JP5520861B2 - Copper alloy fine particle dispersion, method for producing sintered conductor, sintered conductor, and conductive connecting member - Google Patents
Copper alloy fine particle dispersion, method for producing sintered conductor, sintered conductor, and conductive connecting member Download PDFInfo
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- JP5520861B2 JP5520861B2 JP2011058937A JP2011058937A JP5520861B2 JP 5520861 B2 JP5520861 B2 JP 5520861B2 JP 2011058937 A JP2011058937 A JP 2011058937A JP 2011058937 A JP2011058937 A JP 2011058937A JP 5520861 B2 JP5520861 B2 JP 5520861B2
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- Prior art keywords
- copper alloy
- alloy fine
- particle dispersion
- fine particle
- copper
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 110
- 239000006185 dispersion Substances 0.000 title claims description 85
- 239000004020 conductor Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 18
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- 238000009835 boiling Methods 0.000 claims description 24
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
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Description
本発明は、銅−亜鉛からなる銅合金微粒子分散液、該分散液を加熱・焼結する焼結導電体の製造方法、及び該製造方法により得られる焼結導電体、並びに導電接続部材に関する。 The present invention relates to a copper alloy fine particle dispersion comprising copper-zinc, a method for producing a sintered conductor for heating and sintering the dispersion, a sintered conductor obtained by the production method, and a conductive connecting member.
ナノメートルサイズ（１μｍ未満のサイズをいう。以下同じ）の金属微粒子は、比表面積が大きく、粒子径が小さくなるにつれて融点が除々に低下する性質を有し、新しい形態の物質として近年注目されつつある。このナノメートルサイズの金属微粒子は、粒子の種類によって、樹脂との複合化のための微粒子表面修飾、薄膜化技術・粒子の配列、機能素子向けの研究開発が行われ、回路配線、インターコネクター、触媒、電池電極、光機能素子、可視光ＬＥＤ素子などへの応用も検討されている。これらの微粒子の中でも銅−亜鉛からなる銅合金微粒子は、バルク状態でも融点が低いので、ナノメートルサイズの該合金微粒子が商業的に得られれば電気・電子部品等に使用される焼結導電体として有用である。 Metal fine particles of nanometer size (referring to a size of less than 1 μm; hereinafter the same) have a property that the specific surface area is large and the melting point gradually decreases as the particle diameter decreases. is there. This nanometer-sized metal fine particle is subjected to fine particle surface modification for compounding with resin, thin film technology / particle arrangement, research and development for functional elements, depending on the type of particle, circuit wiring, interconnector, Applications to catalysts, battery electrodes, optical functional elements, visible light LED elements, and the like are also being studied. Among these fine particles, copper alloy fine particles made of copper-zinc have a low melting point even in a bulk state, so if nanometer-sized fine particles are commercially obtained, sintered conductors used for electric / electronic parts and the like Useful as.
このようなナノサイズの金属微粒子を製造する方法としては、大きく気相合成法と液相合成法の２種類の製法が知られている。ここで気相合成法とは、気相中に導入した金属蒸気から固体の金属微粒子を形成する方法であり、他方、液相合成法とは、溶液中に分散させた金属イオンを還元することにより金属微粒子を析出させる方法である。また、液相合成法においては、一般にその金属イオンを還元するための還元剤を使用する方法と、電気化学的にカソード電極上で還元を行う方法とが知られている。 As methods for producing such nano-sized metal fine particles, two types of production methods, a gas phase synthesis method and a liquid phase synthesis method, are widely known. Here, the gas phase synthesis method is a method of forming solid metal fine particles from metal vapor introduced into the gas phase, while the liquid phase synthesis method is to reduce metal ions dispersed in a solution. This is a method of depositing metal fine particles. In addition, in the liquid phase synthesis method, there are generally known a method using a reducing agent for reducing the metal ions and a method of electrochemical reduction on the cathode electrode.
また、最近では、金属微粒子を含有するインクを使用して、配線パターンをインクジェットプリンタにより印刷し、焼成して配線を形成する技術が注目されている。しかし、インクジェットプリンタのインクとして、金属微粒子を含有するインクを使用する場合、インク中において分散性を長期間保つことが重要である。そのため、インク中において分散性を長期間保つ金属微粒子の製造方法が提案されている。 In recent years, attention has been paid to a technique for forming a wiring by printing a wiring pattern by an ink jet printer using an ink containing metal fine particles and baking it. However, when ink containing metal fine particles is used as ink for an ink jet printer, it is important to maintain dispersibility in the ink for a long period of time. For this reason, a method for producing fine metal particles that maintains dispersibility in ink for a long period of time has been proposed.
また、金属微粒子分散液を乾燥後に焼成して金属薄膜又は金属細線を得る方法として下記の特許文献が公開されている。銅微粒子を得る方法として、核生成のためのパラジウムイオンを添加すると共に、分散剤としてポリエチレンイミンを添加してポリエチレングリコール又はエチレングリコール溶液中でパラジウムを含有する粒子径５０ｎｍ以下の銅微粒子を形成し、ついでこの銅微粒子分散液を用いて、基板上にパターン印刷を行うために、４％Ｈ２−Ｎ２気流中において２５０℃／３時間の熱処理を行うことによって、微細な銅の導電膜を形成したことが開示されている（特許文献１）。 Further, the following patent documents are disclosed as a method for obtaining a metal thin film or a metal fine wire by drying a metal fine particle dispersion and then baking it. As a method for obtaining copper fine particles, palladium ions for nucleation are added and polyethylene imine is added as a dispersant to form copper fine particles having a particle diameter of 50 nm or less containing palladium in a polyethylene glycol or ethylene glycol solution. Then, in order to perform pattern printing on the substrate using this copper fine particle dispersion, a fine copper conductive film is formed by performing heat treatment at 250 ° C./3 hours in a 4% H 2 —N 2 stream. The formation is disclosed (Patent Document 1).
１次粒子径が１００ｎｍ以下である金属酸化物微粒子を含むインクジェット用インクをインクジェット法により基板上に塗布した後、水素ガス雰囲気下で３５０℃／１時間の熱処理を施して、酸化第一銅の還元を行い、金属配線のパターンを得たことが開示されている（特許文献２）。金属の周りに分散剤として有機金属化合物が付着している金属ナノ粒子をスピンコート法により、基板（ガラス）上に塗布し、１００℃で乾燥し、２５０℃での焼成により銀の薄膜を作製したことが開示されている（特許文献３）。また、ジエチレングリコール中に懸濁された、２次粒子の平均粒子径５００ｎｍの酢酸銅を濃度が３０質量％になるように濃縮し、さらに超音波処理を施して、導電性インクとした後、スライドガラス上に塗布して、還元雰囲気で３５０℃／１時間加熱して銅薄膜を得たことが記載されている（特許文献４）。特許文献５には、ピロリン酸金属塩類から有機分散剤の存在下で液相還元反応により得られた、銅−スズ合金微粒子及び銅−スズ−リン合金微粒子をエチレングリコールに分散させた銅合金微粒子分散溶液が開示されている。 An ink-jet ink containing metal oxide fine particles having a primary particle diameter of 100 nm or less was applied on a substrate by an ink-jet method, and then heat-treated at 350 ° C. for 1 hour in a hydrogen gas atmosphere to obtain cuprous oxide. It is disclosed that a metal wiring pattern is obtained by performing reduction (Patent Document 2). Metal nanoparticles with an organometallic compound attached as a dispersant around the metal are applied onto a substrate (glass) by spin coating, dried at 100 ° C., and then fired at 250 ° C. to produce a silver thin film. (Patent Document 3). Further, copper acetate having an average particle diameter of 500 nm suspended in diethylene glycol was concentrated to a concentration of 30% by mass, further subjected to ultrasonic treatment to obtain a conductive ink, and then slides It is described that it was coated on glass and heated in a reducing atmosphere at 350 ° C./1 hour to obtain a copper thin film (Patent Document 4). Patent Document 5 discloses copper alloy fine particles obtained by dispersing copper-tin alloy fine particles and copper-tin-phosphorous alloy fine particles in ethylene glycol obtained by a liquid phase reduction reaction from metal pyrophosphate in the presence of an organic dispersant. Dispersion solutions are disclosed.
特許文献６には、銅合金微粒子が（ｉ）少なくとも、アミド基を有する有機溶媒５〜９０体積％、常圧における沸点が２０〜１００℃である低沸点の有機溶媒５〜４５体積％、並びに常圧における沸点が１００℃を超え、かつ分子中に１又は２以上のヒドロキシル基を有するアルコール及び／もしくは多価アルコールからなる有機溶媒５〜９０体積％含む有機溶媒（１）、（ii）少なくとも、アミド基を有する有機溶媒５〜９５体積％、及び常圧における沸点が１００℃を超え、かつ分子中に１又は２以上のヒドロキシル基を有するアルコール及び／もしくは多価アルコールからなる有機溶媒５〜９５体積％含む有機溶媒（２）、並びに（iii）常圧における沸点が１００℃を超え、かつ分子中に１又は２以上のヒドロキシル基を有するアルコール及び／もしくは多価アルコールからなる有機溶媒（３）、にそれぞれ分散された銅微粒子分散溶液が開示されている。 In Patent Document 6, copper alloy fine particles are (i) at least 5 to 90% by volume of an organic solvent having an amide group, 5 to 45% by volume of a low boiling organic solvent having a boiling point of 20 to 100 ° C. at normal pressure, and Organic solvent (1), (ii) containing at least 5 to 90% by volume of an organic solvent composed of an alcohol and / or a polyhydric alcohol having a boiling point of more than 100 ° C. at normal pressure and having one or more hydroxyl groups in the molecule 5 to 95% by volume of an organic solvent having an amide group, and 5 to 10% of an organic solvent composed of an alcohol and / or a polyhydric alcohol having a boiling point exceeding 100 ° C. and having one or more hydroxyl groups in the molecule. An organic solvent (2) containing 95% by volume, and (iii) an alcohol having a boiling point of more than 100 ° C. at normal pressure and one or more hydroxyl groups in the molecule The organic solvent consisting of Le and / or polyhydric alcohol (3), copper particulate dispersion solution dispersed respectively is disclosed.
