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JP5611537B2 - 導電性接合材料、それを用いた接合方法、並びにそれによって接合された半導体装置 - Google Patents

導電性接合材料、それを用いた接合方法、並びにそれによって接合された半導体装置 Download PDF

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Publication number
JP5611537B2
JP5611537B2 JP2009109315A JP2009109315A JP5611537B2 JP 5611537 B2 JP5611537 B2 JP 5611537B2 JP 2009109315 A JP2009109315 A JP 2009109315A JP 2009109315 A JP2009109315 A JP 2009109315A JP 5611537 B2 JP5611537 B2 JP 5611537B2
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Japan
Prior art keywords
silver
particles
less
bonding material
bonding
Prior art date
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Expired - Fee Related
Application number
JP2009109315A
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English (en)
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JP2010257880A (ja
Inventor
雄亮 保田
雄亮 保田
俊章 守田
俊章 守田
英一 井出
英一 井出
稲田　禎一
禎一 稲田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Showa Denko Materials Co Ltd
Resonac Corp
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Priority to JP2009109315A priority Critical patent/JP5611537B2/ja
Application filed by Hitachi Chemical Co Ltd, Showa Denko Materials Co Ltd, Resonac Corp filed Critical Hitachi Chemical Co Ltd
Priority to TW99113331A priority patent/TWI437579B/zh
Priority to EP20100004458 priority patent/EP2278032A3/en
Priority to KR20100038827A priority patent/KR101157742B1/ko
Priority to EP20130192408 priority patent/EP2722410A1/en
Priority to US12/768,778 priority patent/US8840811B2/en
Priority to CN2010101717263A priority patent/CN101875158A/zh
Publication of JP2010257880A publication Critical patent/JP2010257880A/ja
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Publication of JP5611537B2 publication Critical patent/JP5611537B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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Description

本発明は、導電性接合材料、それを用いた接合方法、並びにそれによって接合された半導体装置に関し、例えば、半導体モジュールにおいて用いられる接合材料及び接合方法に関するものである。
インバータ等に用いられるパワー半導体装置の一つである非絶縁型半導体装置において、半導体素子を固定する部材は半導体装置の電極の一つでもある。例えば、パワートランジスタを固定部材上にＳｎ−Ｐｂ系はんだ付け材を用いて搭載した半導体装置では、固定部材（ベース材）はパワートランジスタのコレクタ電極となる。このコレクタ電極には半導体装置稼動時には数アンペア以上の電流が流れトランジスタチップは発熱する。この発熱に起因する特性の不安定化や寿命の低下を避けるためは、はんだ付け部の放熱性、長期信頼性（耐熱性）が確保できていなければならない。このため、このはんだ付け部の耐熱性及び放熱性の確保には高放熱性の材料が必要になってくる。
絶縁型半導体装置においても、半導体素子を安全かつ安定に動作させるためには、半導体装置の動作時に発生する熱を半導体装置の外へ効率良く放散させ、さらにはんだ付け部の接続信頼性を確保する必要がある。例えば、自動車のエンジンルームは高温な状態になることが多く、このような環境下でも接合部分の信頼性に問題があってはならない。
接合部分の耐熱性を上げるには高融点の接合材料を使えば良いが、この場合接合温度も上がってしまう。接合温度が高温になると、固定する部材が熱によって損傷してしまったり、接合後冷却時における基板と部材との応力差によって半導体装置全体に歪みが生じてしまう場合もある。つまり、接合材料の耐熱性は上げたいが、接合温度は下げたいという要求がある。
例えば、特許文献１に記載されているように、高い放熱性と信頼性を有する接続材料として、粒子状銀化合物を含む導電性組成物を用いた導電性接着剤が知られている。
また、特許文献２においては１〜１００μｍサイズの粒子を接合層中で焼結させる手法が報告されている。
