JP2004197153A - Diamond-metal composite material and method for manufacturing the same - Google Patents
Diamond-metal composite material and method for manufacturing the same Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は放熱基板として用いるダイヤモンド−金属複合材料およびその製造方法に関する。
【０００２】
【従来の技術】
近年、半導体装置の大出力化、高集積化に伴いヒートシンクに対してより高い熱伝導率が求められている。ヒートシンクとして使用される典型的な材料としてはＣｕがあり、これは３９８Ｗ／ｍＫと比較的高い熱伝導率を有しているものの、熱膨張係数が１７×１０-6／Ｋと代表的な半導体素子のＳｉ（３×１０-6／Ｋ）、ＩｎＰ（４．５×１０-6／Ｋ）、ＧａＡｓ（５．９×１０-6／Ｋ）に比べて大きな値であった。そのため接合時の冷却過程において、あるいは動作時／非動作時の熱サイクルに伴って接合界面近傍に大きな熱応力が発生するため、使用できない場合があった。
【０００３】
このような場合には、Ｗ、Ｍｏといった熱膨張係数の低い材料とＣｕとを合金化することによって熱膨張係数を半導体素子に近づけたＣｕＷ、ＣｕＭｏといった材料が用いられる。しかし、Ｃｕ以外の材料が低熱伝導率であるため、これらの合金の熱伝導率は３００Ｗ／ｍＫ未満となりＣｕの熱伝導率の値以下に低下する。
【０００４】
高熱伝導率のヒートシンクと成り得る材料としては、ダイヤモンドが挙げられる。ダイヤモンドは１０００Ｗ／ｍＫ以上の高い熱伝導率を有する。しかしダイヤモンドは熱膨張係数が２．３×１０-6／Ｋと半導体素子に比べて小さすぎ、ＧａＡｓのような比較的熱膨張係数の大きな半導体素子には対応できない。またダイヤモンドのヤング率は１０５０ＧＰａと非常に大きいため、半導体素子とのロウ付け時の冷却過程において、あるいは使用時の熱サイクルにおいてヒートシンクと半導体素子との間に大きな熱応力が発生し、破壊が起き易くなるという問題がある。
【０００５】
そこでダイヤモンドと金属とを組み合わせた材料をヒートシンクとして用いることが考えられる。その一つとして、ダイヤモンド粒子と金属粉末の混合粉末を加圧しながら溶融凝固させることで金属とダイヤモンド粒子とを複合化させた材料が提案されている（特許文献１参照）。しかしながらこの材料においては、金属とダイヤモンドとの濡れ性が極めて悪く、界面の密着性に乏しいために、使用する金属に対してそれほど熱伝導率は改善されていない。
【０００６】
また、ダイヤモンドとＡｇあるいはＣｕといった金属との濡れ性を向上させたヒートシンクおよびその製法が提案されている（特許文献２参照）。この方法は、Ａｇ−Ｃｕ−Ｔｉ系合金粉末とダイヤモンド粒子を混合し加圧成形した後、該合金の融点以上まで加熱することにより合金中のＴｉがダイヤ表面と反応しＴｉＣを形成し、このＴｉＣによりＡｇあるいはＣｕとダイヤモンドとの濡れ性が改善されダイヤモンド粒子と溶融金属の界面が密着するというものである（焼結法）。また、ダイヤモンド粒子とＡｇ−Ｃｕ−Ｔｉ系合金の粉末又は板材を容器中に充填し、該合金の融点以上に加熱してダイヤモンド表面にＴｉＣ層を形成させ、さらに加熱することで該合金の一部を揮発させて多孔体とし、これにＡｇ−Ｃｕ合金を上から含浸することで焼結法よりも高い相対密度と熱伝導率を持つダイヤモンドと金属の複合材を得ている（溶浸法）。
【０００７】
この他、さらに特徴的なヒートシンクとその製法が提案されている（特許文献３参照）。基本的な製法は前記特許文献２に記載の溶浸法と同様であるが、容器中でＴｉＣをダイヤモンド表面に形成させた後、さらに加熱し続けることで完全にＡｇ−Ｃｕを揮発させてダイヤモンドとＴｉＣからなる多孔体を製造し、それに対して上からＡｇ−Ｃｕ合金を含浸することによって、高い相対密度と熱伝導率を持つダイヤモンドと金属の複合材を得るというものである。この製造法においては、ダイヤモンド粒子がＴｉＣにより連結されており粒子間には金属がほとんど存在していない。このような構造だと格子振動のみで熱が伝わっていくことが予想されるため、従来の材料（熱伝導に電子を介する）に対し熱伝導が大きくなる。また、機械的な密着強度も高くなる。
【０００８】
しかし、上記した特許文献２、３に記載の二例のように、ダイヤモンド多孔体を製造した後に多孔体の上から溶融Ａｇ−Ｃｕ合金を含浸した複合材における問題点として、大型の材料に均一に溶融Ａｇ−Ｃｕ合金を浸透させて相対密度が９５％以上の緻密体とすることは困難であり、製造可能な形状に制約があるということが挙げられる。
【０００９】
上記二例の溶浸法では容器又は型にダイヤモンド粒子を充填した後に、炭化物形成金属を含む合金を入れて融点以上に加熱し、ダイヤモンド粒子に浸透させながら金属炭化物を形成させるという方法が用いられる。この方法では、溶融合金中の炭化物成形金属の含有量が浸透していく過程で減少するために、ダイヤモンド粒子表面に形成される反応層の厚みが変動する。その結果、反応層が最適な厚みよりも厚くなった部分では、金属炭化物の低い熱伝導率に起因して熱伝導率が低下する。また、反応層が最適な厚みよりも薄くなった部分では、界面の密着性が失われるために気孔が多数発生し、密度と熱伝導率が低下する。結果としてヒートシンク全体の密度と熱伝導率が低下する。この傾向はダイヤモンド粒子の粒径が比較的小さい場合およびヒートシンクの厚みが大きい場合にさらに顕著になる。
【００１０】
また、上記の二例の溶浸法では容器又は型にダイヤモンド粒子と炭化物形成金属を含む合金を同時に入れて融点以上に加熱し、ダイヤモンド粒子表面に金属炭化物を形成させながら溶浸するという方法が用いられる。この方法では、溶融時に体積が縮小するためダイヤモンド粒子の分散状態が不均一になり、その結果、形成される金属炭化物を含む反応層の厚みが不均一となり、ヒートシンク全体の熱伝導率が低下する。この傾向はダイヤモンド粒子の粒径が比較的小さい場合およびヒートシンクの厚みが大きい場合にさらに顕著になる。
【００１１】
さらに、上記の二例の溶浸法では金属炭化物を形成した後に金属の一部又は全部を揮発させて多孔体を形成し溶浸をするという方法が用いられる。この方法のように多孔体の比較的小さな隙間に金属を溶浸し緻密化することは、多孔体表面の大部分を占める金属炭化物と金属との濡れ性が悪いため困難である。そのため、１００μｍ以下程度の比較的粒径の小さなダイヤモンド粒子を用いる場合には多孔体の空隙が小さくなるため、緻密体を得ることは困難である。また、製造するヒートシンクの厚みが大きくなる場合にも、溶浸する深さが大きくなるためヒートシンク全体を緻密体とすることは難しい。
【００１２】
特許文献３記載のダイヤモンドが炭化物で連結されている構造となっているもののような場合にはヒートシンクのヤング率が非常に高くなり、前述のように半導体素子との接合界面に大きな熱応力が発生するため好ましくない。また、特許文献２において提案されている焼結法では、相対密度が低い材料しか得られない。
【００１３】
さらに、上記した二例では使用するダイヤモンド粒子の粒径を６０μｍ以上、７００μｍ以下としているが、ダイヤモンドは硬度が高く、粒径の大きなダイヤモンド粒子を使用してヒートシンクを製造した場合、加工性が著しく損なわれ、表面の平坦度が十分に得られないという問題が発生する。その結果、半導体素子との接合時若しくは動作時の熱サイクル負荷に伴って密着性が低下し、熱伝導性が低下するため、半導体素子の動作が不安定になってしまう。
【００１４】
【特許文献１】
特開平４−２５９３０５号公報