上記した特許文献１、２をはじめ、特許文献３及び特許文献４における従来の製造方法では、２５０〜３００℃に近い高温で焼結をしなければ、導電性の焼結金属を得ることができず、また、熱処理のときに、水素ガス等の還元剤を使用しなければならないという問題点もあった。特許文献５には液相還元法により得られた銅−スズ合金微粒子及び銅−スズ−リン合金微粒子分散溶液が開示されているが、銅−亜鉛からなる銅合金微粒子は開示されていない。特許文献６には前記３種類の分散溶液が開示されているが、窒素ガス雰囲気中１８０〜３００℃で焼結して焼結膜を得たことが開示されているが、合金微粒子をより低温で焼成できることが望ましい。また、従来の金属又は合金微粒子に使用する還元性有機溶媒として、ヒドロキシル基を２以上有する、高い沸点を有する多価アルコールを多く含む分散溶媒を使用する必要があった。 In the conventional manufacturing methods in Patent Documents 1 and 2 described above, Patent Document 3 and Patent Document 4, a conductive sintered metal can be obtained if sintering is not performed at a high temperature close to 250 to 300 ° C. In addition, there is a problem that a reducing agent such as hydrogen gas must be used during the heat treatment. Patent Document 5 discloses copper-tin alloy fine particles and copper-tin-phosphorus alloy fine particle dispersion obtained by a liquid phase reduction method, but does not disclose copper alloy fine particles composed of copper-zinc. Patent Document 6 discloses the above three types of dispersion solutions. However, it is disclosed that a sintered film was obtained by sintering at 180 to 300 ° C. in a nitrogen gas atmosphere. It is desirable that it can be fired. Further, as a reducing organic solvent used for conventional metal or alloy fine particles, it is necessary to use a dispersion solvent containing a large amount of polyhydric alcohol having two or more hydroxyl groups and having a high boiling point.
本発明者らは、上記従来技術に鑑みて、銅系合金の中でも融点が低く、比較的低温でも還元触媒活性が高い銅−亜鉛からなる銅合金微粒子を使用して焼結する際に、少なくとも１つのヒドロキシル基を有するアルコールを含む分散溶媒を使用しても、該溶媒が還元性を発現して、低温における焼結でも高い結晶子径を有することに起因する、優れた導電性を有する銅−亜鉛からなる銅合金微粒子が得られることを見出し、本発明を完成するに至った。 In view of the above prior art, the present inventors have at least a copper alloy having a low melting point and a copper alloy fine particle composed of copper-zinc having a high reduction catalytic activity even at a relatively low temperature. Even if a dispersion solvent containing an alcohol having one hydroxyl group is used, the solvent exhibits excellent reducibility, and has excellent conductivity due to having a high crystallite size even when sintered at a low temperature. -It discovered that the copper alloy fine particle which consists of zinc was obtained, and came to complete this invention.
即ち、本発明は、以下の（１）〜（１０）に記載する発明を要旨とする。
（１）銅−亜鉛からなる銅合金微粒子中に３〜３２質量％の亜鉛が固溶している、平均一次粒子径が１〜８０ｎｍの銅合金微粒子が、少なくとも１つのヒドロキシル基を有する有機化合物（Ｓ１）を含有している有機溶媒（Ｓ）中に分散していることを特徴とする、銅合金微粒子分散液（以下、第１の態様ということがある）。
（２）前記有機溶媒（Ｓ）の常圧における沸点が１４０℃以上であることを特徴とする、前記（１）に記載の銅合金微粒子分散液。
That is, this invention makes the summary the invention described in the following (1)-( 10 ).
(1) An organic compound in which copper alloy fine particles having an average primary particle diameter of 1 to 80 nm have at least one hydroxyl group, in which 3 to 32% by mass of zinc is solid-solved in copper alloy fine particles composed of copper- zinc. A copper alloy fine particle dispersion liquid (hereinafter sometimes referred to as a first embodiment) characterized by being dispersed in an organic solvent (S) containing (S1).
( 2 ) The copper alloy fine particle dispersion described in (1) above, wherein the boiling point of the organic solvent (S) at normal pressure is 140 ° C. or higher.
（３）前記有機化合物（Ｓ１）がヒドロキシル基の結合している炭素原子に１又は２の水素原子が結合している有機化合物であることを特徴とする、前記（１）又は（２）に記載の銅合金微粒子分散液。
（４）前記有機溶媒（Ｓ）の常圧における沸点が３００℃以下であることを特徴とする、前記（１）から（３）のいずれかに記載の銅合金微粒子分散液。
（５）前記有機溶媒（Ｓ）が１つのヒドロキシル基を有する有機化合物（Ｓ１１）に２つ以上のヒドロキシル基を有する有機化合物（Ｓ１２）を配合することにより、有機溶媒（Ｓ）の常圧における沸点が１４０℃以上３００℃以下に調整された有機溶媒とすることを特徴とする、前記（１）から（３）のいずれかに記載の銅合金微粒子分散液。
（６）前記１つのヒドロキシル基を有する有機化合物（Ｓ１１）がメタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、２−メチル−１−プロパノール、２−メチル−２−プロパノール、２，２−ジメチル−１−プロパノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、３−メチル−１−ブタノール、２−メチル−１−ブタノール、２，２ジメチル−１−プロパノール、３−メチル−２−ブタノール、２−メチル−２−ブタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、２−メチル−２−ヘキサノール、２−メチル−３−ヘキサノール、１−ヘプタノール、２−ヘプタノール、４−ヘプタノール、２−エチル−１−ヘキサノール、１−オクタノール、及び２−オクタノールから選択される１種又は２種以上であることを特徴とする、前記（５）に記載の銅合金微粒子分散液。
( 3 ) In the above (1) or (2) , the organic compound (S1) is an organic compound in which one or two hydrogen atoms are bonded to a carbon atom to which a hydroxyl group is bonded. The copper alloy fine particle dispersion described.
( 4 ) The copper alloy fine particle dispersion according to any one of (1) to ( 3 ), wherein the organic solvent (S) has a boiling point of 300 ° C. or less at normal pressure.
( 5 ) The organic solvent (S) is mixed with the organic compound (S12) having two or more hydroxyl groups in the organic compound (S11) having one hydroxyl group, so that the organic solvent (S) at normal pressure The copper alloy fine particle dispersion according to any one of (1) to ( 3 ), wherein the organic solvent has a boiling point adjusted to 140 ° C. or higher and 300 ° C. or lower.
( 6 ) The organic compound (S11) having one hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2- Propanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2 dimethyl-1- Propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-heptanol, 2-heptanol, 4-heptanol, 2-ethyl-1-hexanol, 1-octanol, And wherein the at least one selected from the beauty octanol, copper alloy particulate dispersion according to (5).
（７）前記２つ以上のヒドロキシル基を有する有機化合物（Ｓ１２）がエチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−ブテン−１，４−ジオール、２，３−ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、グリセロール、１，１，１−トリスヒドロキシメチルエタン、２−エチル−２−ヒドロキシメチル−１，３−プロパンジオール、１，２，６−ヘキサントリオール、１，２，３−ヘキサントリオール、及び１，２，４−ブタントリオールの中から選択される１種又は２種以上であることを特徴とする、前記（５）に記載の銅合金微粒子分散液。
（８）前記（１）から（７）までのいずれかに記載の銅合金微粒子分散液を基板に塗布し、大気雰囲気中、もしくは不活性ガス雰囲気中で、有機溶媒（Ｓ）の沸点よりも５０〜４０℃低い温度範囲で加熱・焼結することにより、基板上に銅合金微粒子の導電体を形成することを特徴とする焼結導電体の製造方法（以下、第２の態様ということがある）。
（９）前記（８）に記載の導電体の製造方法によって製造された、結晶子径が３０ｎｍ以上であることを特徴とする焼結導電体（以下、第３の態様ということがある）。
（１０）前記（１）から（７）のいずれかに記載の銅合金微粒子分散液を電子部品における半導体素子もしくは回路基板の電極端子又は導電性基板の接合面に載せた後、該銅合金微粒子分散液上に更に接続する他方の電極端子又は導電性基板の接合面を配置して加熱処理により焼結して形成された導電接続部材（以下、第４の態様ということがある）。
( 7 ) The organic compound (S12) having two or more hydroxyl groups is ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol. 1,4-butanediol, 2-butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1,1,1-trishydroxymethylethane, 2-ethyl One or two selected from 2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, and 1,2,4-butanetriol The copper alloy fine particle dispersion according to ( 5 ) above, wherein the copper alloy fine particle dispersion is a seed or more.
( 8 ) The copper alloy fine particle dispersion according to any one of (1) to ( 7 ) above is applied to a substrate, and in an air atmosphere or an inert gas atmosphere, the boiling point of the organic solvent (S) is exceeded. A method for producing a sintered conductor (hereinafter referred to as a second embodiment), characterized in that a copper alloy fine particle conductor is formed on a substrate by heating and sintering in a temperature range lower by 50 to 40 ° C. is there).
( 9 ) A sintered conductor produced by the method for producing a conductor according to ( 8 ) above, having a crystallite diameter of 30 nm or more (hereinafter sometimes referred to as a third embodiment).
( 10 ) After placing the copper alloy fine particle dispersion according to any one of (1) to ( 7 ) on a semiconductor element or an electrode terminal of a circuit board in an electronic component or a bonding surface of a conductive substrate, the copper alloy fine particle A conductive connecting member formed by disposing a bonding surface of the other electrode terminal or the conductive substrate to be further connected on the dispersion and sintering by heat treatment (hereinafter sometimes referred to as a fourth aspect).
