．各種基板（石英ガラス、ポリイミド、ガラスエポキシ）
２．Cu2O粒子を塗布した領域
３．電磁波照射容器
４．導線
５．加熱電極
６．ターンテーブル
７．電磁波
1. Various substrates (quartz glass, polyimide, glass epoxy)
2. 2. Area where Cu 2 O particles are applied 3. Electromagnetic wave
Claims (30)
電磁波吸収性の優れた焼結助剤が、カーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）、Ｃｒ ２ Ｏ ３ 、ＴｉＯ ２ 、ＣｕＯ、ＮｉＯ、Ｃｏ ３ Ｏ ４ 、ＭｎＯ ２ 、α―Ｆｅ ２ Ｏ ３ 、Ｖ ２ Ｏ ３ 、ＳｎＯ ２ 、Ｉｎ ２ Ｏ ３ 、ＧｅＯ ２ 、ＺｎＯ、ＭｇＯ、及びＳｉＯ ２ からなる群から選らばれる少なくとも１つであることを特徴とする還元焼成方法。 After applying or surface patterning a mixture of at least one of metal oxide particles and surface oxidized metal particles and a sintering aid having excellent electromagnetic wave absorption properties on a substrate, irradiating high frequency electromagnetic waves in an inert atmosphere in a reduction firing method of heating and reducing the particle selectively,
Sintering aids excellent in electromagnetic wave absorption include carbon black, carbon nanotubes, carbon fullerene, VGCF (vapor growth carbon fiber), Cr 2 O 3 , TiO 2 , CuO, NiO, Co 3 O 4 , MnO 2 , A reduction firing method characterized by being at least one selected from the group consisting of α-Fe 2 O 3 , V 2 O 3 , SnO 2 , In 2 O 3 , GeO 2 , ZnO, MgO, and SiO 2 .
電磁波吸収性の優れた焼結助剤が、カーボンブラック、カーボンナノチューブ、カーボンフラーレン、ＶＧＣＦ（気相成長カーボンファイバー）、Ｃｒ ２ Ｏ ３ 、ＴｉＯ ２ 、ＣｕＯ、ＮｉＯ、Ｃｏ ３ Ｏ ４ 、ＭｎＯ ２ 、α―Ｆｅ ２ Ｏ ３ 、Ｖ ２ Ｏ ３ 、ＳｎＯ ２ 、Ｉｎ ２ Ｏ ３ 、ＧｅＯ ２ 、ＺｎＯ、ＭｇＯ、及びＳｉＯ ２ からなる群から選らばれる少なくとも１つであることを特徴とする還元焼成用材料。 Mixture only containing the at least one electromagnetic wave absorbing excellent sintering aid metal oxide particles and the surface metal oxide particles, selectively heating the reducing said particles by irradiating high-frequency waves in an inert atmosphere A material for heat reduction firing ,
Sintering aids excellent in electromagnetic wave absorption include carbon black, carbon nanotubes, carbon fullerene, VGCF (vapor growth carbon fiber), Cr 2 O 3 , TiO 2 , CuO, NiO, Co 3 O 4 , MnO 2 , Reduction firing material characterized by being at least one selected from the group consisting of α-Fe 2 O 3 , V 2 O 3 , SnO 2 , In 2 O 3 , GeO 2 , ZnO, MgO, and SiO 2 .
The organic dispersion medium includes at least one selected from the group consisting of amine, alcohol, and thiol capable of coordinating with the metal component of the metal oxide, and the organic binder resin is a butyral resin, an epoxy resin, a phenol resin, The heat reduction baking material according to any one of claims 27 to 29, comprising at least one selected from the group consisting of a polyimide resin and a polyimide resin.
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