【特許文献２】
特開平１１−６７９９１号公報
【特許文献３】
特開平１０−２２３８１２号公報
【発明が解決しようとする課題】
【００１５】
本発明は前記問題を解決し、従来よりも均一に緻密化された、熱伝導率の高いダイヤモンド−金属複合材料及びその製造方法を提供することを目的とする。
【００１６】
【課題を解決するための手段】
本発明者らは従来のダイヤモンドと金属の複合材およびその製造方法における課題を解消するダイヤモンド−金属複合材料およびその製造方法を提供するべく検討した結果、前記課題は本発明の次の構成により解決することができることを見出した。
【００１７】
（１）平均粒径が６０μｍ未満のダイヤモンド粒子と、該ダイヤモンド粒子の表面に形成された４ａ、５ａ及び６ａ族元素から選ばれた一種以上からなる金属２の炭化物を主成分とする反応層と、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属１とからなり、前記金属１によって形成されたマトリックス中に該反応層を有する各ダイヤモンド粒子が金属１によって隔てられて分散していることを特徴とするダイヤモンド−金属複合材料。
（２）室温下での熱伝導率が３５０Ｗ／ｍＫ〜６００Ｗ／ｍＫの範囲であることを特徴とする、上記（１）に記載のダイヤモンド−金属複合材料。
（３）前記ダイヤモンド粒子が平均粒径で１０μｍ以上、６０μｍ未満であることを特徴とする、上記（１）または（２）に記載のダイヤモンド−金属複合材料。
【００１８】
（４）前記ダイヤモンド粒子が平均粒径で２０μｍ以上、４０μｍ以下であることを特徴とする、上記（１）〜（３）のいずれかに記載のダイヤモンド−金属複合材料。
（５）前記ダイヤモンド粒子がダイヤモンド−金属複合材料の３５〜８０ｖｏｌ％を占めることを特徴とする、上記（１）〜（４）のいずれかに記載のダイヤモンド−金属複合材料。
（６）前記金属１がＡｇ、Ｃｕから選ばれた一種以上の金属からなることを特徴とする、上記（１）〜（５）のいずれかに記載のダイヤモンド−金属複合材料。
【００１９】
（７）前記金属１がＡｇとＣｕとの合金であり、金属１中に占めるＡｇの割合が５５ｖｏｌ％〜８５ｖｏｌ％であることを特徴とする、上記（１）〜（６）のいずれかに記載のダイヤモンド−金属複合材料。
（８）前記反応層が平均で０．０１μｍ〜１．０μｍの範囲の厚みでダイヤモンド粒子表面に形成されていることを特徴とする、上記（１）〜（７）のいずれかに記載のダイヤモンド−金属複合材料。
（９）相対密度が９５％以上であり、室温下での熱伝導率が前記金属１の熱伝導率よりも高いことを特徴とする、上記（１）〜（８）のいずれかに記載のダイヤモンド−金属複合材料。
（１０）上記（１）〜（９）のいずれかに記載のダイヤモンド−金属複合材料を用いたヒートシンク。
（１１）上記（１０）に記載のヒートシンクを用いた半導体デバイス。
【００２０】
（１２）ダイヤモンド粒子と金属と金属炭化物とからなるダイヤモンド−金属複合材料の製造方法であって、平均粒径が６０μｍ未満のダイヤモンド粒子と、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属１の粉末と、４ａ、５ａ及び６ａ族元素から選ばれた一種以上からなる金属２の粉末との混合粉末、又は、ダイヤモンド粒子と、該金属１及び該金属２の合金粉末との混合粉末を得る工程１と、該混合粉末を加圧成形する工程２と、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属３の粉末を加圧成形して成形体を得る工程３と、工程２で製造した混合粉末成形体の上に工程３で得た金属３の成形体を配置する工程４と、非酸化雰囲気下において、両成形体を接触した状態に保ちながら金属１及び金属３の融点以上に加熱してダイヤモンド粒子表面に金属２の炭化物を形成するとともに、ダイヤモンド粒子間隙に溶融した金属３を無負荷で溶浸し緻密体とする工程５を含むことを特徴とする、ダイヤモンド−金属複合材料の製造方法。
【００２１】
（１３）ダイヤモンド粒子と金属と金属炭化物からなるダイヤモンド−金属複合材料の製造方法であって、平均粒径が６０μｍ未満のダイヤモンド粒子と、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属１の粉末と、４ａ、５ａ及び６ａ族元素から選ばれた一種以上からなる金属２の粉末との混合粉末、又は、ダイヤモンド粒子と、該金属１と該金属２の合金粉末との混合粉末を得る工程１と、該混合粉末を加圧成形する工程２と、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属３の板材あるいは塊材を準備する工程３と、工程２で製造した混合粉末成形体の上に工程３で準備した金属３の成形体を配置する工程４と、非酸化雰囲気下において、両成形体を接触した状態に保ちながら金属１及び金属３の融点以上に加熱してダイヤモンド粒子表面に金属２の炭化物を形成するとともに、ダイヤモンド粒子間隙に溶融した金属３を無負荷で溶浸し緻密体とする工程５を含むことを特徴とする、ダイヤモンド−金属複合材料の製造方法。
【００２２】
（１４）前記ダイヤモンド粒子が平均粒径が１０μｍ以上、６０μｍ未満のダイヤモンド粒子であることを特徴とする、上記（１２）または（１３）に記載のダイヤモンド−金属複合材料の製造方法。
（１５）前記ダイヤモンド粒子の平均粒径が２０μｍ以上、４０μｍ以下であることを特徴とする、上記（１４）に記載のダイヤモンド−金属複合材料の製造方法。
（１６）前記工程２における成形を冷間または温間で行い、その時の圧力が１００〜１０００ＭＰａの範囲であることを特徴とする、上記（１２）〜（１５）のいずれかに記載のダイヤモンド−金属複合材料の製造方法。
（１７）前記工程３において、金属３の成形体、板材又は塊材の体積が、前記工程２で製造した混合粉末成形体中に存在する気孔の総体積よりも大きいことを特徴とする、上記（１２）〜（１６）のいずれかに記載のダイヤモンド−金属複合材料の製造方法。
【００２３】
（１８）前記工程２において得られた成形体中の金属１、金属２又はその合金の粉末の融点をＴｍ１、前記工程３において成形あるいは準備した金属３の成形体、板材あるいは塊材の融点をＴｍ２とした場合、Ｔｍ１≧Ｔｍ２であることを特徴とする、上記（１２）〜（１７）のいずれかに記載のダイヤモンド−金属複合材料の製造方法。
（１９）前記工程５において、加熱温度をＴ、金属１の融点をＴｍ1、金属３の融点をＴｍ2とした場合、Ｔ≧Ｔｍ1＋２００℃及びＴ≧Ｔｍ2＋２００℃であることを特徴とする、上記（１２）〜（１８）のいずれかに記載のダイヤモンド−金属複合材料の製造方法。
（２０）前記工程５において、加熱時の雰囲気が０．０１３３Ｐａ以下の真空、又はアルゴン、水素もしくはヘリウムを含むガス雰囲気であることを特徴とする、上記（１２）〜（１９）のいずれかに記載のダイヤモンド−金属複合材料の製造方法。
【００２４】
【発明の実施の形態】
本発明のダイヤモンド−金属複合材料は、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属１をマトリックスとし、このマトリックス中に平均粒径が６０μｍ未満のダイヤモンド粒子が分散した構造となっている。ダイヤモンド粒子はそれぞれが接触しておらず、その表面に、４ａ、５ａ及び６ａ族元素から選ばれた一種以上からなる金属２の炭化物とを主成分とする反応層が存在しており、これを介してマトリックス金属１とダイヤモンド粒子とが密着した構造となっている。上記の構造により、本発明のダイヤモンド−金属複合材料は相対密度を９５％以上とし、室温での熱伝導率が３５０Ｗ／ｍＫ〜６００Ｗ／ｍＫの範囲とすることができる。