（イ）前記（１）に記載の銅合金微粒子分散液は、銅−亜鉛からなる銅合金微粒子の表面の触媒活性が著しく高いので、焼結の際にヒドロキシル基を１つ有する有機化合物を含む分散溶液を使用した場合でも、該有機化合物から水素ガスを発生させて還元性ガス雰囲気を形成する。従って、これまで不活性雰囲気中での焼成工程においてヒドロキシル基を２つ以上有する有機化合物を多く含む分散溶液を使用することが不可欠であったが、ヒドロキシル基を少なくとも１つ有する有機化合物を含む分散溶液中でも、１５０℃以下の低温における焼結でも導電性の高い焼結導電体を得ることが可能になる。
（ロ）前記（８）に記載の焼結導電体の製造方法は、前記の通り、銅−亜鉛からなる銅合金微粒子の表面の触媒活性が著しく高いので、焼結の際に還元性ガス雰囲気を形成するので有機溶媒（Ｓ）の沸点よりも５０〜４０℃低い温度範囲で焼結することが可能となる。
（ハ）前記（９）に記載の銅−亜鉛合金からなる焼結導電体は、銅合金微粒子表面で還元と焼結が促進されて焼結される結果、結晶子が成長して結晶子径が３０ｎｍ以上となり、抵抗率が３００μΩｃｍ以下程度の高い導電性を有している。また、銅−亜鉛からなる合金は熱欠陥、比抵抗値、付着力等の特性に優れ、配線材料としての特性に優れ、更に、ガラス基板との高い付着力を有していることが知られている（日本金属学会誌、７２巻Ｎｏ．９、Ｐ．７０３〜７０７参照）。
（ニ）前記（１０）に記載の銅−亜鉛合金からなる導電接続部材は、２００℃以下の低温で焼結させても導電性が高く、電極端子、導電性基板等の接合面との付着力にも優れている。
(A) Since the copper alloy fine particle dispersion described in (1) has a remarkably high catalytic activity on the surface of copper alloy fine particles made of copper-zinc, it contains an organic compound having one hydroxyl group during sintering. Even when a dispersion solution is used, hydrogen gas is generated from the organic compound to form a reducing gas atmosphere. Therefore, it has been essential to use a dispersion solution containing a large amount of an organic compound having two or more hydroxyl groups in the baking step in an inert atmosphere until now. A sintered conductor having high conductivity can be obtained even in a solution or even at a low temperature of 150 ° C. or lower.
(B) As described above, the method for producing a sintered conductor according to ( 8 ) has a remarkably high catalytic activity on the surface of the copper alloy fine particles made of copper-zinc. Therefore, sintering can be performed in a temperature range lower by 50 to 40 ° C. than the boiling point of the organic solvent (S).
(C) The sintered conductor made of the copper-zinc alloy according to ( 9 ) is sintered by promoting reduction and sintering on the surface of the copper alloy fine particles. Is 30 nm or more, and has a high conductivity of about 300 μΩcm or less in resistivity. Also, copper-zinc alloys are known to have excellent characteristics such as thermal defects, specific resistance values, adhesion, etc., excellent properties as wiring materials, and high adhesion to glass substrates. (Refer to the Journal of the Japan Institute of Metals, Vol. 72, No. 9, pages 703-707).
(D) The conductive connecting member made of the copper-zinc alloy described in ( 10 ) has high conductivity even when sintered at a low temperature of 200 ° C. or less, and is attached to the joint surface of an electrode terminal, a conductive substrate or the like. Excellent wearing power.
以下、本発明の〔１〕第１の態様である「銅合金微粒子分散液」、〔２〕第２の態様である「焼結導電体の製造方法」、〔３〕第３の態様である「焼結導電体」、及び〔４〕第４の態様である「導電接続部材」について詳述する。
〔１〕第１の態様である「銅合金微粒子分散液」について
本発明の第１の態様である、銅合金微粒子分散液は、銅−亜鉛からなる銅合金微粒子中に３〜３２質量％の亜鉛が固溶している、平均一次粒子径が１〜８０ｎｍの銅合金微粒子が、少なくとも１つのヒドロキシル基を有する有機化合物（Ｓ１）を含有している有機溶媒（Ｓ）中に分散していることを特徴とする。
（１）銅合金微粒子について
銅合金微粒子は、銅−亜鉛からなる、平均一次粒子径が１〜８０ｎｍの銅合金微粒子である。銅合金微粒子は、常温付近で該合金中の亜鉛量が３〜３２質量％の範囲で固有している合金を形成する。銅に亜鉛が含有された合金は、触媒活性を有している。このような触媒活性は合金中の亜鉛濃度が２０質量％で最も大きくなるので（ＮＩＲＥニュース、工業技術院資源環境技術研究所、Ｎｏ．６、２０００年、Ｐ．５〜８参照）、銅−亜鉛からなる銅合金微粒子を焼結する際には、銅合金微粒子中に好ましくは５〜２０質量％の亜鉛が固溶していると、銅単独よりは高い触媒活性が発揮される。これにより、アルコール、ポリオール等の還元能がより高くなり、焼結された導電体の導電性がより高いものを得ることができる。
Hereinafter, [1] “Copper alloy fine particle dispersion” according to the first aspect of the present invention, [2] “Method for producing sintered conductor” according to the second aspect, and [3] Third aspect. The “sintered conductor” and [4] “conductive connection member” as the fourth aspect will be described in detail.
[1] About the “copper alloy fine particle dispersion” as the first aspect The copper alloy fine particle dispersion as the first aspect of the present invention is 3 to 32 mass% in the copper alloy fine particles composed of copper- zinc . Copper alloy fine particles having an average primary particle diameter of 1 to 80 nm in which zinc is dissolved are dispersed in an organic solvent (S) containing an organic compound (S1) having at least one hydroxyl group. It is characterized by that.
(1) About copper alloy fine particles Copper alloy fine particles are copper alloy fine particles comprising copper-zinc and having an average primary particle diameter of 1 to 80 nm. The copper alloy fine particles form an alloy having an intrinsic zinc content in the range of 3 to 32% by mass in the vicinity of room temperature. An alloy containing zinc in copper has catalytic activity. Such catalytic activity is the highest when the zinc concentration in the alloy is 20% by mass (see NIRE News, National Institute of Advanced Industrial Science and Technology, No. 6, 2000, P. 5-8). When sintering copper alloy fine particles made of zinc, when 5 to 20% by mass of zinc is preferably dissolved in the copper alloy fine particles, higher catalytic activity than copper alone is exhibited. Thereby, reducing ability, such as alcohol and polyol, becomes higher, and a sintered conductor having higher conductivity can be obtained.
平均一次粒子径が１〜８０ｎｍの銅合金微粒子は、例えば還元反応水溶液として下記（ｉ）〜（iv）の還元反応水溶液１〜４のいずれかを選択して、ｐＨ４．５〜１３とすれば、通常の電解還元反応により製造することが可能である。
（ｉ）少なくとも硫酸銅、硫酸亜鉛、錯化剤（ａ）、有機分散剤、及び無機分散剤を含む、還元反応水溶液（還元反応水溶液１）、
（ii）少なくとも塩化第一銅、水溶性亜鉛化合物、錯化剤（ｂ）、有機分散剤、及び無機分散剤を含む、還元反応水溶液（還元反応水溶液２）、
（iii）少なくとも酒石酸銅、酸化亜鉛、有機分散剤、及び無機分散剤を含む、還元反応水溶液（還元反応水溶液３）、又は
（iv）少なくとも酢酸銅、酢酸亜鉛、有機分散剤、及び無機分散剤を含む、還元反応水溶液（還元反応水溶液４）
尚、銅合金微粒子を電解還元反応で製造する際、一次粒子の平均粒径の制御は、電極間の電圧、金属イオン濃度、有機分散剤、無機分散剤、温度、時間、ｐＨ等の調整により行うことが可能である。
尚、上記錯化剤（ａ）としてはグリセリン、トリエタノールアミン等、錯化剤（ｂ）としてはチオ硫酸ナトリウム等、を使用でき、有機分散剤、及び無機分散剤は特許文献５、６に記載されているものを使用することができる。
上記製造方法により製造が可能である、本発明の銅−亜鉛からなる銅合金微粒子は、平均一次粒子径が１〜８０ｎｍであり、また平均アスペクト比は好ましくは１０以下、より好ましくは５以下である。尚、一次粒子の平均一次粒子径と平均アスペクトは、透過型電子顕微鏡（ＴＥＭ）で観察して求めることができる。本発明において平均一次粒子径は透過型電子顕微鏡で観察可能な粒子の数平均粒子径である。
If the copper alloy fine particles having an average primary particle diameter of 1 to 80 nm are, for example, selected from the following (i) to (iv) reduction reaction aqueous solutions 1 to 4 as the reduction reaction aqueous solution, the pH is 4.5 to 13: It can be produced by a usual electrolytic reduction reaction.
(I) A reduction reaction aqueous solution (reduction reaction aqueous solution 1) containing at least copper sulfate, zinc sulfate, a complexing agent (a), an organic dispersant, and an inorganic dispersant,
(Ii) a reduction reaction aqueous solution (reduction reaction aqueous solution 2) containing at least cuprous chloride, a water-soluble zinc compound, a complexing agent (b), an organic dispersant, and an inorganic dispersant;
(Iii) Reduction reaction aqueous solution (reduction reaction aqueous solution 3) containing at least copper tartrate, zinc oxide, an organic dispersing agent, and an inorganic dispersing agent, or (iv) At least copper acetate, zinc acetate, an organic dispersing agent, and an inorganic dispersing agent. Reduction reaction aqueous solution (reduction reaction aqueous solution 4)
When producing copper alloy fine particles by electrolytic reduction reaction, the average particle size of primary particles is controlled by adjusting the voltage between electrodes, metal ion concentration, organic dispersant, inorganic dispersant, temperature, time, pH, etc. Is possible.
As the complexing agent (a), glycerin, triethanolamine and the like can be used, and as the complexing agent (b), sodium thiosulfate and the like can be used, and organic dispersants and inorganic dispersants are disclosed in Patent Documents 5 and 6. What is described can be used.
The copper alloy fine particles comprising copper-zinc of the present invention that can be produced by the above production method have an average primary particle diameter of 1 to 80 nm and an average aspect ratio of preferably 10 or less, more preferably 5 or less. is there. In addition, the average primary particle diameter and average aspect of a primary particle can be calculated | required by observing with a transmission electron microscope (TEM). In the present invention, the average primary particle diameter is the number average particle diameter of particles observable with a transmission electron microscope.