さらに、金属粒子の粒径が１００ｎｍ以下のサイズまで小さくなり構成原子数が少なくなると、粒子の体積に対する表面積比は急激に増大し、焼結温度がバルク状態に比較して大幅に低下する（焼結性が上がる、或いは表面エネルギーが大きくなる）ことが知られている。例えば、特許文献３には、この低温焼成機能を利用し、有機物で表面が被覆された平均粒径１００ｎｍ以下の金属粒子を接合材料として用い、加熱により有機物を分解させて金属粒子同士を焼結させることで接合を行うことが記載されている。この接合方法では、接合後の金属粒子はバルク金属へと変化すると同時に接合界面では金属結合により接合されているため、非常に高い耐熱性と信頼性及び高放熱性を有する。
特開２００３−３０９３５２ 特開２００５−１２９３０３ 特開２００４−１０７７２８ 特開２００８−１６１９０７ 特開２００８−１７８９１１
しかしながら、特許文献１及び２に記載の接合材料（導電性接着剤）は、界面での接合機構が樹脂からなるバインダーを用いた方法であるために、界面において金属結合を達成した場合と比較すると、放熱性及び接合信頼性という点では劣っている。
また、特許文献３に記載の接合材料では、平均粒径が１００ｎｍ以下の金属粒子を用いているが、上述の通り、接合界面では金属結合による接合が行われていることから、高い耐熱性と信頼性及び高放熱性を有する。その反面、平均粒径が１００ｎｍ以下と非常に微細な金属粒子は凝集を起こしやすく、このような金属粒子は安定化させるために有機物の保護膜を形成する必要がある。この有機物の保護膜は接合時には除去する必要があるが、その際に粒子表面から大量の有機物が揮発し、体積収縮を起こすことから、接合時に加圧する必要がある。接合時に加圧すると、半導体チップへのダメージを与えてしまう恐れがある。また、通常はんだ付けの工程には加圧する工程はないため、この手法を適用するには接合時に加圧するためのプロセス（設備）が必要となり、汎用性に乏しい。このように、平均粒径が１００ｎｍ以下の金属粒子を用いた接合方法では、金属粒子の作製、作製後の不純物の除去や保管、取り扱い等、実用面での課題が残されている。
本発明はこのような状況に鑑みてなされたものであり、接合後には耐熱性に優れ、接合時には樹脂を含有した導電性接合材料と比較して接合界面での金属結合をより低温で実現可能であり、接合プロセスにおいて加圧を必須としない無加圧での接合が可能な導電性接合材料及びそれを用いた接合方法、並びにそれによって接合された半導体装置を提供するものである。
上記課題を解決するために、本発明では、今まで着目されていなかった粒径が０．１〜１００μｍ（マイクロ粒子）の銀粉（銀粒子）と酸化銀粉（酸化銀粒子）を用いることで接合部の金属接合を可能としている。また、樹脂を用いない（有機物の含有量を少なくする）ことによって、接合過程における無加圧化を可能とし、接合プロセスの簡略化を達成する。
さらに、はんだの鉛フリー対応が迫られているが、高温はんだに関してはその代替となる材料が出ていない。実装においては階層はんだを用いることが必要不可欠なため、この高温はんだに代わる材料の出現が望まれている。従って、本接合技術はこの高温はんだに代わる材料としても期待されている。
本発明者らは、（Ａ）銀粉、（Ｂ）酸化銀粉、（Ｃ）炭素数３０以下で構成される有機物からなる分散剤必須成分とする全導電性接合材料中において、（Ａ）銀粉と（Ｂ）酸化銀粉と（Ｃ）炭素数３０以下で構成される有機物からなる分散剤の合計が９９.０〜１００重量％であることを特徴とする導電性接合材料を用いることによって、２００℃以下という低温で銀粒子の焼結が開始され、かつ無加圧での接合が可能であることを見出した。このとき、混合した酸化銀粒子が有機物からなる分散剤と１５０℃以下低温で酸化還元反応を起こして銀に還元し、その際に融合を起こすため、２００℃以下での焼結を進行させ、銀粒子単体で用いた場合よりもさらなる接合強度の向上を可能とする。さらに、本発明者らは、この際には樹脂のバインダーを用いずに接合材料に用いた銀粒子と酸化銀粒子から還元した銀により相手電極との接合が可能であることを見出した。
即ち、本発明による導電性接合材料は、銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、を必須成分とし、銀粒子と酸化銀粒子と分散剤の合計が９９.０〜１００重量％であることを特徴としている。ここでは、銀粒子と酸化銀粒子の粒径が０．１μｍ以上１００μｍ以下である。銀粒子がフレーク状の形状をなすようにしても良い。また、銀粒子及び酸化銀粒子の少なくとも一方が、分散剤により被覆されている。酸化銀粒子の量は、分散剤の量以下であることが望ましい。なお、銀粒子と酸化銀粒子の混合率は、銀粒子を１００質量部とした場合に、酸化銀粒子が０．０１質量部以上１００質量部以下である。
別の態様の導電性接合材料は、銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、沸点が３５０℃以下の有機溶剤と、を必須成分とし、銀粒子と酸化銀粒子と分散剤と有機溶剤の合計を１００質量部とした場合に、有機溶剤の量が９０質量部以下であり、銀粒子と酸化銀粒子と分散剤と有機溶剤との合計が９９.０〜１００重量％で、ペースト状をなしていることを特徴とする。
また、別の態様の導電性接合材料は、銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、銀以外の金属粒子と、を必須成分とし、銀粒子と酸化銀粒子と分散剤と銀以外の金属粒子との合計が９９.０〜１００重量％であることを特徴とする。
さらに、別の態様の導電性接合材料は、銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、沸点が３５０℃以下の有機溶剤と、銀以外の金属粒子と、を必須成分とし、銀粒子と酸化銀粒子と分散剤と有機溶剤と金属粒子の合計を１００質量部とした場合に、有機溶剤の量が９０質量部以下であり、銀粒子と酸化銀粒子と分散剤と有機溶剤と銀以外の金属粒子との合計が９９.０〜１００重量％で、ペースト状をなしていることを特徴とする。
本発明による半導体装置は、上述の何れかの導電性接合材料を用いて接合され、接合部が金属部分のみからなり、その空隙率が０．１％より大きく９０％より小さいことを特徴としている。
本発明による接合方法は、半導体素子の電極と金属部材との間に上述の何れかの導電性接合材料を配置し、水素中、窒素中、又はアルゴン雰囲気中において加熱することで導電性接合材料を焼結させ、半導体素子の電極と金属部材とを金属接合することを特徴としている。
さらなる本発明の特徴は、以下本発明を実施するための最良の形態および添付図面によって明らかになるものである。