【００２５】
上記本発明のダイヤモンド−金属複合材料は相対密度が少なくとも９５％以上であり、さらには相対密度が９８％以上であることが望ましい。ダイヤモンド−金属複合材料中に気孔が多数残存していると、メッキをする場合にメッキ液がダイヤモンド−金属複合材料中に染み込み、実装時に加熱されて膨張することでダイヤモンド−金属複合材料が変形してしまうため好ましくない。
【００２６】
熱伝導性に優れたダイヤモンド−金属複合材料を得るには、ダイヤモンド粒子と複合化する金属１に関しても熱伝導率の高いＡｇ，Ｃｕ又はそれらを基とした合金を用いることが好ましい。さらにＡｇとＣｕを合金化することにより、金属１の融点が低下するため、純金属に比べて溶融時の表面張力が低下して濡れ性が改善されるうため、ダイヤモンド粒子間隙に浸透しやすくなり、その結果、気孔の少ない緻密なダイヤモンド−金属複合材料が製造可能となる。そのため、金属１中のＡｇの割合は５５ｖｏｌ％〜８５ｖｏｌ％であることが望ましい。
【００２７】
ダイヤモンド粒子の平均粒径は１０μｍ以上、６０μｍ未満であることが望ましく、２０μｍ以上、４０μｍ以下であることがさらに望ましい。ダイヤモンド粒子の粒径が大きすぎると加工性が著しく損なわれるため、加工コストが増大すると共に、ヒートシンクとしての仕様に耐えうる加工精度を得ることが非常に困難となる。また、ダイヤモンド粒子の粒径が細かすぎると、ダイヤモンド粒子と金属との界面が増大し、界面での熱伝導率ロスが大きくなるためダイヤモンド−金属複合材料の熱伝導率が低下し、ダイヤモンドの高熱伝導率が生かされず、ダイヤモンド−金属複合材料の熱伝導率は使用した金属の熱伝導率を下回ってしまう。
【００２８】
このため本発明のダイヤモンド−金属複合材料においては、ダイヤモンド粒子は平均粒径で１０μｍ以上、６０μｍ未満であることが望ましく、２０μｍ以上、４０μｍ以下であることがさらに望ましい。
また、ダイヤモンド−金属複合材料中のダイヤモンド粒子の比率は、ダイヤモンド−金属複合材料の熱膨張係数を搭載時の半導体素子の熱膨張係数に合わせるために３５〜８０ｖｏｌ％とすることが望ましい。
【００２９】
また、ダイヤモンド粒子と金属１との界面が十分に密着していなければ、熱伝導性に優れたダイヤモンド−金属複合材料は得られない。本発明においては、金属１が溶融し、ダイヤモンド粒子間隙に浸透するのと同時に金属２がダイヤモンド粒子表面に金属炭化物を含む反応層を形成することで密着効果が得られる。
この金属炭化物を含む反応層はダイヤモンド粒子と金属の密着性を得るために必要不可欠である反面、それ自体は熱伝導率が低いため、この反応層は界面における熱抵抗として働く。
【００３０】
粒子分散型複合材料において界面で熱伝導のロスが生じる場合、熱伝導率は以下の式で求められる
【００３１】
【数１】
ここでＫｍはマトリックスの熱伝導率、Ｋｄは分散粒子の熱伝導率、Ｖｄは分散粒子の体積分率、ａは分散粒子の半径である。界面における熱伝達率はｈｃ（熱バリアコンダクタンス）で表され、この値が大きいほど熱伝導率のロスが少ないことを意味する。すなわち界面に形成される炭化物量が多くなるほどｈｃは小さくなり、ダイヤモンド−金属複合材料の熱伝導率は低下する。
【００３３】
従って、反応層が多量に形成されて反応層が厚くなりすぎるとダイヤモンド−金属複合材料の熱伝導率が低下してしまう。
また、炭化物の形成量が少なく反応層の厚みが薄すぎるとダイヤモンド粒子表面に均一に反応層が形成されず、ダイヤモンドと金属との界面の密着性が低下して界面に気孔が多数発生するためにダイヤモンド−金属複合材料の熱伝導率は低下する。高熱伝導率のダイヤモンド−金属複合材料を得るためには、反応層の厚みが０．０１〜１．０μｍの範囲であることが望ましく、０．０５〜０．３μｍの範囲に制御することがさらに望ましい。反応層の厚みは使用するダイヤモンド粒子の粒径と、金属２の添加量によって決定される。
【００３４】
本発明のダイヤモンド−金属複合材料の製造方法は、次の工程を含んでいる。
▲１▼工程１：平均粒径が６０μｍ未満のダイヤモンド粒子と、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属１の粉末と、４ａ、５ａ及び６ａ族元素から選ばれた一種以上からなる金属２の粉末との混合粉末、又は、ダイヤモンド粒子と該金属１と該金属２の合金粉末との混合粉末を得る工程
▲２▼工程２：該混合粉末を加圧成形する工程
▲３▼工程３：Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎより選ばれた一種以上からなる金属３の粉末を加圧成形して成形体を得る工程
▲４▼工程４：工程２で製造した混合粉末成形体の上に工程３で得た金属３の成形体を配置する工程
▲５▼工程５：非酸化雰囲気下において、両成形体を接触した状態に保ちながら金属３の融点以上に加熱してダイヤモンド粒子表面に金属２の炭化物を形成するとともに、ダイヤモンド粒子間隙に溶融した金属３を無負荷で溶浸し緻密体とする工程
【００３５】
ここで、金属１及び金属３は単体である必要はなく、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎのいずれかを主成分とする金属であってもよい。また、金属２も単体である必要はなく、４ａ、５ａ及び６ａ族元素から選ばれた一種を主成分とするものであってもよい。
また、上記金属１と金属３とは同一の金属であっても良いし異なる金属であっても良い。
【００３６】
また、前記の金属３の粉末を加圧成形する工程３を金属３の板材あるいは塊材を準備する工程とし、前記工程４において金属３の板材あるいは塊材を工程２で製造した混合粉末成形体の上に配置しても良い。
前記合金粉末としては、市販の活性銀ロウ（例えば７０ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ−２ｗｔ％Ｔｉ）のように予め合金化した粉末を用いても良い。
【００３７】
前記工程２において、混合粉末を得る方法としては、金属１の粉末と金属２の粉末とダイヤモンド粒子とを混合する方法、金属１の粉末と金属２の粉末を混合してのち、これにダイヤモンド粒子を混合する方法及び金属１と金属２との合金粉末にダイヤモンド粒子を混合する方法等がある。
またこの混合粉末を成形する際には、冷間成形でも良いが、温間成形であればより密度の高い成形体が得られるため最終的な気孔率を低く抑えたい時には有効である。また、その時の圧力は１００〜１０００ＭＰａの範囲で高いほど気孔率の小さい成形体が得られる。
【００３８】
本発明のダイヤモンド−金属複合材料の製造方法ではこの工程２における冷間または温間での加圧成形工程によりダイヤモンド−金属複合材料の最終的な形状と性能が決定される。そのため、いかなる場合においてもダイヤモンド粒子と金属１および金属２の粉末又はその合金粉末とを混合した後に、加圧成形を行うことが大きな特徴である。このようにすると成形時の体積が工程終了後まで維持されるため、従来の溶浸法に比べて材料設計が容易である。また、容器中から加工して取り出すといった工程は不要であり、ニアネット製造が可能である。
【００３９】
前記工程３において、金属３の粉末加圧成形体に替えて金属３の板材あるいは塊材を用いても良い。これらの材料は同体積の粉末材と比較して表面積が小さいため、酸素含有量が少なく表面に形成される酸化物の量も少ない。そのため溶融時の表面張力が低下し濡れ性が向上する。
【００４０】
前記工程４において粉末成形体の上に配置する金属３の粉末成形体あるいは板材、塊材の体積は混合粉末成形体中に存在する気孔の総体積よりも大きくしなければ溶浸時に金属が十分に溶浸されず９５％以上の緻密なダイヤモンド−金属複合材料は得られない。