（２）有機溶媒（Ｓ）について
有機溶媒（Ｓ）は、少なくとも１つのヒドロキシル基を有する有機化合物（Ｓ１）を含有している有機溶媒である。このような有機溶媒を選択することにより、本発明の銅合金微粒子を焼結する際に、有機化合物（Ｓ１）が還元雰囲気を形成して１５０℃以下の比較的低温でも焼結が可能となる。このような還元性雰囲気は、銅−亜鉛からなる銅合金微粒子を焼結する際に、有機化合物（Ｓ１）に結合しているヒドロキシル基部分が該銅合金微粒子の触媒作用により還元されて水素ガスを発生することにより形成されると推定される。この場合、銅−亜鉛からなる銅合金微粒子以外で、触媒活性を示さないか低い触媒活性しか有しない金属、合金の場合には、１つのヒドロキシル基を有する有機化合物（Ｓ１１）では還元性雰囲気が形成されず、２つ以上のヒドロキシル基を有する有機化合物（Ｓ１２）を多く含む有機溶媒（Ｓ）の使用が必要となる。
(2) Organic solvent (S) The organic solvent (S) is an organic solvent containing an organic compound (S1) having at least one hydroxyl group. By selecting such an organic solvent, when the copper alloy fine particles of the present invention are sintered, the organic compound (S1) forms a reducing atmosphere and can be sintered even at a relatively low temperature of 150 ° C. or lower. . In such a reducing atmosphere, when the copper alloy fine particles made of copper-zinc are sintered, the hydroxyl group bonded to the organic compound (S1) is reduced by the catalytic action of the copper alloy fine particles so that hydrogen gas It is presumed that it is formed by generating In this case, in the case of a metal or alloy having no catalytic activity or low catalytic activity other than copper alloy fine particles composed of copper-zinc, the reducing compound has a reducing atmosphere in the organic compound (S11) having one hydroxyl group. It is not formed, and it is necessary to use an organic solvent (S) containing a large amount of an organic compound (S12) having two or more hydroxyl groups.
有機溶媒（Ｓ）中の、少なくとも１つのヒドロキシル基を有する有機化合物（Ｓ１）の含有量は、５体積％以上が好ましく、より好ましくは２０体積％以上、更に好ましくは４０体積％以上である。有機溶媒（Ｓ）中の、少なくとも１つのヒドロキシル基を有する有機化合物（Ｓ１）濃度の上限範囲は特に制限されるものではなく、他の有機溶媒との組合せなどにより適宜設定することができる。又、有機溶媒（Ｓ）の常圧における沸点は、前記銅−亜鉛からなる銅合金微粒子の触媒活性と銅合金微粒子の焼結温度を考慮すると、１４０℃以上が好ましい。又、２５０℃以下の低温で熱処理する事が望ましい点から有機溶媒（Ｓ）の常圧における沸点が３００℃以下であることが好ましい。このような有機溶媒（Ｓ）の沸点は、１つのヒドロキシル基を有する有機化合物（Ｓ１１）に２つ以上のヒドロキシル基を有する有機化合物（Ｓ１２）を配合して、有機溶媒（Ｓ）の常圧における沸点が１４０℃以上３００℃以下に調整することが可能である。 The content of the organic compound (S1) having at least one hydroxyl group in the organic solvent (S) is preferably 5% by volume or more, more preferably 20% by volume or more, and still more preferably 40% by volume or more. The upper limit of the concentration of the organic compound (S1) having at least one hydroxyl group in the organic solvent (S) is not particularly limited, and can be appropriately set depending on the combination with other organic solvents. Further, the boiling point of the organic solvent (S) at normal pressure is preferably 140 ° C. or higher in consideration of the catalytic activity of the copper alloy fine particles made of copper-zinc and the sintering temperature of the copper alloy fine particles. Moreover, it is preferable that the boiling point in the normal pressure of an organic solvent (S) is 300 degrees C or less from the point that it is desirable to heat-process at a low temperature of 250 degrees C or less. The boiling point of such an organic solvent (S) is obtained by blending an organic compound (S12) having two or more hydroxyl groups into an organic compound (S11) having one hydroxyl group, and the normal pressure of the organic solvent (S). The boiling point in can be adjusted to 140 ° C. or more and 300 ° C. or less.
前記有機化合物（Ｓ１）中にヒドロキシル基が結合している炭素原子に１又は２の水素原子が結合している有機化合物が含有されていると、銅−亜鉛合金微粒子による触媒作用を受けて、水素ガスを発生し易くなるので、銅−亜鉛合金微粒子の焼結が促進される。
前記１つのヒドロキシル基を有する有機化合物（Ｓ１１）として、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、２−メチル−１−プロパノール、２−メチル−２−プロパノール、２，２−ジメチル−１−プロパノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、３−メチル−１−ブタノール、２−メチル−１−ブタノール、２，２ジメチル−１−プロパノール、３−メチル−２−ブタノール、２−メチル−２−ブタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、２−メチル−２−ヘキサノール、２−メチル−３−ヘキサノール、１−ヘプタノール、２−ヘプタノール、４−ヘプタノール、２−エチル−１−ヘキサノール、１−オクタノール、及び２−オクタノールから選択される１種又は２種以上が挙げられる。
When the organic compound (S1) contains an organic compound in which one or two hydrogen atoms are bonded to a carbon atom to which a hydroxyl group is bonded, the organic compound (S1) is catalyzed by copper-zinc alloy fine particles, Since hydrogen gas is easily generated, sintering of copper-zinc alloy fine particles is promoted.
As the organic compound having one hydroxyl group (S11), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2 dimethyl-1-propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-heptanol, 2- Heptanol, 4-heptanol, 2-ethyl-1-hexanol, 1-octanol, and One or more selected from 2-octanol and the like.
前記２つ以上のヒドロキシル基を有する有機化合物（Ｓ１２）として、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−ブテン−１，４−ジオール、２，３−ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、グリセロール、１，１，１−トリスヒドロキシメチルエタン、２−エチル−２−ヒドロキシメチル−１，３−プロパンジオール、１，２，６−ヘキサントリオール、１，２，３−ヘキサントリオール、及び１，２，４−ブタントリオールの中から選択される１種又は２種以上が挙げられる。 Examples of the organic compound (S12) having two or more hydroxyl groups include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, 2-butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1,1,1-trishydroxymethylethane, 2-ethyl-2 One or more selected from hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, and 1,2,4-butanetriol Is mentioned.
また、有機溶媒（Ｓ１２）として、トレイトール、エリトリト−ル、ペンタエリスリト−ル、ペンチト−ル、キシリトール、リビトール、アラビトール、ヘキシト−ル、マンニトール、ソルビトール、ズルシトール、グリセルアルデヒド、ジオキシアセトン、トレオース、エリトルロース、エリトロース、アラビノース、リボース、リブロース、キシロース、キシルロース、リキソース、グルコ−ス、フルクト−ス、マンノース、イドース、ソルボース、グロース、タロース、タガトース、ガラクトース、アロース、アルトロース、ラクト−ス、キシロ−ス、アラビノ−ス、イソマルト−ス、グルコヘプト−ス、ヘプト−ス、マルトトリオース、ラクツロース、及びトレハロース、等の糖類も使用することが可能であるが、これらの中で融点が高いものについては他の有機溶媒と混合して使用することができる。
有機化合物（Ｓ１）は、優れた分散性を有しており、一般に時間の経過により分散溶液中の微粒子同士は接合する傾向にあるが、有機化合物（Ｓ１）を混合溶媒中に存在させるとこのような接合をより効果的に抑制して、分散液の一層の長期安定化を図ることが可能になる。また有機化合物（Ｓ１）を有機溶媒（Ｓ）中に存在させると、その微粒子分散液を基板上に塗布して焼結した際、その焼結膜の均一性が向上し、導電性の高い焼成膜を得ることが出来る。
Further, as the organic solvent (S12), threitol, erythritol, pentaerythritol, pentitol, xylitol, ribitol, arabitol, hexitol, mannitol, sorbitol, dulcitol, glyceraldehyde, dioxyacetone, Throse, erythrulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, gulose, talose, tagatose, galactose, allose, altrose, lactose, xylo -Sugars such as sucrose, arabinose, isomaltose, glucoheptose, heptose, maltotriose, lactulose and trehalose can also be used, of which the melting point For high it can be used as a mixture with other organic solvents.
The organic compound (S1) has excellent dispersibility, and generally the fine particles in the dispersion solution tend to join with the passage of time. However, when the organic compound (S1) is present in the mixed solvent, Such bonding can be suppressed more effectively, and further long-term stabilization of the dispersion can be achieved. In addition, when the organic compound (S1) is present in the organic solvent (S), when the fine particle dispersion is applied on the substrate and sintered, the uniformity of the sintered film is improved, and the fired film having high conductivity. Can be obtained.
有機溶媒（Ｓ）として、有機化合物（Ｓ１）以外に使用できる溶媒は特に限定されるものではないが、以下に記載する有機溶媒（Ａ）、有機溶媒（Ｂ）等が挙げられる。
有機溶媒（Ａ）は、アミド基（−ＣＯＮＨ−）を有する化合物であり、特に比誘電率が高いものが好ましい。アミド基を有する有機溶媒（Ａ）として、Ｎ−メチルアセトアミド（１９１．３ ａｔ ３２℃）、Ｎ−メチルホルムアミド（１８２．４ ａｔ ２０℃）、Ｎ−メチルプロパンアミド（１７２．２ ａｔ ２５℃）、ホルムアミド（１１１．０ ａｔ ２０℃）、Ｎ，Ｎ−ジメチルアセトアミド（３７．７８ ａｔ ２５℃）、１，３−ジメチル−２−イミダゾリジノン（３７．６ ａｔ ２５℃）、Ｎ，Ｎ−ジメチルホルムアミド（３６．７ ａｔ ２５℃）、１−メチル−２−ピロリドン（３２．５８ ａｔ ２５℃）、ヘキサメチルホスホリックトリアミド（２９．０ ａｔ ２０℃）、２−ピロリジノン、ε−カプロラクタム、アセトアミド等が挙げられるが、これらを混合して使用することもできる。尚、上記アミド基を有する化合物名の後の括弧中の数字は各溶媒の測定温度における比誘電率を示す。これらの中でも比誘電率が１００以上である、Ｎ−メチルアセトアミド、Ｎ−メチルホルムアミド、ホルムアミド、アセトアミドなどが好適に使用できる。尚、Ｎ−メチルアセトアミド（融点：２６〜２８℃）のように常温で固体の場合には他の溶媒と混合して作業温度で液状として使用することができる。有機溶媒（Ａ）は、混合溶媒中で微粒子の分散性と保存安定性を向上する作用を有し、また本発明の微粒子分散液を基板上に塗布後焼成して得られる焼成膜の導電性を向上する作用をも有する。
As the organic solvent (S), a solvent that can be used other than the organic compound (S1) is not particularly limited, and examples thereof include the organic solvent (A) and the organic solvent (B) described below.