本発明によれば、平均粒径が１００ｎｍ以下の金属粒子を用いた接合用材料と比較して、接合界面での金属結合による接合をより低温で実現可能な接合用材料、接合方法を提供することができる。また、樹脂のようなバインダーを用いないため無加圧で接合プロセスを構築でき、接合後における接合部の高耐熱化、高放熱化が可能となる。
銀フレークと酸化銀粒子を用いて接合を行った際の概念図である。 銀フレークに酸化銀粒子を加えた場合の接合強度変化を示す図である。 銀フレークに加える酸化銀粒子の割合の影響を示す図である。 本発明の実施例の一つである非絶縁型半導体装置の構造を示す図である。 本発明絶縁型半導体装置のサブアッセンブリ部を示す図である。 半導体素子と基板接合部の拡大概略図である。 本実施例絶縁型半導体装置の断面模式図である。 本実施例ミニモールド型非絶縁型半導体装置の断面模式図である。
以下、本発明の実施形態について具体的に説明し、続いて実施例及び適用例について説明する。
＜接合材料の組成＞
本発明は（Ａ）銀粉と、（Ｂ）酸化銀粉と、（Ｃ）炭素数３０以下で構成される有機物からなる分散剤と、を必須成分とする全導電性接合材料に関する。このような組成を有する導電性接合材料において、（Ａ）銀粉と（Ｂ）酸化銀粉と（Ｃ）炭素数３０以下で構成される有機物からなる分散剤の合計が９９.０〜１００重量％となっている。つまり、従来の樹脂は含まれない構成となっている。接合時にこの導電性接合材料を加熱し、銀粒子と酸化銀粒子を焼結させて金属的な接合を行う。銀粉に酸化銀を混合させることで、接合時に分散剤と酸化銀が１５０℃以下の温度で酸化還元反応を起こし、銀粉の焼結を促進することで低温での接合強度向上が可能となる。
また、本発明における接合材料を利用した接合機構は樹脂を用いない金属接合であることから、接合後における接合部の高耐熱化、高放熱化が可能となる。このように低温で金属接合が可能であるため、例えば、半導体素子のアクティブエリア上に設けた電極とこれを搭載する配線基板の搭載部との接合に適用可能である。また、接合後の接合層は従来のはんだ材と比較して高い耐熱性を有しているため、二次実装等の熱工程において半導体素子搭載部の溶融等の問題もなく、半導体装置の小型化と高信頼化を実現することができる。
さらに、当該接合材料によれば、平均粒径１００ｎｍ以下の金属ナノ粒子を用いた場合よりも無加圧での大幅な接合強度向上が可能となる。これにより、従来技術では困難であった無加圧下における金属接合が可能となり、接合時の加圧プロセスの省略が可能となり、接合プロセスの大幅な簡略化が可能となる。また、接合時に加圧しないことから、半導体チップ等への接合時のダメージを大きく軽減できる。
＜粒子のサイズ及び形状＞
ここで用いる銀粒子と酸化銀粒子の粒径は、平均粒径が０．１μｍ以上１００μｍ以下としている。金属粒子の平均粒径１００μｍより大きくなると、導電性接合材料中における分散性が悪くなり、緻密な接合層を得ることが困難になるためである。また、平均粒径を０．１μｍ以上としたのは、平均粒子が０．１μｍ以下の金属粒子を作製するには多くの有機物で金属粒子の周囲を被覆する必要があり（この有機物は平常状態で粒子同士が結合してしまうのを防止するためのものである）、そのような粒子を接合に用いると、その有機物を除去する際に体積収縮が起こるため、無加圧での接合が困難になるためである。
酸化銀粒子としては、Ａｇ2Ｏ やＡｇＯなどが挙げられ、これらのうちから少なくとも１種類の金属あるいは２種類の金属からなる接合材料を用いることが可能である。また、酸化銀粒子以外にも、酸化金、酸化銅からなる金属酸化物を同時に加えて用いてもよい。
用いる酸化銀と銀粒子の形状はフレーク状からなるものを用いることが可能である（後述の実施例（図1等）では銀粒子のみがフレーク形状となっている）。フレーク状の平均粒子径は、１００μｍ以下が好ましく、より好ましくは５０μｍ以下、最も好ましくは１０μｍ以下である。下限は、０．１μｍ以上が好ましい。平均粒子径が１００μｍを超えるとスクリーン印刷をする場合はスクリーンに目詰まりをおこしたり、該フレーク状粒子の沈降によるペーストの貯蔵安定性が低下する可能性がある。一方、平均粒子径が０．１μｍ未満では、ペーストの粘度が高くなり該フレーク状粒子を充分充填できなくなる可能性がある。
また、このフレーク状粒子は、平均厚さが５．０μｍ以下であることが好ましく、より好ましくは、１μｍ以下である。下限は特に限定されないが、０．１μｍ以上が好ましい。２．０μｍ超では、アスペクト比が小さくなり導電性が低下する可能性がある。
さらに、このフレーク状粒子のアスペクト比は１．０より上が好ましく、２以上がより好ましい。上限は特に定めるものではないが、２００以下が好ましく、より好ましくは１５０以下である。
なお、粒子形状は、上述の球状やフレーク状に限らず、四面体や八面体、ロッド状、繊維状のものを用いることが可能である。フレーク形状の場合、粒子同士が面で接することができるので、接触面積は大きくなる。
＜銀粒子と酸化銀粒子の混合率＞
銀粒子と酸化銀粒子の混合率は、銀粒子１００質量部（重量％）に対して酸化銀粒子を０．０１質量部以上１００質量部以下の範囲とするのがよい。０．０１質量部以上としたのは、これより少ないと酸化銀からの還元銀の量も少なくなり、低温での銀粒子を融合する効果が表れなくなるからである。１００質量部以下としたのは、これよりも加える酸化銀粒子の量が多くなると接合層にといて酸化銀の体積収縮が占める割合が多くなり、結果として接合強度が低下するようになるためである。接合強度を考慮すると、より好ましくは、４０重量％程度が好適である（図３参照）。
＜分散剤の例＞
炭素数３０以下の有機物からなる分散剤（かつ、酸化銀の還元剤）としては、アルコール類、カルボン酸類、アミン類から選ばれた１種以上の混合物を用いることができる。これらは混合粒子の溶媒への金属粒子の周りを有機物で被覆し、有機溶剤への分散性を向上する作用がある。ここで、分散剤（銀粒子同士が付着しないようにするためのもの）として例えばステアリン酸を用いた場合、酸化銀と、銀粒子に付着していたステアリン酸とが１４０〜１５０℃で還元反応を起こし、ステアリン酸が銀粒子から除去される。このため、酸化銀の混合割合がステアリン酸の量に比べて多すぎると、十分に還元反応を起こすことができずに酸化銀が接合材内に残ってしまう。これでは接合強度が上がらない。よって、酸化銀と分散剤との混合比は１対１を限度とするのが好ましい。