【００４１】
工程５における加熱温度は、加熱温度をＴ、金属１の融点をＴｍ1 、金属３の融点をＴｍ2 、とした場合、金属１及び金属３の表面張力を下げて濡れ性を良くするためにＴ≧Ｔｍ1＋２００℃及びＴ≧Ｔｍ2＋２００℃の関係であることが望ましい。また、加熱時の雰囲気は０．０１３３Ｐａ以上の真空下かＡｒ，Ｈｅ，Ｈ2等のガス雰囲気下である必要がある。金属が酸化してしまうような雰囲気下では溶融金属の濡れ性が阻害されるため溶浸法により緻密なダイヤモンド−金属複合材料を得ることは困難である。
【００４２】
上記した本発明のダイヤモンド−金属複合材料製造法では、均一に分散したダイヤモンド粒子表面において、金属２の金属炭化物が形成されるのと同時にダイヤモンド粒子の隙間を溶融した金属１、金属３が浸透し、緻密体とすることが特徴である。そのため、ダイヤと混合し成形体とする合金は、その上に配置する金属３と融点が同じであり、両者が同時に溶融状態となることが望ましい。
【００４３】
さらに、凝固時に金属が大きく収縮することによって引け巣が発生し内部欠陥となる可能性があるため、成形体の上に配置する金属３の融点が成形体中の合金の融点以下であることが望ましい。上に配置する金属３の融点を低くすることにより、成形体中の合金が収縮した時にできた気孔に、溶融状態にある金属３が浸透し、より緻密なダイヤモンド−金属複合材料が得られる。
すなわち、成形体中の金属１、金属２又はその合金の粉末の融点をＴｍ１、前記工程３において成形あるいは準備した金属３の成形体、板材あるいは塊材の融点をＴｍ２とした場合、Ｔｍ１≧Ｔｍ２であるようにする。
【００４４】
本発明のダイヤモンド−金属複合材料は高熱伝導率かつ従来のダイヤモンドヒートシンクに比べて易加工性であるため、半導体レーザーやマイクロ波素子などの発熱量の大きいデバイスに用いるヒートシンクとして最適である。
【００４５】
【実施例】
以下に本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。
【００４６】
［実施例１］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇ−Ｃｕ合金粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）、Ｔｉ粉末を用意した。
これらの各粉末を下記表１に示すように、ダイヤモンド粒子が７０ｖｏｌ％、Ａｇ−Ｃｕ合金粉末が２０．０〜３０．０ｖｏｌ％、Ｔｉ粉末が０．０〜１０．０ｖｏｌ％となるように混合し、成形圧力８００ＭＰaで直径１０ｍｍ×厚み３ｍｍに加圧成形した。成形体の気孔率は２５％前後であった。
【００４７】
得られた成形体の上にＡｇ−Ｃｕ合金を直径１０ｍｍ×厚み１ｍｍに成形したものを乗せ、０．０１３３ＭＰa以下の高真空下において下記表１に示す温度で２ｈ加熱処理した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。Ｔｉを添加しない場合はこの方法では試料が形成されなかったので黒鉛製のルツボ中に成形体を挿入し、溶製して試料を作製した。
【００４８】
【表１】
得られた各溶浸材料を厚さ２ｍｍまで研磨して密度を測定した後、レーザーフラッシュ法によって熱伝導率を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成されたＴｉＣを含む反応層の厚みを測定した。
【００５０】
測定によって得られた各溶浸材料のダイヤ含有量、密度、ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成されるＴｉＣを含む反応層の厚み、熱伝導率の数値を下記表２に示した。この結果から分かるように、反応層の厚みが厚くなるとＡｇ−Ｃｕ合金とダイヤモンド粒子の密着性が改善されるため、密度が向上する。熱伝導率は反応層の厚みが０．０５〜０．５μｍの範囲の時に比較的高く、０．１５μｍで最大となる。また、融点に対して加熱温度が高いほど、溶融金属の表面張力が低下して溶浸されやすくなるため密度は向上し、気孔による熱伝導のロスが抑えられるため熱伝導率が向上する。
【００５１】
【表２】
［実施例２］
原料粉末として平均粒径が5〜１００μｍのダイヤモンド粒子とＡｇ−Ｃｕ合金粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）、Ｔｉ粉末を用意した。
これらの各粉末を下記表３に示すように、ダイヤモンド粒子が７０ｖｏｌ％、Ａｇ−Ｃｕ合金粉末が１７．５〜２９．４ｖｏｌ％、Ｔｉ粉末が０．６〜１２．５ｖｏｌ％となるように混合し、成形圧力８００ＭＰaで直径２０ｍｍ×厚み１０ｍｍに加圧成形した。成形体の気孔率は２０から３５％前後であった。
得られた成形体の上にＡｇ−Ｃｕ合金粉末を直径２０ｍｍ×厚み１０ｍｍに成形したものを乗せ、０．０１３３ＭＰa以下の高真空下において加熱温度１０００℃で２ｈ加熱処理した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。
【００５３】
【表３】
得られた各溶浸材料より直径１０ｍｍ×厚さ２ｍｍに切り出してレーザーフラッシュ法によって熱伝導率を測定した。また、直径５ｍｍ×厚み１０ｍｍに加工して密度を測定した後、作動トランス式熱膨張係数測定装置により熱膨張係数を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成されたＴｉＣを含む反応層の厚みを測定した。
【００５５】
測定によって得られた各溶浸材料のダイヤモンド粒径、ダイヤ含有量、密度、ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成されるＴｉＣを含む反応層の厚み、熱伝導率の数値を下記表４に示した。この結果から分かるように、使用するダイヤモンド粒子の粒径に比例して熱伝導率は高くなる。単味金属の熱伝導率と比較するとＡｇ：４１０Ｗ／ｍＫ、Ｃｕ：３９０Ｗ／ｍＫであり、それらを超える高性能のヒートシンクとなるのは２０μｍ以上のダイヤモンド粒子を使用した場合であった。
【００５６】
【表４】
［実施例３」
実施例２で作製した試料１１〜１８を１０ｍｍ×１０ｍｍ×１ｍｍに加工し、表面にロウ付けを可能にするための金属接合層としてＡｕ−Ｓｎを厚み３μｍまで真空蒸着して表面粗さ（Ｒａ）を測定した。そしてその上に０．３×０．３×０．１ｍｍのＧａＡｓ製の半導体レーザー素子をＡｕ−Ｓｎ合金ロウ材によって接合した。
【００５８】
得られた各レーザー素子の飽和光出力を測定した結果を表５に示す。ヒートシンクに用いたダイヤモンド粒子の粒径が小さいほどメッキ後の表面品質は向上し、ロウ付け時にＡｕ−Ｓｎ合金の層が均一に形成される。その結果、半導体素子との密着性が良好かつ半導体素子の均熱性が保たれるため動作時の安定性が向上し、高い飽和光出力が得られる。また、粒径を５μｍまで小さくすると熱伝導率が３００を切ってしまい放熱性が低下するため飽和光出力は低下してしまう。
【００５９】
【表５】
［実施例４］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇおよびＣｕ、Ｔｉ粉末をそれぞれ用意した。
これらの各粉末を下記表６に示すように、ダイヤモンド粒子が７０ｖｏｌ％、Ａｇ粉末が１９．３ｖｏｌ％、Ｃｕ粉末が９．１ｖｏｌ％、Ｔｉ粉末が１．６ｖｏｌ％となるように混合し、成形圧力８００ＭＰaで直径１０ｍｍ×厚み３ｍｍに加圧成形し成形体とした。成形体の気孔率は２５％前後であった。
【００６１】
次に表６に示すように配合比の異なるＡｇ−Ｃｕ合金の板材を用意し、直径１０ｍｍ×厚み１ｍｍの円板形に加工して成形体の上に乗せ、０．０１３３ＭＰa以下の高真空下において加熱温度１０００℃で２ｈ加熱処理した。成形体の金属成分の融点は７８０℃、金属円板の融点は約７８０℃〜９７３℃である。