The organic solvent (A) is a compound having an amide group (—CONH—), and preferably has a high relative dielectric constant. As an organic solvent (A) having an amide group, N-methylacetamide (191.3 at 32 ° C.), N-methylformamide (182.4 at 20 ° C.), N-methylpropanamide (172.2 at 25 ° C.) , Formamide (111.0 at 20 ° C.), N, N-dimethylacetamide (37.78 at 25 ° C.), 1,3-dimethyl-2-imidazolidinone (37.6 at 25 ° C.), N, N— Dimethylformamide (36.7 at 25 ° C.), 1-methyl-2-pyrrolidone (32.58 at 25 ° C.), hexamethylphosphoric triamide (29.0 at 20 ° C.), 2-pyrrolidinone, ε-caprolactam, Acetamide and the like can be mentioned, but these can also be mixed and used. The number in parentheses after the name of the compound having an amide group indicates the relative dielectric constant at the measurement temperature of each solvent. Among these, N-methylacetamide, N-methylformamide, formamide, acetamide and the like having a relative dielectric constant of 100 or more can be preferably used. In addition, when it is solid at normal temperature like N-methylacetamide (melting point: 26-28 degreeC), it can mix with another solvent and can be used as a liquid state at working temperature. The organic solvent (A) has the effect of improving the dispersibility and storage stability of the fine particles in the mixed solvent, and the conductivity of the fired film obtained by applying the fine particle dispersion of the present invention to the substrate and baking it. It also has the effect of improving.
有機溶媒（Ｂ）として、一般式Ｒ１−Ｏ−Ｒ２（Ｒ１、Ｒ２は、それぞれ独立にアルキル基で、炭素原子数は１〜４である。）で表されるエーテル系化合物（Ｂ１）、一般式Ｒ４−Ｃ（＝Ｏ）−Ｒ５（Ｒ４、Ｒ５は、それぞれ独立にアルキル基で、炭素原子数は１〜２である。）で表されるケトン系化合物（Ｂ２）、及び一般式Ｒ６−（Ｎ−Ｒ７）−Ｒ８（Ｒ６、Ｒ７、Ｒ８は、それぞれ独立にアルキル基、又は水素原子で、炭素原子数は０〜２である。）で表されるアミン系化合物（Ｂ３）、の中から選択される１種又は２種以上が挙げられる。
前記エーテル系化合物（Ｂ１）としては、ジエチルエーテル（３５℃）、メチルプロピルエーテル（３１℃）、ジプロピルエーテル（８９℃）、ジイソプロピルエーテル（６８℃）、メチル−ｔ−ブチルエーテル（５５．３℃）、ｔ−アミルメチルエーテル（８５℃）、ジビニルエーテル（２８．５℃）、エチルビニルエーテル（３６℃）、アリルエーテル（９４℃）等が例示出来る。
前記ケトン系化合物（Ｂ２）としては、アセトン（５６．５℃）、メチルエチルケトン（７９．５℃）、ジエチルケトン（１００℃）等が例示できる。
また、前記アミン系化合物（Ｂ３）としては、トリエチルアミン（８９．７℃）、ジエチルアミン（５５．５℃）等が例示できる。
As the organic solvent (B), an ether compound represented by the general formula R 1 —O—R 2 (wherein R 1 and R 2 are each independently an alkyl group and has 1 to 4 carbon atoms). B1), a ketone compound represented by the general formula R 4 —C (═O) —R 5 (wherein R 4 and R 5 are each independently an alkyl group and has 1 to 2 carbon atoms). B2), and the general formula R 6 - (N-R 7 ) -R 8 (R 6, R 7, R 8 each independently represent an alkyl group, or a hydrogen atom, the number of carbon atoms is 0-2. 1 type (s) or 2 or more types selected from among the amine compounds (B3) represented by
Examples of the ether compound (B1) include diethyl ether (35 ° C.), methyl propyl ether (31 ° C.), dipropyl ether (89 ° C.), diisopropyl ether (68 ° C.), methyl-t-butyl ether (55.3 ° C.). ), T-amyl methyl ether (85 ° C.), divinyl ether (28.5 ° C.), ethyl vinyl ether (36 ° C.), allyl ether (94 ° C.) and the like.
Examples of the ketone compound (B2) include acetone (56.5 ° C.), methyl ethyl ketone (79.5 ° C.), diethyl ketone (100 ° C.) and the like.
Examples of the amine compound (B3) include triethylamine (89.7 ° C.) and diethylamine (55.5 ° C.).
有機溶媒（Ｂ）は、混合溶媒中で溶媒分子間の相互作用を低下させ、分散粒子の溶媒に対する親和性を向上する作用を有していると考えられる。このような効果は一般に沸点の低い溶媒において期待され、特に常温における沸点が１００℃以下の有機溶媒は、有効な溶媒分子間の相互作用を低減する効果が得られることから好ましい。有機溶媒（Ｂ）の中でも特にエーテル系化合物（Ｂ１）が、その溶媒分子間の相互作用を低減する効果が大きいことから好ましい。
更に、上記以外の他の有機溶媒成分を配合する場合には、テトラヒドロフラン、ジグライム、エチレンカルボナート、プロピレンカルボナート、スルホラン、ジメチルスルホキシド等の極性有機溶媒を使用することができる。
The organic solvent (B) is considered to have an action of reducing the interaction between solvent molecules in the mixed solvent and improving the affinity of the dispersed particles to the solvent. Such an effect is generally expected in a solvent having a low boiling point. Particularly, an organic solvent having a boiling point of 100 ° C. or less at normal temperature is preferable because an effect of reducing the interaction between effective solvent molecules is obtained. Among the organic solvents (B), ether compounds (B1) are particularly preferable because they have a large effect of reducing the interaction between the solvent molecules.
Furthermore, when other organic solvent components other than the above are blended, polar organic solvents such as tetrahydrofuran, diglyme, ethylene carbonate, propylene carbonate, sulfolane, dimethyl sulfoxide, and the like can be used.
〔２〕第２の態様である「焼結導電体の製造方法」について
第２の態様である「焼結導電体の製造方法」は、第１の態様である「銅合金微粒子分散液」を基板に塗布し、大気雰囲気中、もしくは不活性ガス雰囲気中で、有機溶媒（Ｓ）の沸点よりも５０〜４０℃低い温度範囲で焼結することにより、基板上に銅合金微粒子の導電体を形成することを特徴とする。
第１の態様である、銅−亜鉛からなる銅合金微粒子中に３〜３２質量％の亜鉛が固溶している、平均一次粒子径が１〜８０ｎｍの銅合金微粒子が、有機溶媒（Ｓ）に分散されている銅合金微粒子分散液は、例えば百数拾℃から２００℃程度の比較的低温でかつ水素ガス等の還元剤を使用することなくインクジェット等により基板上に配置して焼成し、導電性を有する焼結導電体を形成することが可能である。
前述の通り、銅−亜鉛からなる銅合金微粒子はその合金表面の触媒活性度が著しく高いので、有機化合物（Ｓ１）から水素ガスを発生させる還元作用を発揮するので、１５０℃以下での焼結温度でも焼結導電体を形成することが可能となる。
上記基板は特に制限はなく使用目的等により、ガラス、ポリイミド等が使用でき、焼成前に予め乾燥工程を設けることが望ましい。乾燥条件は、使用する有機溶媒（Ｓ）にもよるが例えば１００〜２００℃で１５〜３０分程度であり、焼成条件は、塗布厚みにもよるが有機溶媒（Ｓ）の沸点よりも５０〜４０℃低い温度範囲で焼結することが望ましい。例えば１９０〜２５０℃、２０〜４０分間程度で焼結することができる。
[2] About “Method for Producing Sintered Conductor” as Second Aspect “Method for Producing Sintered Conductor” as Second Aspect is the “Copper Alloy Fine Particle Dispersion” as the first aspect. The conductor of copper alloy fine particles is applied on the substrate by applying it to the substrate and sintering it in an air atmosphere or in an inert gas atmosphere at a temperature range lower by 50 to 40 ° C. than the boiling point of the organic solvent (S). It is characterized by forming.
The copper alloy fine particles having an average primary particle diameter of 1 to 80 nm, in which 3 to 32% by mass of zinc is solid-solved in copper alloy fine particles made of copper-zinc , which is the first aspect, are an organic solvent (S). The copper alloy fine particle dispersion dispersed in the substrate is fired by placing it on the substrate by inkjet or the like without using a reducing agent such as hydrogen gas at a relatively low temperature of, for example, hundreds of degrees Celsius to 200 ° C., It is possible to form a sintered conductor having conductivity.
As described above, the copper alloy fine particles made of copper-zinc have a remarkably high catalytic activity on the surface of the alloy, so that the reduction effect of generating hydrogen gas from the organic compound (S1) is exhibited. A sintered conductor can be formed even at a temperature.
There is no restriction | limiting in particular in the said board | substrate, Glass, a polyimide, etc. can be used by a use purpose etc., It is desirable to provide a drying process previously before baking. Although drying conditions depend on the organic solvent (S) to be used, it is, for example, about 15 to 30 minutes at 100 to 200 ° C., and the firing conditions are 50 to 50% higher than the boiling point of the organic solvent (S), depending on the coating thickness. It is desirable to sinter at a temperature range as low as 40 ° C. For example, sintering can be performed at 190 to 250 ° C. for about 20 to 40 minutes.
〔３〕第３の態様である「焼結導電体」について
第３の態様である「焼結導電体」は、第２の態様の「焼結導電体の製造方法」によって製造された、結晶子径が３０ｎｍ以上であることを特徴とする。第２の態様である「焼結導電体の製造方法」により得られた第３の態様の焼結導電体は、前記銅合金微粒子の表面での還元と焼結が促進されて焼結された結晶粒子が成長する結果、結晶子径が３０ｎｍ以上の焼結導電体となる。このような結晶子径の大きい焼結導電体は、抵抗率が３００μΩｃｍ以下程度の高い導電性を有する。銅−亜鉛合金微粒子焼結体は、前述の通り、銅−スズ合金微粒子焼結体よりも耐酸化性、電気伝導率、熱伝導率、および基板との密着力が高い。
[3] About the “sintered conductor” as the third aspect The “sintered conductor” as the third aspect is a crystal manufactured by the “method for manufacturing a sintered conductor” according to the second aspect. The child diameter is 30 nm or more. The sintered conductor of the third aspect obtained by the “method for producing a sintered conductor” which is the second aspect was sintered by promoting reduction and sintering on the surface of the copper alloy fine particles. As a result of the growth of crystal grains, a sintered conductor having a crystallite diameter of 30 nm or more is obtained. Such a sintered conductor having a large crystallite diameter has high conductivity with a resistivity of about 300 μΩcm or less. As described above, the copper-zinc alloy fine particle sintered body has higher oxidation resistance, electrical conductivity, thermal conductivity, and adhesion to the substrate than the copper-tin alloy fine particle sintered body.