ここで、炭素数３０以下としたのは、炭素数が多くなりすぎると、分散剤の沸点が高くなってしまって、接合時に加熱（例えば２００℃）しても分散剤が接合部分に残ってしまい、接合強度及び信頼性に問題となる可能性があるからである。
また、利用可能なアルコール基を含む化合物としては、アルキルアルコールが挙げられ、例えば、エタノール、プロパノール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ウンデシルアルコール、ドデシルアルコール、トリデシルアルコール、テトラデシルアルコール、ペンタデシルアルコール、ヘキサデシルアルコール、ヘプタデシルアルコール、オクタデシルアルコール、ノナデシルアルコール、イコシルアルコール、がある。さらには１級アルコール型に限らず、２級アルコール型、３級アルコール型、及びアルカンジオール、環状型の構造を有するアルコール化合物を用いることが可能である。それ以外にも、エチレングリコール、トリエチレングリコール、または、クエン酸、アスコルビン酸、グルコースなど多数のアルコール基を有する化合物を用いてもよい。
また、利用可能なカルボン酸を含む化合物としてアルキルカルボン酸がある。具体例としては、ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、ノナデカン酸、イコサン酸、オレイン酸が挙げられる。また、上記アルコール基と同様に１級アルコール型に限らず、２級カルボン酸型、３級カルボン酸型、及びジカルボン酸、環状型の構造を有するカルボキシル化合物を用いることが可能である。
さらに、利用可能なアミノ基を含む化合物としてアルキルアミンを挙げることができる。例えば、ブチルアミン、ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、ヘキサデシルアミン、ヘプタデシルアミン、オクタデシルアミン、ノナデシルアミン、イコデシルアミンがある。アミノ基を有する化合物としては分岐構造を有していてもよく、そのような例としては、２−エチルヘキシルアミン、１、５ジメチルヘキシルアミンなどがある。また、１級アミン型に限らず、２級アミン型、３級アミン型を用いることも可能である。さらにこのような有機物としては環状の形状を有していてもよい。
また、用いる分散剤は上記アルコール、カルボン酸、アミンを含む有機物に限らず、アルデヒド基やエステル基、スルファニル基、ケトン基などを含む有機物を用いることが可能である。ここで、被覆とは有機物中の官能基と銀もしくは酸化銀が結合していることであり、凝集を防ぐような役割を果たすことである。このような構造は赤外分光法を用いて区別することが出来る。カルボン酸が銀粉や酸化銀の周りを被覆する際にはカルボニル塩を形成する。
赤外線分光法を用いて、分散剤添加の銀を解析すると、スペクトル解析を行うと、１５２０ｃｍ−１付近と１４２０ｃｍ−１付近に弱いピークが表れる。これらのピークは銀と結合していない場合には観測できない。したがってこのように赤外分光測定を用いることで、粒子を被覆している有機物を特定することが可能である。また、特定できる有機物はカルボン酸だけではなく、官能基を有する有機物においてはどの物質を用いても上記と同様に特定が可能である。
＜分散剤の混合率＞
分散剤の使用量は銀粒子と酸化銀粒子の合計を１００質量部とした場合に０．０１〜２０質量部の範囲にて用いることが出来る。これは分散剤の量が０．０１質量部より少ないと銀粒子と酸化銀粒子の分散性が悪く、２次凝集を起こし、接合部分への均一な塗布が困難となり、無加圧での接合が不可能となるからである。また、２０質量部以下としたのは、２０質量部より多くなると、接合時の銀粒子同士の融合を妨げるようになり、接合強度の大きな低下が見られるからである。
銀粒子と、酸化銀粒子と、炭素数３０以下からなる分散剤と、を有する導電性接合材料において、これらの混合量は全導電性接合材料中において９９．０〜１００ｗｔ％（重量％）になるように用いる。樹脂バインダーのようなものが混合されてしまうと、銀粒子間の焼結を大きく阻害し、接合強度が大きく低下してしまうためである。９９．０重量％としたのは、不純物の含まれていない銀は稀であり、通常入手できる銀の純度を考慮した数値としたためである。
＜他の組成物＞
接合材料中には比較的粒径の大きい平均粒径０．１μｍ〜１００μｍの銀粒子以外の粒子を混合して用いることも可能である。これは導電性接合材料中に混合された銀粒子と酸化銀粒子が平均粒径０．１μｍ〜１００μｍの他の金属粒子同士を焼結させる役割を果たすからである。この金属粒子の種類としては、金、銅があげられる。上記以外にも白金、パラジウム、ロジウム、オスミウム、ルテニウム、イリジウム、鉄、錫、亜鉛、コバルト、ニッケル、クロム、チタン、タンタル、タングステン、インジウム、ケイ素、アルミニウム等の中から少なくとも１種類の金属あるいは２種類以上の金属からなる合金を用いることが可能である。
また、接合材料中には平均粒径が１００ｎｍ以下の金属粒子を予め混合しておいてもよい。このような金属の種類としては金、銀、銅、あるいは、これらの酸化物である酸化金、酸化銀、酸化銅があげられる。上記以外にも白金、パラジウム、ロジウム、オスミウム、ルテニウム、イリジウム、鉄、錫、亜鉛、コバルト、ニッケル、クロム、チタン、タンタル、タングステン、インジウム、ケイ素、アルミニウム等の中から少なくとも１種類の金属あるいは２種類以上の金属からなる合金を用いることが可能である。これらは本発明における導電性接合材料の特性を大きく低下させない範囲で混合させて用いてもよい。
ただし、このように他の金属を混合した場合でも、上述した理由から樹脂を含有させてはいけない。
＜ペースト状の接合材料＞
本実施形態で用いられる導電性接合材料は銀粒子と酸化銀粒子と分散剤（プラス他の金属粒子）のみで生成してもよいが、ペースト状の接合材料として用いる場合には沸点が３５０℃以下の溶媒を加えて用いてもよい。このような溶媒としては例えばアルコール類等が挙げられる。ここで、沸点３５０℃以下としたのは、接合温度のターゲットが２００〜２５０℃であるので、あまり沸点が高いと蒸発するのに時間が掛かりすぎるからであり、３５０℃を限度にするのが適当と考えられるからである。ただし、その温度を超える沸点を有するアルコール類等の有機物が絶対に不適かというとそうではない。用途によってはそのような有機物を用いても良いのはもちろんである。