【００６２】
【表６】
得られた各溶浸材料を厚さ２ｍｍまで研磨して密度を測定した後、レーザーフラッシュ法によって熱伝導率を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成されたＴｉＣを含む反応層の厚みを測定した。
【００６４】
測定によって得られたダイヤ含有量、各溶浸材料の密度、ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成されるＴｉＣを含む反応層の厚み、熱伝導率の値を下記表７に示した。この結果から、上に置くＡｇ−Ｃｕ合金円板の融点が低いほど溶浸後の相対密度は高くなり、特にＡｇ−Ｃｕ合金円板中のＡｇ濃度が５５０〜８５ｖｏｌ％の時に密度が９５％以上と比較的高くなることが分かる。
【００６５】
【表７】
［実施例５］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇ−Ｃｕ合金粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）、Ｔｉ粉末を用意した。
これらの各粉末を実施例１で示した方法において試料７の条件で直径２０ｍｍ×厚み１０ｍｍの試料を作製した。溶浸後の試料はダイヤ含有量が約５５ｖｏｌ％であった。
【００６７】
また、石英容器中に混合した粉末を充填し０．０１３３ＭＰa以下の高真空下において１０００℃で２ｈ加熱処理して完全に試料が形成されたのを確認した後、さらに真空中で加熱して金属成分の大部分を揮発させて直径２０ｍｍ×厚み１０ｍｍの多孔体とした。多孔体の気孔率は約４５％であった。
得られた多孔体を石英容器に再度挿入し、その上にＡｇ−Ｃｕ合金を直径２０ｍｍ×厚み５ｍｍに成形した物を乗せ、１０００℃で２ｈ加熱処理してＡｇ−Ｃｕ合金を多孔体中に溶浸した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。溶浸後の試料はダイヤ含有量が約５５ｖｏｌ％であった。
【００６８】
２種類の製法によって得られた試料の密度を測定した結果、前者は９６％、後者は９２％であった。また、表８に示した板厚方向の密度分布を調査した結果、前者は９６％前後でほぼ一定であるのに対し、後者の試料内においては密度が変動しており、深さ方向に対して密度が低下していく傾向にあった。この結果より、多孔体の隙間にＡｇ−Ｃｕ合金を溶浸させて緻密体とすることは困難であることが分かる。
【００６９】
［実施例６］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇおよびＣｕ、Ｔｉ粉末をそれぞれ用意した。
これらの各粉末を下記表８に示すように、ダイヤモンド粒子が７０ｖｏｌ％、Ａｇ粉末が１９．３ｖｏｌ％、Ｃｕ粉末が９．１ｖｏｌ％、Ｔｉ粉末が１．６ｖｏｌ％となるように混合し、成形圧力と成形温度を変えながら直径２０ｍｍ×厚み１０ｍｍに加圧成形し成形体とした。
【００７０】
得られた成形体の上にＡｇ−Ｃｕ混合粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）を直径２０ｍｍ×厚み４ｍｍに成形した物を乗せ、０．０１３３ＭＰa以下の高真空下において加熱温度１０００℃で２ｈ加熱処理した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。
【００７１】
【表８】
得られた各溶浸材料より直径１０ｍｍ×厚さ２ｍｍに切り出してレーザーフラッシュ法によって熱伝導率を測定した。また、直径５ｍｍ×厚み１０ｍｍに加工して密度を測定した後、作動トランス式熱膨張係数測定装置により熱膨張係数を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成されたＴｉＣを含む反応層の厚みを測定した。
【００７３】
測定によって得られた各溶浸材料のダイヤ含有量、密度、 ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成されるＴｉＣを含む反応層の厚み、熱伝導率、熱膨張係数の値を下記表９に示した。この結果から分かるように、試料形成のためには１００ＭＰａ以上の成形圧が必要であり、成形圧が高いほど得られた試料の密度が高くなる。これは溶浸後の試料の密度が成形体の密度に依存していることを示す。また、温間成形によって溶浸後の密度は９８％まで向上する。成形密度によって溶浸材料のダイヤ含有量が決定されるため、熱膨張係数を低く抑えたいときには、温間成形が有利である。
【００７４】
【表９】
［実施例７］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇおよびＣｕ、Ｔｉ粉末をそれぞれ用意した。
これらの各粉末を下記表１０に示すように、ダイヤモンド粒子の含有量が異なる粉末をそれぞれ混合し、成形圧力と成形温度を変えながら直径２０ｍｍ×厚み１０ｍｍに加圧成形し成形体とした。
【００７６】
得られた成形体の上にＡｇ−Ｃｕ混合粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）を直径２０ｍｍ×厚み４ｍｍに成形したものを乗せ、０．０１３３ＭＰa以下の高真空下において加熱温度１０００℃で２ｈ加熱処理した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。試料３３は加熱処理時に溶融した金属が浸み出し、健全な溶浸材料を形成することはできなかった。
【００７７】
【表１０】
得られた各溶浸材料より直径１０ｍｍ×厚さ２ｍｍに切り出してレーザーフラッシュ法によって熱伝導率を測定した。また、直径５ｍｍ×厚み１０ｍｍに加工して密度を測定した後、作動トランス式熱膨張係数測定装置により熱膨張係数を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成されたＴｉＣを含む反応層の厚みを測定した。
【００７９】
測定によって得られた各溶浸材料の相対密度、溶浸後のダイヤ含有量、ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成されるＴｉＣを含む反応層の厚み、熱伝導率、熱膨張係数の値を下記表１１に示した。この結果から分かるように、健全な溶浸材料を作製可能なダイヤ含有量はダイヤモンド−金属複合材料中３５〜８０ｖｏｌ％の範囲であった。また、ダイヤ含有量の多い試料ほど熱伝導率が高く熱膨張係数が小さいことが分かる。
【００８０】
【表１１】
［実施例８］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇ−Ｃｕ合金粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）、Ｔｉ、Ｚｒ、Ｈｆ、V、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの各粉末をそれぞれ用意した。
これらの各粉末を下記表１２に示すような比率で混合し、成形圧力８００ＭＰaで直径１０ｍｍ×厚み３ｍｍに加圧成形し成形体とした。成形体の気孔率は２５％前後であった。
【００８２】
得られた成形体の上にＡｇ−Ｃｕ混合粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）を直径１０ｍｍ×厚み１ｍｍに成形した物を乗せ、０．０１３３ＭＰa以下の高真空下において加熱温度１０００℃で２ｈ加熱処理した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。