〔４〕第４の態様である「導電接続部材」について
第４の態様の「導電接続部材」は、前記第１の態様に記載された銅合金微粒子分散液（以下、銅合金微粒子分散液（Ａ）ということがある）を電子部品における半導体素子もしくは回路基板の電極端子又は導電性基板の接合面に載せた後、該銅合金微粒子分散液上に更に接続する他方の電極端子又は導電性基板の接合面を配置して加熱処理により焼結して形成された導電接続部材である。
[4] About the “conductive connection member” according to the fourth aspect The “conductive connection member” according to the fourth aspect is the copper alloy fine particle dispersion described in the first aspect (hereinafter, copper alloy fine particle dispersion ( A)) is placed on the electrode surface of the semiconductor element or circuit board of the electronic component or the bonding surface of the conductive substrate, and the other electrode terminal or conductive substrate further connected on the copper alloy fine particle dispersion This is a conductive connection member formed by arranging the joint surfaces and sintering by heat treatment.
（１）導電接続部材の作製
導電接続部材としては半導体素子間を接合するための導電性バンプ、半導体素子と導電性基板間を接合するための導電性ダイボンド部等が挙げられるがこれらに限定されない。
導電性バンプは、銅合金微粒子分散液（Ａ）を電子部品における半導体素子もしくは回路基板の電極端子の接合面に載せ（塗布、印刷等も含まれる）、該銅合金微粒子分散液（Ａ）上に更に接続する他方の電極端子の接合面を配置した後、加熱処理、又は加圧下に加熱処理により焼結して形成される。前記接続する他方の電極端子にはワイヤボンディングを行う場合の金ワイヤ等のワイヤも含まれる。尚、前記銅合金微粒子分散液（Ａ）上に更に接続する他方の電極端子の接合面を配置する際に位置合わせを行うことが望ましい。
導電性ダイボンド部は、通常、銅合金微粒子分散液（Ａ）を電子部品における回路基板の接合面に載せ（塗布、印刷等も含まれる）、該銅合金微粒子分散液（Ａ）上に更に接続する他方の電極端子の接合面を配置した後、加熱処理、又は加圧下に加熱処理により焼結して形成される。
(1) Production of conductive connection member Examples of the conductive connection member include, but are not limited to, a conductive bump for bonding between semiconductor elements, and a conductive die bond part for bonding between a semiconductor element and a conductive substrate. .
The conductive bump is formed by placing the copper alloy fine particle dispersion (A) on the bonding surface of the electrode terminal of the semiconductor element or circuit board in the electronic component (including coating and printing), and on the copper alloy fine particle dispersion (A). After the bonding surface of the other electrode terminal to be further connected is arranged, it is formed by sintering by heat treatment or heat treatment under pressure. The other electrode terminal to be connected includes a wire such as a gold wire when wire bonding is performed. In addition, it is desirable to perform alignment when arranging the joining surface of the other electrode terminal to be further connected on the copper alloy fine particle dispersion (A).
The conductive die bond part usually places the copper alloy fine particle dispersion (A) on the bonding surface of the circuit board in the electronic component (including coating and printing) and further connects on the copper alloy fine particle dispersion (A). After the bonding surface of the other electrode terminal to be arranged is disposed, the heat treatment is performed or the heat treatment is performed under pressure and the heat treatment is performed.
前記加圧下の加熱処理は、両電極端子間、又は電極端子と基板間の加圧により導電接続部材前躯体と両電極端子接合面、又は電極端子と導電性基板間との接合を確実にするか、または導電接続部材前躯体に適切な変形を生じさせて電極端子接合面との確実な接合を行うことができるとともに、導電接続部材前躯体と電極端子接合面との接合面積が大きくなり、接合信頼性を一層向上することができる。また、半導体素子と導電接続部材前躯体間を加圧型ヒートツ−ル等を用いて加圧下で焼成すると、接合部での焼結性が向上してより良好な接合部が得られる。
前記両電極端子間、又は電極端子と基板間の加圧は、０．５〜１５ＭＰａが好ましい。
The heat treatment under pressure ensures the bonding between the conductive connecting member precursor and both electrode terminal bonding surfaces, or between the electrode terminals and the conductive substrate by pressing between the electrode terminals or between the electrode terminals and the substrate. Or, it is possible to cause an appropriate deformation in the conductive connection member precursor and perform reliable bonding with the electrode terminal joint surface, and the joint area between the conductive connection member precursor and the electrode terminal joint surface is increased. Bonding reliability can be further improved. Further, when the semiconductor element and the conductive connecting member precursor are fired under pressure using a pressure-type heat tool or the like, the sinterability at the joint is improved and a better joint is obtained.
The pressure between the electrode terminals or between the electrode terminal and the substrate is preferably 0.5 to 15 MPa.
銅合金微粒子分散液（Ａ）を半導体素子の電極端子等の上に載せて導電性バンプ前躯体、導電性ダイボンド部前躯体等の導電接続部材前躯体を形成する手段としては、例えば公知のスクリーン印刷、後述するレジスト等により、電極端子の接続部に開口部を形成して該開口部に銅合金微粒子分散液（Ａ）を載せるために塗布する方法等が挙げられる。スクリーン印刷を使用する場合には、半導体素子の電極端子等の上に版膜（レジスト）が設けられたスクリーン版を配置して、その上に銅合金微粒子分散液（Ａ）を載せてスキージで該分散液（Ａ）を摺動すると、銅合金微粒子分散液（Ａ）はレジストのない部分のスクリーンを通過して、電極端子等の上に転移して、導電性バンプ前躯体、導電性ダイボンド部前躯体等の導電接続部材前躯体が形成される。
銅合金微粒子分散液（Ａ）を充填するための開口部形成方法としては、露光・現像工程を経て感光性樹脂層にパターンを形成するフォトリソグラフィー方法、レーザー光、電子線、イオンビーム等の高エネルギー線を素子上に設けた絶縁樹脂層に照射して、加熱による溶融もしくは樹脂の分子結合を切断するアブレーションにより該樹脂層に開口部を形成する方法がある。これらの中で、実用性の点からフォトリソグラフィー法、又はレーザー光を用いたアブレーションによる開口部形成方法が好ましい。加熱処理（焼結）後に、半導体素子上の電極端子と、回路基板の電極端子とが電気的接続を確保できるように接触させるための位置合わせは、例えば、半導体素子上の電極端子と、テープリール等で搬送されてきた導電性基板の接続電極端子部とを光学装置等を用いて行うことができる。
As a means for forming a conductive connection member precursor such as a conductive bump precursor or a conductive die bond part precursor by placing the copper alloy fine particle dispersion (A) on an electrode terminal or the like of a semiconductor element, for example, a known screen Examples thereof include a method of forming an opening at the connection portion of the electrode terminal by printing, a resist described later, and applying the copper alloy fine particle dispersion (A) on the opening. When screen printing is used, a screen plate provided with a plate film (resist) is placed on an electrode terminal or the like of a semiconductor element, and a copper alloy fine particle dispersion (A) is placed on the screen plate with a squeegee. When the dispersion liquid (A) is slid, the copper alloy fine particle dispersion liquid (A) passes through the screen where there is no resist and is transferred onto the electrode terminal or the like to form a conductive bump precursor, a conductive die bond. A conductive connecting member precursor such as a part precursor is formed.
As an opening forming method for filling the copper alloy fine particle dispersion (A), a photolithographic method in which a pattern is formed on the photosensitive resin layer through an exposure / development process, a laser beam, an electron beam, an ion beam, etc. There is a method of irradiating an insulating resin layer provided on an element with an energy beam and forming an opening in the resin layer by ablation that melts by heating or breaks a molecular bond of the resin. Among these, from the viewpoint of practicality, a photolithography method or an opening formation method by ablation using laser light is preferable. After the heat treatment (sintering), the electrode terminal on the semiconductor element and the electrode terminal on the circuit board are aligned so as to ensure electrical connection, for example, the electrode terminal on the semiconductor element and the tape The connection electrode terminal portion of the conductive substrate conveyed by a reel or the like can be performed using an optical device or the like.
半導体素子の電極端子上等の上に形成され、対となる端子電極と接している状態のバンプ前駆体、ダイボンド部前駆体等の導電接続部材前駆体は、好ましくは２００℃以下の、有機溶媒（Ｓ）の沸点よりも５０〜４０℃低い温度範囲で加熱処理（焼結）して導電接続部材を形成することにより、半導体素子の電極端子等と相対する端子電極等を該導電接続部材を介して電気的、機械的に接合する。 Conductive connection member precursors such as bump precursors and die bond part precursors formed on the electrode terminals of the semiconductor element and in contact with the paired terminal electrodes are preferably an organic solvent at 200 ° C. or lower. The conductive connection member is formed by heat treatment (sintering) in a temperature range lower by 50 to 40 ° C. than the boiling point of (S), so that the terminal electrode facing the electrode terminal of the semiconductor element is connected to the conductive connection member. It is joined electrically and mechanically.
以下に本発明を実施例により具体的に説明するが、本発明は以下の実施例に記載される方法に限定されるものではない。
［実施例１］
まず、銅イオンとして酢酸銅０．１モル／Ｌ、亜鉛イオンとして酢酸亜鉛０．００３モル／Ｌ、無機分散剤として酢酸ナトリウム０．０１モル／Ｌ、有機分散剤としてポリビニルピロリドン（数平均分子量：３５００）５ｇ／Ｌを含有する１０００ｍｌの還元反応水溶液を調製した。ｐＨは約５．０であった。
次にこの溶液中で２ｃｍ四方の銅シートからなる陽極（アノード電極）と白金基板からなる陰極（カソード電極）間を浴温２５℃、電流密度１５Ａ／ｄｍ２で３０分間通電を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅と亜鉛からなる合金微粒子を得た。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the methods described in the following examples.