利用可能なアルコール基を有する有機物としては、メタノール、エタノール、プロパノール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルルコール、ウンデシルアルコール、ドデシルアルコール、トリデシルアルコール、テトラデシルアルコール、ペンタデシルアルコール、ヘキサデシルアルコール、ヘプタデシルアルコール、オクタデシルアルコール、ノナデシルアルコール、イコシルアルコール、がある。また、ジエチレングリコール、エチレングリコール、トリエチレングリコールなどのグリコール系を用いることができる。さらには１級アルコール型に限らず、２級アルコール型、３級アルコール型、及びアルカンジオール、環状型の構造を有するアルコール化合物を用いることが可能である。それ以外にも、テルピネオール、エチレングリコール、トリエチレングリコール、または、クエン酸、アスコルビン酸、グルコースなど多数のアルコール基を有する化合物を用いてもよい。この中でも特に２級アルコール、３級アルコール型の化合物を用いることが望ましい。これは、１級アルコール型では酸化銀と混合した際に１日後には酸化銀表面の一部を還元し塩を形成すると同時に銀粒子を析出させてしまうために酸化銀粒子の保存安定性が悪くなるためである。２級アルコール、３級アルコール型では、酸化銀と反応してこのような塩が表面に形成されることがないために安定性に優れている。また、これらの中でもグリコール系の溶媒を用いることが好ましい。これはグリコール系の溶媒は安価で、人体等に対する毒性も少ないからである。さらに、これらのアルコール系の溶媒は溶媒としてだけでなく、酸化銀に対する還元剤としても作用することが可能であるため、酸化銀粒子の量に対する還元剤として適度な量に調整して用いることができる。
また、上記アルコール基を含む有機物に限らず、カルボン酸、アミン、アルデヒド基やエステル基、スルファニル基、ケトン基などを含む有機物を用いることができる。さらには、上記のような官能基を有さない、トルエンや、炭化水素のみからなる有機物を用いてもよく、そのような例としてはヘキサン、シクロへキサンなどが挙げられる。このように用いる有機溶剤としては沸点が３５０℃以下であればよく、そのような中からは１種のみではなく、２種類以上の混合物を用いることが可能である。ここで、３５０℃以下の沸点を有する有機物とは、一般に市販されている、Seiko Instruments 製ＴＧ／ＤＴＡ６２００や、島津製作所製ＴＧＡ−５０等の熱重量測定が可能な装置を用いて１０℃／min において窒素中において測定を行った場合に３５０℃までに９９ｗｔ％の重量減少を起こす有機物とする。
混合する有機溶剤の量は本発明における導電性接合材料を１００重量％とした場合に９０重量％以内（より好適には５０重量％以内）であればよい。この際には乳鉢、擂潰機、振動ボールミル、ローラーミル、遊星ボールミル等を用いて攪拌して混合すればよい。
ペースと状の導電性接合材料は、インクジェット法により微細なノズルから導電性接合材料を噴出させて基板上の電極あるいは電子部品の接続部に塗布する方法や、あるいは塗布部分を開口したメタルマスクやメッシュ状マスクを用いて必要部分にのみ塗布を行う方法、ディスペンサを用いて必要部分に塗布する方法、シリコーンやフッ素等を含む撥水性の樹脂を必要な部分のみ開口したメタルマスクやメッシュ状マスクで塗布したりする方法がある。これらの塗布方法は、接合する電極の面積、形状に応じて組み合わせ可能である。また、これら導電性接合材料加圧を加えることでシート状に成形して接合材料として用いる方法がある。
＜加熱条件＞
本導電性接合材料を用いた接合では、接合時に銀粒子同士の焼結と酸化銀の還元及び電極面との金属接合を達成するために熱を加えることが必須である。接合条件としては、１秒以上１８０分以内で４０℃以上３５０℃以下の加熱を加えることが好ましい。
従来の平均粒径が１００ｎｍ以下の金属粒子では有機物の脱離に伴い金属粒子が体積収縮を起こすため、接合時の加圧が必要であったが本発明においては、無加圧で接合界面での金属結合による接合が達成可能である。これにより接合プロセスの簡略化が可能となる。しかしながら、接合強度向上のために、必要があれば加圧をかけて用いてもよい。
加熱温度を４０℃以上としたのは、これよりも低温での加熱であると、銀粒子の焼結と酸化銀の還元を十分に起こし接合を達成することが不可能だからである。
加熱時間を１８０分以下としたのは加熱時間を１８０分以上とすると、一つの製品を作製するのにあまりにも多くの時間がかかり、大量生産を行うことが難しくなるからである。
また、このときの接合雰囲気としては、大気中に限らず、還元雰囲気、例えば、水素雰囲気、または不活性雰囲気である窒素雰囲気、アルゴン雰囲気などを用いることが可能である。このような雰囲気で接合を行うことで、電子部品等の大気中酸化当の問題を軽減することが可能となる。
本発明の（Ａ）銀粒子、（Ｂ）酸化銀、（Ｃ）炭素数３０以下で構成される有機物からなる分散剤を必須成分とする全導電性接合材料中において、（Ａ）銀粉と（Ｂ）酸化銀粉と（Ｃ）炭素数３０以下で構成される有機物からなる分散剤の合計が９９.０〜１００重量％である、導電性接合材料を用いて接合された半導体装置の接合部は、接合時に加圧をかけないために、用いた粒子の形状がそのまま接合部反映される。
したがって、その接合層には必ず空隙が存在し、ある接合層の断面を見たときにその空隙率（空孔を接合層の面積で割ったもの）は０．１〜９９．９％（より好適には９０％以下）である。このように空隙率が存在することでバルク銀からなる接合層よりも密度と弾性率が低くなり、チップへの応力負荷が軽減され、接合部の長期信頼性が高くなる。
以下、本発明の実施例及び適用例について図面を用いて説明する。
＜実施例１＞
実施例１では平均粒径が１μｍ程度、平均厚さが０．５μｍ以程度、アスペクト比が２．０程度の銀フレークに１．０ｗｔ％のステアリン酸が被覆された銀フレーク０．９ｇと平均粒径が約２μｍ程度の酸化銀（Ａｇ２Ｏ ）粒子０．１ｇを用い、有機溶剤にはエタノール（和光純薬製）０．２ｇを用いた。これらは乳鉢を用いて１時間程度混合を行い導電性接合材料を作製した。
比較例１として市販されている従来Ａｇペーストを用いた。また、比較例２として平均粒径が１μｍ程度、平均厚さが０．３μｍ程度、アスペクト比が２．０程度の銀フレークに１．０ｗｔ％のステアリン酸が被覆された銀フレーク１００質量部に対し、２０質量部のエタノールを加えて乳鉢で１０分程度混合した導電性接合材料を作製した。