【００８３】
【表１２】
得られた各溶浸材料を厚さ２ｍｍまで研磨して密度を測定した後、レーザーフラッシュ法によって熱伝導率を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成された金属炭化物を含む反応層の厚みを測定した。
【００８５】
測定によって得られた各溶浸材料の相対密度、ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成される金属炭化物を含む反応層の厚み、熱伝導率を下記表１３に示した。分析より、それぞれダイヤモンド粒子表面に金属炭化物の存在が確認された。いずれの場合も金属炭化物によりダイヤモンド粒子と金属の密着性が十分に得られ、単味金属と比較して高い熱伝導率が得られた。
【００８６】
【表１３】
［実施例９］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇおよびＣｕ、Ｔｉ粉末をそれぞれ用意した。これらの各粉末を下記表１４に示すように、ダイヤモンド粒子が７０ｖｏｌ％、Ａｇ粉末が１９．３ｖｏｌ％、Ｃｕ粉末が９．１ｖｏｌ％、Ｔｉ粉末が１．６ｖｏｌ％となるように混合し、成形圧力８００ＭＰaで直径１０ｍｍ×厚み３ｍｍに加圧成形し成形体とした。成形体の気孔率は２５％前後であった。
【００８８】
次に表１４に示すようにＡｇ−Ｃｕ合金（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｍｇ、Ｚｎの板材を用意し、直径１０ｍｍ×厚み１ｍｍの円板形に加工して成形体の上に乗せ、０．０１３３ＭＰa以下の高真空下において試料５０から５３は加熱温度１０９０℃で２ｈ、試料５４から５７は加熱温度９００℃で２ｈ加熱処理した。
【００８９】
【表１４】
得られた各溶浸材料を厚さ２ｍｍまで研磨して密度を測定した後、レーザーフラッシュ法によって熱伝導率を測定した。また、ダイヤモンド粒子と金属の界面を透過型電子顕微鏡で観察し、ダイヤモンド粒子表面に形成されたＴｉＣを含む反応層の厚みを測定した。
【００９１】
測定によって得られたダイヤ含有量、各溶浸材料の密度、ダイヤモンド粒子とＡｇ−Ｃｕ合金との界面に形成されるＴｉＣを含む反応層の厚み、熱伝導率の値を下記表１５に示した。この結果から、上に置く金属円板としてＡｇ、Ｃｕおよびその合金以外の金属を用いた場合においても試料形成は可能であるが、金属部分の低熱伝導率が低下するため、得られたダイヤモンド−金属複合材料の熱伝導率も比較的低くなることが分かる。
【００９２】
【表１５】
［実施例１０］
実施例５で作製した試料３２の表面にロウ付けを可能にするための金属接合層としてＡｕ−Ｓｎを厚み３μｍまで真空蒸着した。そしてその上に０．３×０．３×０．１ｍｍのＧａＡｓ製の半導体レーザー素子をＡｕ−Ｓｎ合金ロウ材によって接合した。
得られた各レーザー素子の飽和光出力を測定した結果を表１６に示す。比較のためにダイヤモンドヒートシンクおよびＣｕ−Ｗヒートシンクを用いた場合の結果も表１６に合わせて示した。本発明のダイヤモンド粒子と金属よりなるダイヤモンド−金属複合材料は高い飽和光出力が得られた。これはダイヤモンド−金属複合材料の熱伝導率が高いために放熱性に優れていることと、ダイヤモンドに比べてヤング率が低いこと、熱膨張係数が半導体に近いため半導体素子に熱応力による歪みが生じにくいことによって、レーザー発生効率が高くなるためと考えられる。
【００９４】
【表１６】
［実施例１１］
実施例５で作製した試料３２の表面にロウ付けを可能にするための金属接合層としてＡｕ−Ｓｎを厚み３μｍまで真空蒸着した。そしてその上に０．３×０．３×０．１ｍｍのＧａＡｓ製の半導体レーザー素子をＡｕ−Ｓｎ合金ロウ材によって接合した。
得られた各レーザー素子を力１５０ｍＷで連続発振させて、半導体レーザーの温度変動から発振状態を評価した。結果を表１７に示す。比較のためにダイヤモンドヒートシンクおよびＣｕ−Ｗヒートシンクを用いた場合の結果も表１７に合わせて示した。
【００９６】
本発明の金属とダイヤよりなるダイヤモンド−金属複合材料を用いることにより、安定した発振状態が得られた。これはダイヤモンド−金属複合材料の熱伝導率が高いために放熱性に優れていることと、ダイヤモンドに比べてヤング率が低いこと、熱膨張係数が半導体に近いため半導体素子に熱応力による歪みが生じにくいことによって、半導体素子に熱応力による歪みが生じにくくなり、安定したレーザー発振状態が得られるためと考えられる。
【００９７】
【表１７】
［実施例１２］
原料粉末として平均粒径が４０μｍのダイヤモンド粒子とＡｇ−Ｃｕ合金粉末（７２ｗｔ％Ａｇ−２８ｗｔ％Ｃｕ）、Ｔｉ粉末を用意した。
これらの各粉末を実施例１で示した方法（製法１とする）において試料７の条件で直径２０ｍｍ×厚み１０ｍｍの試料を作製した。溶浸後の試料はダイヤ含有量が約５５ｖｏｌ％であった。
【００９９】
また、石英容器中に混合した粉末を充填し０．０１３３ＭＰa以下の高真空下において１０００℃で２ｈ加熱処理して完全に試料が形成されたのを確認した後、さらに真空中で加熱して金属成分を完全に揮発させて直径２０ｍｍ×厚み１０ｍｍの多孔体とした。多孔体はダイヤモンド粒子がＴｉＣで連結した構造となっており、その気孔率は約４５％であった。
【０１００】
得られた多孔体を石英容器に再度挿入し、その上にＡｇ−Ｃｕ合金を直径２０ｍｍ×厚み５ｍｍに成形した物を乗せ、１０００℃で２ｈ加熱処理してＡｇ−Ｃｕ合金を多孔体中に溶浸した。Ａｇ−Ｃｕ合金の融点は約７８０℃である。溶浸後の試料はダイヤ含有量が約５５ｖｏｌ％であった。（以上、製法２とする）
【０１０１】
２種類の製法によって得られた試料の表面にロウ付けを可能にするための金属接合層としてＡｕ−Ｓｎを厚み３μｍまで真空蒸着し、表面粗さを測定した。そしてその上に０．３×０．３×０．１ｍｍのＧａＡｓ製の半導体レーザー素子をＡｕ−Ｓｎ合金ロウ材によって接合した。
【０１０２】
得られた各レーザー素子を力１５０ｍＷで連続発振させて、半導体レーザーの温度変動から発振状態を評価した。結果を表１８に示す。製法１で作製したダイヤモンド−金属複合材料において安定した発振状態が得られた。これはダイヤモンド粒子が連結した構造となっていないために加工後の面精度が良好であり、半導体素子との密着性が良好であること、ヤング率が低いことによって、半導体素子に熱応力による歪みが生じにくくなり、安定したレーザー発振状態が得られるためと考えられる。
【０１０３】
【表１８】
【発明の効果】
本発明によれば、高密度且つ高熱伝導率なダイヤモンド−金属複合材料を提供できる。この高性能なダイヤモンド−金属複合材料をヒートシンクとして用いることによって半導体レーザーやマイクロ波デバイスなどの性能を最大限に発揮させることができる。
【図面の簡単な説明】
【図１】本発明のダイヤモンド−金属複合材料の微細構造を示す概略図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a diamond-metal composite material used as a heat dissipation substrate and a method for producing the same.
[0002]
[Prior art]