[Example 1]
First, copper acetate 0.1 mol / L as copper ions, zinc acetate 0.003 mol / L as zinc ions, sodium acetate 0.01 mol / L as inorganic dispersant, polyvinylpyrrolidone as organic dispersant (number average molecular weight: 3500) A 1000 ml reduction reaction aqueous solution containing 5 g / L was prepared. The pH was about 5.0.
Next, in this solution, a current was applied between an anode (anode electrode) made of a 2 cm square copper sheet and a cathode (cathode electrode) made of a platinum substrate at a bath temperature of 25 ° C. and a current density of 15 A / dm 2 for 30 minutes. The obtained colloidal solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain alloy fine particles composed of copper and zinc.
その後、得られた銅合金微粒子と５０ｍｌのエタノールとを試験管に入れ、超音波ホモジナイザーを用いてよく撹拌した後、遠心分離機で粒子成分を回収するエタノール洗浄を３回、続いて、同じく試験管中で、得られた銅合金微粒子と５０ｍｌの１−ブタノールとを入れよく撹拌した後、遠心分離機で銅合金微粒子を回収する１−ブタノール洗浄を３回行った。
上記の方法によって得られた銅合金微粒子を、分散溶媒である１−オクタノールに添加、超音波ホモジナイザーを用いて攪拌し、本発明の銅合金微粒子分散液が得られた。得られた銅合金微粒子分散液をカーボン蒸着された銅メッシュ上に塗布後、乾燥し、上記透過型電子顕微鏡（ＴＥＭ）で観察を行ったところ、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９７質量％、亜鉛３質量％の合金（以下、銅−３％亜鉛合金のように表示することがある。）であった。また、動的光散乱型粒度分布測定装置による測定で、二次凝集サイズが５００ｎｍ以下であることが確認できた。
After that, the obtained copper alloy fine particles and 50 ml of ethanol are put in a test tube, stirred well using an ultrasonic homogenizer, and then washed with ethanol three times to collect the particle components with a centrifuge, followed by the same test. In a tube, the obtained copper alloy fine particles and 50 ml of 1-butanol were put and stirred well, and then 1-butanol washing for recovering the copper alloy fine particles with a centrifuge was performed three times.
The copper alloy fine particles obtained by the above method were added to 1-octanol as a dispersion solvent and stirred using an ultrasonic homogenizer to obtain a copper alloy fine particle dispersion of the present invention. The obtained copper alloy fine particle dispersion was applied onto a carbon-deposited copper mesh, dried, and observed with the transmission electron microscope (TEM). The primary particle diameter of 90% or more of the particles was 5 to 5%. In the range of 50 nm, the average aspect ratio was 1.5. Further, as a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition is an alloy of 97% by mass of copper and 3% by mass of zinc (hereinafter sometimes referred to as a copper-3% zinc alloy). Met. Moreover, it was confirmed by the measurement with a dynamic light scattering type particle size distribution measuring device that the secondary aggregation size was 500 nm or less.
［実施例２］
酢酸亜鉛濃度を０．０１モル／Ｌとした以外は実施例１と同様に、還元反応水溶液を調製し、電解還元反応を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅と亜鉛からなる合金微粒子を得た。
その後、得られた銅合金微粒子と５０ｍｌのエタノールとを試験管に入れ、超音波ホモジナイザーを用いてよく撹拌した後、遠心分離機で粒子成分を回収するエタノール洗浄を３回、続いて、同じく試験管中で、得られた銅合金微粒子と５０ｍｌの１−ブタノールとを入れよく撹拌した後、遠心分離機で銅合金微粒子を回収する１−ブタノール洗浄を３回行った。
上記の方法によって得られた銅合金微粒子を、分散溶媒である１−オクタノールに添加、超音波ホモジナイザーを用いて攪拌し、本発明の銅合金微粒子分散液が得られた。
得られた銅合金微粒子分散液をカーボン蒸着された銅メッシュ上に塗布後、乾燥し、上記透過型電子顕微鏡（ＴＥＭ）で観察を行ったところ、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９０質量％、亜鉛１０質量％の合金であった。
また、動的光散乱型粒度分布測定装置による測定で、二次凝集サイズが５００ｎｍ以下であることが確認できた。
[Example 2]
A reduction reaction aqueous solution was prepared and an electrolytic reduction reaction was performed in the same manner as in Example 1 except that the zinc acetate concentration was 0.01 mol / L. The obtained colloidal solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain alloy fine particles composed of copper and zinc.
After that, the obtained copper alloy fine particles and 50 ml of ethanol are put in a test tube, stirred well using an ultrasonic homogenizer, and then washed with ethanol three times to collect the particle components with a centrifuge, followed by the same test. In a tube, the obtained copper alloy fine particles and 50 ml of 1-butanol were put and stirred well, and then 1-butanol washing for recovering the copper alloy fine particles with a centrifuge was performed three times.
The copper alloy fine particles obtained by the above method were added to 1-octanol as a dispersion solvent and stirred using an ultrasonic homogenizer to obtain a copper alloy fine particle dispersion of the present invention.
The obtained copper alloy fine particle dispersion was applied onto a carbon-deposited copper mesh, dried, and observed with the transmission electron microscope (TEM). The primary particle diameter of 90% or more of the particles was 5 to 5%. In the range of 50 nm, the average aspect ratio was 1.5. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 90% by mass of copper and 10% by mass of zinc.
Moreover, it was confirmed by the measurement with a dynamic light scattering type particle size distribution measuring device that the secondary aggregation size was 500 nm or less.
［実施例３］
酢酸亜鉛濃度を０．０５モル／Ｌとした以外は実施例１と同様に、還元反応水溶液を調製し、電解還元反応を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅と亜鉛からなる合金微粒子を得た。
その後、得られた銅合金微粒子と５０ｍｌのエタノールとを試験管に入れ、超音波ホモジナイザーを用いてよく撹拌した後、遠心分離機で粒子成分を回収するエタノール洗浄を３回、続いて、同じく試験管中で、得られた銅合金微粒子と５０ｍｌの１−ブタノールとを入れよく撹拌した後、遠心分離機で銅合金微粒子を回収する１−ブタノール洗浄を３回行った。
上記の方法によって得られた銅合金微粒子を、分散溶媒である１−オクタノールに添加、超音波ホモジナイザーを用いて攪拌し、本発明の銅合金微粒子分散液が得られた。
得られた銅合金微粒子分散液をカーボン蒸着された銅メッシュ上に塗布後、乾燥し、上記透過型電子顕微鏡（ＴＥＭ）で観察を行ったところ、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅７０質量％、亜鉛３０質量％の合金であった。また、動的光散乱型粒度分布測定装置による測定で、二次凝集サイズが５００ｎｍ以下であることが確認できた。
[Example 3]
A reduction reaction aqueous solution was prepared and an electrolytic reduction reaction was performed in the same manner as in Example 1 except that the zinc acetate concentration was 0.05 mol / L. The obtained colloidal solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain alloy fine particles composed of copper and zinc.
After that, the obtained copper alloy fine particles and 50 ml of ethanol are put in a test tube, stirred well using an ultrasonic homogenizer, and then washed with ethanol three times to collect the particle components with a centrifuge, followed by the same test. In a tube, the obtained copper alloy fine particles and 50 ml of 1-butanol were put and stirred well, and then 1-butanol washing for recovering the copper alloy fine particles with a centrifuge was performed three times.
The copper alloy fine particles obtained by the above method were added to 1-octanol as a dispersion solvent and stirred using an ultrasonic homogenizer to obtain a copper alloy fine particle dispersion of the present invention.
The obtained copper alloy fine particle dispersion was applied onto a carbon-deposited copper mesh, dried, and observed with the transmission electron microscope (TEM). The primary particle diameter of 90% or more of the particles was 5 to 5%. In the range of 50 nm, the average aspect ratio was 1.5. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 70 mass% copper and 30 mass% zinc. Moreover, it was confirmed by the measurement with a dynamic light scattering type particle size distribution measuring device that the secondary aggregation size was 500 nm or less.
［実施例４］
酢酸亜鉛濃度を０．０１モル／Ｌとした以外は実施例１と同様に、還元反応水溶液を調製し、電解還元反応を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅と亜鉛からなる合金微粒子を得た。
その後、得られた銅合金微粒子と５０ｍｌのエタノールとを試験管に入れ、超音波ホモジナイザーを用いてよく撹拌した後、遠心分離機で粒子成分を回収するエタノール洗浄を３回、続いて、同じく試験管中で、得られた銅合金微粒子と５０ｍｌの１−ブタノールとを入れよく撹拌した後、遠心分離機で銅合金微粒子を回収する１−ブタノール洗浄を３回行った。
上記の方法によって得られた銅合金微粒子を、分散溶媒であるエタノール１０体積％とエチレングリコール９０体積％の混合溶媒に添加、超音波ホモジナイザーを用いて攪拌し、本発明の銅合金微粒子分散液が得られた。
得られた銅合金微粒子分散液をカーボン蒸着された銅メッシュ上に塗布後、乾燥し、上記透過型電子顕微鏡（ＴＥＭ）で観察を行ったところ、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９０質量％、亜鉛１０質量％の合金であった。
また、動的光散乱型粒度分布測定装置による測定で、二次凝集サイズが５００ｎｍ以下であることが確認できた。
[Example 4]
A reduction reaction aqueous solution was prepared and an electrolytic reduction reaction was performed in the same manner as in Example 1 except that the zinc acetate concentration was 0.01 mol / L. The obtained colloidal solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain alloy fine particles composed of copper and zinc.
After that, the obtained copper alloy fine particles and 50 ml of ethanol are put in a test tube, stirred well using an ultrasonic homogenizer, and then washed with ethanol three times to collect the particle components with a centrifuge, followed by the same test. In a tube, the obtained copper alloy fine particles and 50 ml of 1-butanol were put and stirred well, and then 1-butanol washing for recovering the copper alloy fine particles with a centrifuge was performed three times.