次に実施例１と比較例１〜２の導電性接合材料を用いて接合を行った後、せん断強度測定を行った。測定用に用いた試験片の大きさは上側が直径５ｍｍ、厚さ２ｍｍで下側が直径１０ｍｍ、厚さ５ｍｍのものであり、表面にＡｇめっきがされたものである。この下側の試験片の上に上記実施例１と比較例１〜２の導電性接合材料を塗布した後、上側の試験片を接合材料の上に設置し、２００℃で加熱することで接合を行った。加熱時間は５、１５、３０、６０分で行った（表１参照）。
Figure 0005611537
図１に示すように、接合部材２０１の間に配置された上記導電性接合材料同士が加熱により焼結を起こすことで、焼結銀層２０５が形成される。この際、焼結銀層２０５と接合部材２０１の接合界面は金属結合による接合が達成される。次に、上記接合材料を用いて接合を行うことにより得られた試料を用い、純粋せん断応力下での接合部強度を測定した。せん断試験には西進商事製ボンドテスターＳＳ−１００ＫＰ（最大荷重１００ｋｇ）を用いた。せん断速度は３０ｍｍ／ｍｉｎ とし、試験片をせん断ツールで破断させ、破断時の最大荷重を測定した。この最大荷重を接合面積で割り、せん断強度とした。
図２に実施例１と比較例１、２の接合材料を用いて得られたせん断強度試験結果を示す。ここで接合強度の値は、比較例２の試料を用いて無加圧で６０分間、２００℃にて加熱した場合の接合強度に対する相対比で値を示した。比較例２の平均粒径が１μｍ程度、平均厚さが０．３μｍ程度、アスペクト比が２．０程度の銀フレークに１．０ｗｔ％のステアリン酸が被覆された銀フレーク１００質量部に対し、２０質量部のエタノールを加えて乳鉢で１０分程度混合した導電性接合材料を用いた接合材料では接合強度比が低いが、実施例１の平均粒径が１μｍ程度、平均厚さが０．５μｍ以程度、アスペクト比が２．０程度の銀フレークに１．０ｗｔ％のステアリン酸が被覆された銀フレーク０．９ｇと平均粒径が約２μｍ程度の酸化銀（Ａｇ２Ｏ）粒子０．１ｇを用い、有機溶剤にはエタノール（和光純薬製）０．２ｇを用い、乳鉢により１時間程度混合した導電性接合材料では接合強度比が大きく向上し、６０分間加熱した場合には相対強度比にて２．０にまでなった。これより銀フレークに酸化銀を混合することで接合強度が大きく向上する効果が確認できた。
次に、比較例３と４との実施例１との比較を行った。比較例３は特許文献４（特願２００６−３５３６４９）に記載されたオクチルアミンで被覆された銀ナノ粒子を用いた。比較例４は特許文献５（特開２００８−１７８９１１）に記載された酸化銀粒子とミリスチルアルコールで混合された接合材料を作製した。比較例５の接合材料は酸化銀粒子（Ａｇ２Ｏ）とミリスチルアルコールを重量比において９：１の割合にて混合し、乳鉢によりすり潰して作製した。これらの材料を用いて接合強度試験を行った。測定用に用いた試験片の大きさは上側が直径５ｍｍ、厚さ２ｍｍで下側が直径１０ｍｍ、厚さ５ｍｍのものであり、表面にＡｇめっきがされたものである。この下側の試験片の上に上記比較例３及び４の導電性接合材料を塗布した後、上側の試験片を接合材料の上に設置し、２００℃で加熱することで接合を行った。接合強度は純粋せん断応力下での接合部強度を測定した。せん断試験には西進商事製ボンドテスターＳＳ−１００ＫＰ（最大荷重１００ｋｇ）を用いた。せん断速度は３０ｍｍ／ｍｉｎとし、試験片をせん断ツールで破断させ、破断時の最大荷重を測定した。この最大荷重を接合面積で割り、せん断強度とした。表に示すように接合強度比で比較を行った。このように従来の金属接合を達成できる接合技術と比較すると、大きな接合強度の向上が見られ、本発明の導電性接合材料が優れた特性を有していることがわかる（上記表１参照）。
＜実施例２＞
実施例２では、平均粒径が１μｍ程度、平均厚さが０．５μｍ以程度、アスペクト比が２．０程度の銀フレークを用いた。そして、１．０ｗｔ％のステアリン酸が被覆された銀フレークに対して、平均粒径が約２μｍ程度の酸化銀（Ａｇ２Ｏ）粒子を混合させる割合を重量比において９５：５、９０：１０、８０：２０、５０：５０と変化させて試料を作製した。さらに、それぞれの試料１００質量部に対して、有機溶媒としてエタノール（和光純薬製）２０質量部を混合し、乳鉢を用いて１時間程度混合を行い、それぞれ１ｇの導電性接合材料を得た。その後せん断強度の測定を行った。測定用に用いた試験片の大きさは、上側が直径５ｍｍ、厚さ２ｍｍで下側が直径１０ｍｍ、厚さ５ｍｍのものであり、表面にＡｇめっきがされたものである。この下側の試験片の上に上記実施例１と比較例１及び２の導電性接合材料を塗布した後、上側の試験片を接合材料の上に設置し、２００℃で加熱することで接合を行った。加熱時間は６０分である。それぞれの強度は、比較例２の試料を用いて無加圧で６０分間、２００℃にて加熱した場合の接合強度に対する相対比で値を示した。
図３に示した結果のように酸化銀（Ａｇ２Ｏ）粒子を５ｗｔ％混合させた場合に最も高い接合強度が得られる。これは加えたステアリン酸と酸化銀粒子の酸化還元する割合が最適な比率であっためである。酸化銀が多いと、酸化銀が残り、また、酸化銀が少ないと、銀フレークの周りの有機物がなくならないため、接合強度の大幅な向上が見られなくなる。
次に、実施例２、比較例１乃至４の熱伝導率測定の値を比較した。熱伝導率は式（１）で定義される。
熱伝導率（Ｗ／ｍＫ）＝熱拡散率（ｍ２／ｓ）×比熱（Ｊ／ｇ・Ｋ）
×密度密度（ｇ／ｃｍ３） ・・・ （１）
熱伝導率を算出するために必要な熱拡散率（ｍ２／ｓ）、密度（ｇ／ｃｍ３）、比熱（Ｊ／ｇ・Ｋ）は、以下の装置を用いて測定した。熱拡散率は、サンプル形状を５ｍｍ×１０ｍｍ×０．１μｍとし、ＵＬＶＡＣ ＳＩＮＫＵ−ＲＩＫＯ製ＰＩＴ１型により測定した。密度は、アルファミラージュ製ＳＤ−２００Ｌにより測定した。また、比熱は、ＴＡ ｉｎｓｔｒｕｍｅｎｔ製Ｑ２０００により測定した。これらの値を用いて熱伝導率を算出した。表２に結果を示した。
この値は、比較例２の試料を用いて無加圧で６０分間、２００℃にて加熱した場合の熱伝導率に対する相対比で示した。比較例１と３と４では熱伝導率の値が比較例２よりも小さい。これは接合強度とも対応しており、比較例１では熱伝導率の小さな樹脂を混合しているため、比較例３と４では加圧をかけないために密度が小さいためである。しかし、実施例２（ここでは銀フレークと酸化銀粒子を混合させる割合を重量比において９０：１０の試料を用いた）では比較例２よりも大きな熱伝導率を有していた。これは酸化銀を混合することで、焼結温度が下がり、同じ温度においても作製されたフィルムの焼結がより進行していたためである。以上より、実施例２の接合材料は接合強度だけでなく、熱伝導率においても優れている。
Figure 0005611537
＜適用例１＞