2. Description of the Related Art In recent years, as the output of a semiconductor device has been increased and the integration thereof has been increased, a higher heat conductivity has been required for a heat sink. A typical material used as a heat sink is Cu, which has a relatively high thermal conductivity of 398 W / mK, but has a coefficient of thermal expansion of 17 × 10-6/ K and Si (3 × 10-6/ K), InP (4.5 × 10-6/ K), GaAs (5.9 × 10-6/ K). As a result, large thermal stress is generated in the vicinity of the bonding interface during the cooling process during the bonding or in accordance with the thermal cycle during operation / non-operation.
[0003]
In such a case, a material such as CuW or CuMo having a coefficient of thermal expansion close to that of a semiconductor element by alloying Cu with a material having a low coefficient of thermal expansion such as W or Mo is used. However, since materials other than Cu have low thermal conductivity, the thermal conductivity of these alloys is less than 300 W / mK, which is lower than the value of Cu thermal conductivity.
[0004]
A material that can serve as a heat sink having high thermal conductivity includes diamond. Diamond has a high thermal conductivity of 1000 W / mK or more. However, diamond has a coefficient of thermal expansion of 2.3 × 10-6/ K is too small compared to a semiconductor element, and cannot be applied to a semiconductor element having a relatively large thermal expansion coefficient such as GaAs. In addition, since the Young's modulus of diamond is very large at 1050 GPa, a large thermal stress is generated between the heat sink and the semiconductor element in a cooling process at the time of brazing to the semiconductor element or in a heat cycle during use, and breakage occurs. There is a problem that it becomes easier.
[0005]
Therefore, it is conceivable to use a material combining diamond and metal as the heat sink. As one of them, a material has been proposed in which a mixed powder of diamond particles and metal powder is melted and solidified while applying pressure, thereby combining the metal and diamond particles (see Patent Document 1). However, in this material, the wettability between the metal and the diamond is extremely poor, and the adhesiveness at the interface is poor, so that the thermal conductivity of the material used is not so much improved.
[0006]
In addition, a heat sink having improved wettability between diamond and a metal such as Ag or Cu and a method for manufacturing the same have been proposed (see Patent Document 2). In this method, Ag-Cu-Ti alloy powder and diamond particles are mixed and pressed, and then heated to a temperature equal to or higher than the melting point of the alloy so that Ti in the alloy reacts with the diamond surface to form TiC. The wettability of Ag or Cu and diamond is improved by TiC, and the interface between the diamond particles and the molten metal is brought into close contact (sintering method). Also, a powder or plate material of diamond particles and an Ag-Cu-Ti alloy is filled in a container, heated to a temperature equal to or higher than the melting point of the alloy to form a TiC layer on the diamond surface, and further heated to form a TiC layer. By evaporating the portion to form a porous body and impregnating the porous body with an Ag-Cu alloy from above, a diamond-metal composite material having a higher relative density and higher thermal conductivity than the sintering method is obtained (infiltration method). ).