The copper alloy fine particles obtained by the above method are added to a mixed solvent of 10% by volume of ethanol and 90% by volume of ethylene glycol, which is a dispersion solvent, and stirred using an ultrasonic homogenizer. Obtained.
The obtained copper alloy fine particle dispersion was applied onto a carbon-deposited copper mesh, dried, and observed with the transmission electron microscope (TEM). The primary particle diameter of 90% or more of the particles was 5 to 5%. In the range of 50 nm, the average aspect ratio was 1.5. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 90% by mass of copper and 10% by mass of zinc.
Moreover, it was confirmed by the measurement with a dynamic light scattering type particle size distribution measuring device that the secondary aggregation size was 500 nm or less.
［比較例１］
下記方法により、評価用の銅微粒子分散液を調製した。
酢酸亜鉛濃度を０モル／Ｌとした以外は実施例１と同様に、還元反応水溶液を調製し、電解還元反応を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅微粒子を得た。
その後、得られた銅微粒子と５０ｍｌのエタノールとを試験管に入れ、超音波ホモジナイザーを用いてよく撹拌した後、遠心分離機で粒子成分を回収するエタノール洗浄を３回、続いて、同じく試験管中で、得られた銅微粒子と５０ｍｌの１−ブタノールとを入れよく撹拌した後、遠心分離機で銅微粒子を回収する１−ブタノール洗浄を３回行った。
上記の方法によって得られた銅微粒子を、分散溶媒である１−オクタノールに添加、超音波ホモジナイザーを用いて攪拌し、評価用の銅微粒子分散液が得られた。
得られた銅微粒子分散液をカーボン蒸着された銅メッシュ上に塗布後、乾燥し、上記透過型電子顕微鏡（ＴＥＭ）で観察を行ったところ、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、動的光散乱型粒度分布測定装置による測定で、二次凝集サイズが５００ｎｍ以下であることが確認できた。
[Comparative Example 1]
A copper fine particle dispersion for evaluation was prepared by the following method.
A reduction reaction aqueous solution was prepared and an electrolytic reduction reaction was performed in the same manner as in Example 1 except that the zinc acetate concentration was changed to 0 mol / L. The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper fine particles.
After that, the obtained copper fine particles and 50 ml of ethanol are put into a test tube, stirred well using an ultrasonic homogenizer, and then washed with ethanol three times to collect the particle components with a centrifuge, followed by the same test tube. Inside, the obtained copper fine particles and 50 ml of 1-butanol were put and stirred well, and then 1-butanol was washed three times to collect the copper fine particles with a centrifuge.
The copper fine particles obtained by the above method were added to 1-octanol as a dispersion solvent and stirred using an ultrasonic homogenizer to obtain a copper fine particle dispersion for evaluation.
The obtained copper fine particle dispersion was applied onto a carbon-deposited copper mesh, dried, and observed with the transmission electron microscope (TEM). The primary particle size of 90% or more of the particles was 5 to 50 nm. In this range, the average aspect ratio was 1.5. Moreover, it was confirmed by the measurement with a dynamic light scattering type particle size distribution measuring device that the secondary aggregation size was 500 nm or less.
［実施例５、比較例２］
上記実施例１〜４で得られた銅合金微粒子分散液、及び比較例１で得られた銅微粒子分散液をスピンコータでガラス基板（サイズ：２ｃｍ×２ｃｍ）に塗布して、窒素ガス雰囲気中１５０℃で３０分間加熱・焼成して塗膜を乾燥させた後、熱処理炉中でゆっくりと室温まで炉冷した。以上の工程により、銅−亜鉛からなる合金で構成された導電部材（焼成膜）と銅のみで構成された焼成膜が形成された。直流四端子法（使用測定機：三菱化学製、ロレスターＧＰ（四端子電気抵抗測定モード））にて該焼成膜の抵抗値を測定した。
比較例１で得たサンプルから調製した焼成膜についての比抵抗値は、５０Ωｃｍと高い値であったのに対し、実施例１で得たサンプルから調製した焼成膜についての比抵抗値は、３００μΩｃｍ、実施例２で得たサンプルから調製した焼成膜についての比抵抗値は、２５μΩｃｍ、実施例３で得たサンプルから調製した焼成膜についての比抵抗値は、８０μΩｃｍ、実施例４で得たサンプルから調製した焼成膜についての比抵抗値は、１５μΩｃｍ、と小さい比抵抗値を示した。このように、銅と亜鉛からなる合金微粒子分散液を用いることで、１５０℃程度の低い温度の焼成でも導電性を示す導電部材が形成可能であり、微粒子中の合金組成によって、焼成した導電部材の電気抵抗が調整できることが判った。
[Example 5, Comparative Example 2]
The copper alloy fine particle dispersions obtained in Examples 1 to 4 and the copper fine particle dispersion obtained in Comparative Example 1 were applied to a glass substrate (size: 2 cm × 2 cm) with a spin coater, and 150 in a nitrogen gas atmosphere. The coating film was dried by heating and baking at 30 ° C. for 30 minutes, and then slowly cooled to room temperature in a heat treatment furnace. Through the above steps, a conductive member (fired film) made of an alloy made of copper-zinc and a fired film made only of copper were formed. The resistance value of the fired film was measured by a direct current four-terminal method (use measuring machine: Mitsubishi Chemical, Lorester GP (four-terminal electric resistance measurement mode)).
The specific resistance value for the fired film prepared from the sample obtained in Comparative Example 1 was as high as 50 Ωcm, whereas the specific resistance value for the fired film prepared from the sample obtained in Example 1 was 300 μΩcm. The specific resistance value for the fired film prepared from the sample obtained in Example 2 is 25 μΩcm, the specific resistance value for the fired film prepared from the sample obtained in Example 3 is 80 μΩcm, and the sample obtained in Example 4 The specific resistance value of the fired film prepared from No. 1 was as small as 15 μΩcm. In this way, by using an alloy fine particle dispersion composed of copper and zinc, a conductive member exhibiting conductivity can be formed even when firing at a low temperature of about 150 ° C., and depending on the alloy composition in the fine particles, the fired conductive member It was found that the electrical resistance can be adjusted.
［実施例６］
上記実施例１〜４で得られた銅合金微粒子分散液、及び比較例１で得られた銅微粒子分散液を銅基板（サイズ：２ｃｍ×２ｃｍ）に焼結後の導電接続部材の厚みが８０μｍとなるようにそれぞれ塗布した後、熱処理炉中で、半導体シリコンチップ（サイズ：４ｍｍ×４ｍｍ）を塗布膜上に押し付けて、窒素ガス雰囲気中２００℃で３０分間加熱・焼成させた後、ゆっくりと室温まで炉冷した。以上の工程により、銅−亜鉛からなる合金で構成された焼結体を介して半導体素子と導体基板が接合された。基板表面に接合されたシリコンチップを米国ＭＩＬ‐ＳＴＤ‐８８３に準拠したダイシェア強度評価装置を用いて、２５℃において、ダイシェア強度を評価したところ、実施例１で得られた銅合金微粒子分散液を用いて基板表面に接合されたシリコンチップのダイシェア強度は１５Ｎ／ｍｍ２、実施例２で得られた銅合金微粒子分散液を用いて基板表面に接合されたシリコンチップのダイシェア強度は２５Ｎ／ｍｍ２、実施例３で得られた銅合金微粒子分散液を用いて基板表面に接合されたシリコンチップのダイシェア強度は２０Ｎ／ｍｍ２、実施例４で得られた銅合金微粒子分散液を用いて基板表面に接合されたシリコンチップのダイシェア強度は４０Ｎ／ｍｍ２であった。比較として、上記比較例１で得られた銅微粒子分散液を用いて基板表面に接合されたシリコンチップのダイシェア強度を評価したところ、５Ｎ／ｍｍ２であった。このように、銅と亜鉛からなる合金微粒子分散液を用いることで、２００℃程度の低い温度の焼成でも半導体素子と導体基板を接合できることが判った。
[Example 6]
The thickness of the conductive connecting member after sintering the copper alloy fine particle dispersion obtained in Examples 1 to 4 and the copper fine particle dispersion obtained in Comparative Example 1 on a copper substrate (size: 2 cm × 2 cm) is 80 μm. After each coating, a semiconductor silicon chip (size: 4 mm × 4 mm) was pressed onto the coating film in a heat treatment furnace, heated and fired at 200 ° C. for 30 minutes in a nitrogen gas atmosphere, and then slowly The furnace was cooled to room temperature. Through the above steps, the semiconductor element and the conductor substrate were joined through the sintered body made of an alloy made of copper-zinc. When the die shear strength of the silicon chip bonded to the substrate surface was evaluated at 25 ° C. using a die shear strength evaluation device compliant with US MIL-STD-883, the copper alloy fine particle dispersion obtained in Example 1 was obtained. die shear strength of the silicon chip bonded to the substrate surface using the 15N / mm 2, the die shear strength of the silicon chip bonded to the substrate surface using a copper alloy particle dispersion obtained in example 2 25 N / mm 2 The die shear strength of the silicon chip bonded to the substrate surface using the copper alloy fine particle dispersion obtained in Example 3 is 20 N / mm 2 , and the substrate surface using the copper alloy fine particle dispersion obtained in Example 4 is used. The die shear strength of the silicon chip bonded to was 40 N / mm 2 . As a comparison, the die shear strength of the silicon chip bonded to the substrate surface using the copper fine particle dispersion obtained in Comparative Example 1 was evaluated to be 5 N / mm 2 . Thus, it was found that the semiconductor element and the conductor substrate can be joined even by firing at a low temperature of about 200 ° C. by using the alloy fine particle dispersion liquid composed of copper and zinc.
Claims (10)
The copper alloy fine particle dispersion according to any one of claims 1 to 7 is placed on an electrode terminal of a semiconductor element or a circuit board in an electronic component or a bonding surface of a conductive substrate, and further connected onto the copper alloy fine particle dispersion. A conductive connecting member formed by placing the other electrode terminal or the bonding surface of the conductive substrate and sintering by heat treatment.
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| JP2009286934A (en) * | 2008-05-30 | 2009-12-10 | Toshiba Corp | INK COMPOSITION HAVING Cu NANOPARTICLES DISPERSED THEREIN |
| JP5566743B2 (en) * | 2010-03-26 | 2014-08-06 | 古河電気工業株式会社 | Method for producing copper alloy fine particles |
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