図４は、本発明の適用例の一つである非絶縁型半導体装置の構造を示した図である。図４（ａ）は上面図、図４（ｂ）は図４（ａ）Ａ−Ａ′部の断面図である。半導体素子（ＭＯＳＦＥＴ）３０１をセラミックス絶縁基板３０２上に、セラミックス絶縁基板３０２をベース材３０３上にそれぞれ搭載した後、エポキシ系樹脂ケース３０４、ボンディングワイヤ３０５、エポキシ系樹脂製のふた３０６を設け、同一ケース内にシリコーンゲル樹脂３０７を充填した。ここで、ベース材３０３上のセラミックス絶縁基板３０２は実施例１の導電性接合用材料を用いて接合された接合層３０８で接合され、セラミックス絶縁基板３０２の銅板３０２ａ上には８個のＳｉからなるＭＯＳＦＥＴ素子３０１が上記実施例１の導電性接合材料により接合された接合層３０９で接合されている。この接合層３０８及び３０９による接合は、先ず、セラミックス絶縁基板３０２の銅板３０２ａ（Ｎｉめっきが施されている）上、及びベース材３０３上に実施例１の導電性接合材料を銅板３０２ａ（Ｎｉめっきが施されている）上とベース材３０３上にそれぞれ塗布する。
そして、実施例１で示した導電性接合材料の上に半導体素子３０１、及びセラミックス絶縁基板３０２を配置させ接続する。このとき大気中において１５０℃程度において１２０分間加熱することで接合を行った。
各素子３０１に形成されたゲート電極、エミッタ電極等と、絶縁基板上に形成した電極３０２ａ、３０２ｂ、エポキシ系樹脂ケース３０４にあらかじめ取り付けられている端子３１０の間は、直径３００μｍのＡｌ線３０５を用い超音波接合法によりでワイヤボンディングした。３１１は温度検出用サーミスタ素子で、実施例１の導電性接合材料により接合された接合層３０９で構成され、電極３０２ｂと端子３１０との間を直径３００μｍのＡｌ線３０５でワイヤボンディングし外部へ連絡されている。
なお、エポキシ系樹脂製のケース３０４とベース材３０３の間はシリコーン接着樹脂（図示せず）を用いて固定した。エポキシ系樹脂製のふた３０６の内厚部には凹み３０６′、端子３１０には穴３１０′がそれぞれ設けられ、絶縁型半導体装置１０００を外部回路と接続するためのネジ（図示せず）が装着されるようになっている。端子３１０はあらかじめ所定形状に打抜き、成形された銅板にＮｉめっきを施したものであり、エポキシ系樹脂ケース３０４に取り付けられている。
図５は図４に示した絶縁型半導体装置のサブアッセンブリ部を示した図である。当該絶縁型半導体装置は、セラミック基板と半導体素子をベース材としての複合材３０３に搭載している。ベース材には周辺部に取付穴３０３Ａが設けられている。ベース材はＣｕで構成されており、表面にＮｉめっきが施してある。ベース材３０３上には実施例１の導電性接合材料による接合層でセラミックス絶縁基板３０２を、そしてセラミックス絶縁基板３０２上にも同様に実施例１の導電性接合材料により接合された接合層によりＭＯＳＦＥＴ素子３０１がそれぞれ搭載されている。このときの接合は大気雰囲気で恒温槽を２５０℃で６０分間加熱することで接合されている。
図６は、図５におけるＭＯＳＦＥＴ素子搭載部の接合前の断面の拡大概略図である。図６に示すように、接合層に実施例１の導電性接合用材料を用いることが可能である。また実施例１の導電性接合材料の塗布時の溶液流れ防止のために、ベース材３０３上にはセラミックス絶縁基板３０２搭載領域に対応するように撥水膜３２２が施されている。さらに、セラミックス絶縁基板３０２上には、半導体素子３０１の搭載領域に対応するように撥水膜３２１が施されており、上記ペースト塗布時の溶液流れ防止を図っている。
＜適用例２＞
適用例２は、セルラー電話機等の送信部に用いる高周波電力増幅装置としての絶縁型半導体装置に関するものである。当該絶縁型半導体装置（サイズ１０．５ｍｍ×４ｍｍ×１．３ｍｍ）の構成は以下に示すとおりである。
図７は、適用例２による絶縁型半導体装置の断面模式図である。ここでは、支持部材１００としての多層ガラスセラミック基板（サイズ１０．５ｍｍ×４ｍｍ×０．５ｍｍ、３層配線、熱膨張率６．２ｐｐｍ／℃、熱伝導率２．５Ｗ／ｍ．Ｋ、曲げ強度０．２５ＧＰａ 、ヤング率１１０Ｇｐａ、誘電率５．６（１ＭＨｚ））上に、ＭＯＳＦＥＴ素子（サイズ２．４ｍｍ×１．８ｍｍ×０．２４ｍｍ）１、チップ抵抗（約７ｐｐｍ／℃）１０１、チップコンデンサ（約１１．５ｐｐｍ／℃）１０２を含むチップ部品が搭載されている。
ＭＯＳＦＥＴ素子１と多層ガラスセラミック基板１００の間には、例えばＣｕ−Ｃｕ２Ｏ複合材からなる中間金属部材１０３が装備されている。多層ガラスセラミック基板１００の内部には厚膜内層配線層（Ａｇ−１ｗｔ％Ｐｔ、厚さ１５μｍ）、多層配線間の電気的連絡のための厚膜スルーホール導体（Ａｇ−１ｗｔ％Ｐｔ、直径１４０μｍ）、放熱路のための厚膜サーマルビア（Ａｇ−１ｗｔ％Ｐｔ、直径１４０μｍ）が設けられている。
また、多層ガラスセラミック基板１００の一方の主面上に厚膜配線パターン（Ａｇ−１ｗｔ％Ｐｔ、厚さ１５μｍ）１０４が設けられる。この厚膜配線パターン１０４上にはチップ抵抗１０１、チップコンデンサ１０２を含むチップ部品が搭載されるが、まず実施例１の導電性接合材料において有機溶媒にエタノールの代わりにデカノールを同程度加えて乳鉢で１０分間混合してペースト状にした後、厚膜配線パターン上に塗布し、水素置換した恒温槽中において２００℃で３０分間加熱することにより、焼結銀層１０５により導電的にチップ部品が固着されている。
ＭＯＳＦＥＴ素子（Ｓｉ、３．５ｐｐｍ／℃）１は、多層ガラスセラミック基板１００の一方の主面に設けた凹みの部分に中間金属部材１０３を介して搭載される。搭載は１０のマイナス３乗の真空中で行った。中間金属部材１０３のサイズは２．８ｍｍ×２．２ｍｍ×０．２ｍｍである。ここで、ＭＯＳＦＥＴ素子１と中間金属部材１０３を接続する焼結銀層１０５や、中間金属部材１０３と多層ガラスセラミック基板１００を接続する接合層１０６は、いずれも実施例１の導電性接合材料において有機溶媒にエタノールの代わりにデカノールを同程度加えて乳鉢で１０分間混合し、ペースト状にした導電性接合用ペースト材料を用いて接合された層である。ＭＯＳＦＥＴ素子１と厚膜配線パターン１０４の所定部間には、Ｃｕからなるクリップ型の接続端子１０７は実施例１の導電性接合用材料を用いて接合されている。このときの接合は水素置換した恒温槽中において２００℃で３０分間加熱して行った。多層ガラスセラミック基板１００の他方の主面には、厚膜外部電極層１０４′（Ａｇ−１ｗｔ％Ｐｔ、厚さ１５μｍ）が設けられている。厚膜外部電極層１０４′は多層ガラスセラミック基板１００の内部に設けられた内部配線層やスルーホール配線を中継して厚膜配線パターン１０４と電気的に接続されている。多層ガラスセラミック基板１００の一方の主面側にはエポキシ樹脂層１０８が設けられ、これにより搭載チップ部品等は封止されている。
＜適用例３＞
適用例３は、ミニモールド型トランジスタ用のリードフレームとして複合材を適用した非絶縁型半導体装置に関する。
図８は、適用例３によるミニモールド型非絶縁型半導体装置の断面模式図である。半導体素子１としてのＳｉからなるトランジスタ素子（サイズ１ｍｍ×１ｍｍ×０．３ｍｍ）は、例えばＣｕ−Ｃｕ２Ｏ複合材からなるリードフレーム（厚さ０．３ｍｍ）６００に実施例１の導電性接合用材料を塗布した後、窒素置換された恒温槽において２００℃で６０分間加熱を行うことで、焼結銀層６０１により接合されている。トランジスタ素子１のコレクタも実施例１の導電性接合材料を用いて接合された側に配置されている。エミッタ及びベースは実施例１の導電性接合材料により接合された側と反対側に設けられ、トランジスタ素子１から引出されたクリップ形状の端子６０２によりリードフレーム６００に実施例１の導電性接合材料を塗布し、クリップ形状の端子に同様に窒素置換された恒温槽において２００℃において６０分間の加熱を加えることにより接合されている。また、トランジスタ素子１の搭載とクリップ形状の端子６０２が施された主要部は、トランスファモールドによってエポキシ樹脂６０３で覆われている。リードフレーム６００はエポキシ樹脂６０３によるモールドが完了した段階で切り離され、それぞれ独立した端子としての機能が付与される。
＜その他の適用例＞
ＬＥＤを基板に実装する際に本発明の導電性接合材料を用いて接合を行うことで、従来の半田、Ａｇペースト導電性接着材よりも放熱性を向上させることが可能になる。
２０１ 接合部材
２０２ Ａｇフレーク
２０３ Ａｇ２Ｏ
２０５ 焼結銀層
３０１ 半導体素子
３０２ セラミックス絶縁基板
３０２ａ 銅板
３０３ ベース材
３０４ エポキシ系樹脂ケース
３０５ ボンディングワイヤ
３０６ エポキシ系樹脂ふた
３０７ シリコーンゲル樹脂
３０８、３０９ 接合層
３１０ 端子

Claims (9)

  1. 銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、を必須成分とし、前記銀粒子と前記酸化銀粒子と前記分散剤の合計が全導電性接合材料中において９９.０〜１００重量％であり、前記銀粒子と前記酸化銀粒子の粒径が０．１μｍ以上１００μｍ以下であり、前記銀粒子がフレーク形状をなし、当該フレーク形状の銀粒子の厚さが０．１μｍ以上５．０μｍ以下であり、前記酸化銀と前記フレーク形状の銀粒子の重量比が５／９５以上２０／８０以下であり、前記銀粒子は前記分散剤により被覆されていることを特徴とする導電性接合材料。
  2. さらに、前記酸化銀粒子が、前記分散剤により被覆されていることに特徴を有する請求項１に記載の導電性接合材料。
  3. 前記銀粒子と前記酸化銀粒子の混合率は、前記銀粒子を１００質量部とした場合に、前記酸化銀粒子が０．０１質量部以上１００質量部以下であることを特徴とする請求項１に記載の導電性接合材料。
  4. 前記酸化銀粒子の量は、前記分散剤の量以下であることを特徴とする請求項３に記載の導電性接合材料。
  5. 銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、沸点が３５０℃以下の有機溶剤と、を必須成分とし、
    前記銀粒子と前記酸化銀粒子の粒径が０．１μｍ以上１００μｍ以下であり、
    前記銀粒子がフレーク形状をなし、前記分散剤で被覆されており、
    前記フレーク形状の銀粒子の厚さが０．１μｍ以上５．０μｍ以下であり、
    前記酸化銀と前記フレーク形状の銀粒子の重量比が５／９５以上２０／８０以下であり、
    前記銀粒子と前記酸化銀粒子と前記分散剤と前記有機溶剤の合計を１００質量部とした場合に、前記有機溶剤の量が９０質量部以下であり、
    前記銀粒子と前記酸化銀粒子と前記分散剤と前記有機溶剤との合計が、全導電性接合材料中において９９.０〜１００重量％で、ペースト状をなしていることを特徴とする導電性接合材料。
  6. 銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、銀以外の金属粒子と、を必須成分とし、
    前記銀粒子と前記酸化銀粒子の粒径が０．１μｍ以上１００μｍ以下であり、
    前記銀粒子がフレーク形状をなし、前記分散剤で被覆されており、
    前記フレーク形状の銀粒子の厚さが０．１μｍ以上５．０μｍ以下であり、
    前記酸化銀と前記フレーク形状の銀粒子の重量比が５／９５以上２０／８０以下であり、
    前記銀粒子と前記酸化銀粒子と前記分散剤と前記銀以外の金属粒子との合計が、全導電性接合材料中において９９.０〜１００重量％であることを特徴とする導電性接合材料。
  7. 銀粒子と、酸化銀粒子と、炭素数３０以下で構成される有機物を含む分散剤と、沸点が３５０℃以下の有機溶剤と、銀以外の金属粒子と、を必須成分とし、
    前記銀粒子と前記酸化銀粒子の粒径が０．１μｍ以上１００μｍ以下であり、
    前記銀粒子がフレーク形状をなし、前記分散剤で被覆されており、
    前記フレーク形状の銀粒子の厚さが０．１μｍ以上５．０μｍ以下であり、
    前記酸化銀と前記フレーク形状の銀粒子の重量比が５／９５以上２０／８０以下であり、
    前記銀粒子と前記酸化銀粒子と前記分散剤と前記有機溶剤と前記金属粒子の合計を１００質量部とした場合に、前記有機溶剤の量が９０質量部以下であり、
    前記銀粒子と前記酸化銀粒子と前記分散剤と前記有機溶剤と前記銀以外の金属粒子との合計が、全導電性接合材料中において９９.０〜１００重量％で、ペースト状をなしていることを特徴とする導電性接合材料。
  8. 請求項１に記載の導電性接合材料を用いて接合され、接合部が金属部分のみからなり、その空隙率が０．１％より大きく９０％より小さいことを特徴とする半導体装置。
  9. 半導体素子の電極と金属部材との間に請求項１に記載の導電性接合材料を配置し、水素中、窒素中、又はアルゴン雰囲気中において加熱することで前記導電性接合材料を焼結させ、前記半導体素子の電極と前記金属部材とを金属接合することを特徴とする接合方法。
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