[0007]
In addition, a more characteristic heat sink and its manufacturing method have been proposed (see Patent Document 3). The basic manufacturing method is the same as that of the infiltration method described in Patent Document 2, but after forming TiC on the diamond surface in a container, the heating is further continued to completely volatilize the Ag-Cu so that the diamond is removed. By producing a porous body made of Ti and TiC and impregnating it with an Ag-Cu alloy from above, a diamond-metal composite material having a high relative density and a high thermal conductivity is obtained. In this production method, diamond particles are connected by TiC, and there is almost no metal between the particles. With such a structure, it is expected that heat will be transmitted only by lattice vibration, so that heat conduction will be higher than that of a conventional material (via electrons for heat conduction). Further, the mechanical adhesion strength is also increased.
[0008]
However, as in the two examples described in Patent Literatures 2 and 3 described above, a problem in a composite material in which a molten Ag-Cu alloy is impregnated from above a porous body after the porous body is manufactured is that a large-sized material is uniformly formed. It is difficult to make a dense body having a relative density of 95% or more by infiltrating a molten Ag-Cu alloy into the alloy, and the shape that can be manufactured is limited.
[0009]
In the infiltration method of the above two examples, a method is used in which after the diamond particles are filled in a container or a mold, an alloy containing a carbide forming metal is put into the vessel or the mold and heated to a temperature equal to or higher than the melting point, and the metal carbide is formed while penetrating the diamond particles. . In this method, since the content of the carbide forming metal in the molten alloy decreases in the course of infiltration, the thickness of the reaction layer formed on the diamond particle surface varies. As a result, in portions where the reaction layer is thicker than the optimum thickness, the thermal conductivity is reduced due to the low thermal conductivity of the metal carbide. In addition, in the portion where the reaction layer is thinner than the optimum thickness, the adhesion at the interface is lost, so that a large number of pores are generated, and the density and the thermal conductivity decrease. As a result, the density and thermal conductivity of the entire heat sink are reduced. This tendency becomes more remarkable when the diameter of the diamond particles is relatively small and when the thickness of the heat sink is large.
[0010]
In addition, in the infiltration method of the above two examples, there is a method in which an alloy containing diamond particles and a carbide forming metal is simultaneously placed in a container or a mold, heated to a temperature equal to or higher than the melting point, and infiltrated while forming metal carbide on the diamond particle surface. Used. In this method, since the volume is reduced upon melting, the dispersion state of the diamond particles becomes uneven, and as a result, the thickness of the reaction layer containing the formed metal carbide becomes uneven, and the thermal conductivity of the entire heat sink decreases. . This tendency becomes more remarkable when the diameter of the diamond particles is relatively small and when the thickness of the heat sink is large.
[0011]
Further, in the above two infiltration methods, a method is used in which after forming a metal carbide, part or all of the metal is volatilized to form a porous body and infiltrate. It is difficult to infiltrate and densify a metal into a relatively small gap in a porous body as in this method because the metal carbide occupying most of the surface of the porous body and the metal have poor wettability. Therefore, when diamond particles having a relatively small particle size of about 100 μm or less are used, the pores of the porous body become small, and it is difficult to obtain a dense body. Further, even when the thickness of the heat sink to be manufactured is large, it is difficult to make the entire heat sink into a dense body because the infiltration depth is large.
[0012]
In the case of the structure described in Patent Document 3 in which diamond is connected by carbide, the Young's modulus of the heat sink becomes extremely high, and a large thermal stress is generated at the bonding interface with the semiconductor element as described above. Is not preferred. Further, in the sintering method proposed in Patent Document 2, only a material having a low relative density can be obtained.
[0013]
Further, in the above two examples, the particle size of the diamond particles used is set to be not less than 60 μm and not more than 700 μm. However, when the heat sink is manufactured using diamond particles having high hardness and large diameter, the workability is remarkable. As a result, there arises a problem that the flatness of the surface cannot be sufficiently obtained. As a result, the adhesion decreases with the thermal cycle load during the bonding or operation with the semiconductor element, and the thermal conductivity decreases, so that the operation of the semiconductor element becomes unstable.
[0014]
[Patent Document 1]
JP-A-4-259305
[Patent Document 2]
JP-A-11-67991
[Patent Document 3]
JP-A-10-223812
[Problems to be solved by the invention]
[0015]
An object of the present invention is to solve the above-mentioned problems and to provide a diamond-metal composite material having a higher thermal conductivity, which is more uniformly densified than before, and a method for producing the same.
[0016]
[Means for Solving the Problems]
The present inventors have studied to provide a diamond-metal composite material and a method for manufacturing the same, which solve the problems in the conventional composite material of diamond and metal and the method for manufacturing the same, and as a result, the problems are solved by the following structure of the present invention. I found that I can do it.
[0017]
(1) a diamond particle having an average particle diameter of less than 60 μm, and a reaction layer formed on the surface of the diamond particle and containing, as a main component, a metal 2 carbide made of at least one element selected from Group 4a, 5a and 6a elements. , Ag, Cu, Au, Al, Mg, and Zn, each of which has a reaction layer in a matrix formed by the metal 1. And a diamond-metal composite material.
(2) The diamond-metal composite material according to (1), wherein the thermal conductivity at room temperature is in the range of 350 W / mK to 600 W / mK.
(3) The diamond-metal composite material according to the above (1) or (2), wherein the average diameter of the diamond particles is 10 μm or more and less than 60 μm.
[0018]
(4) The diamond-metal composite material according to any one of (1) to (3), wherein the diamond particles have an average particle diameter of 20 μm or more and 40 μm or less.
(5) The diamond-metal composite material according to any one of (1) to (4), wherein the diamond particles occupy 35 to 80 vol% of the diamond-metal composite material.
(6) The diamond-metal composite material according to any one of (1) to (5), wherein the metal 1 is made of one or more metals selected from Ag and Cu.
[0019]
(7) The metal according to any one of (1) to (6), wherein the metal 1 is an alloy of Ag and Cu, and the ratio of Ag in the metal 1 is 55 vol% to 85 vol%. A diamond-metal composite according to any of the preceding claims.
(8) The diamond as described in any of (1) to (7) above, wherein the reaction layer is formed on the surface of the diamond particles with an average thickness in the range of 0.01 μm to 1.0 μm. -Metal composites.
(9) The method according to any one of (1) to (8) above, wherein the relative density is 95% or more, and the thermal conductivity at room temperature is higher than the thermal conductivity of the metal 1. Diamond-metal composite.
(10) A heat sink using the diamond-metal composite material according to any one of (1) to (9).
(11) A semiconductor device using the heat sink according to (10).
[0020]
(12) A method for producing a diamond-metal composite material comprising diamond particles, a metal and a metal carbide, wherein the diamond-metal composite material has an average particle diameter of less than 60 μm and is selected from Ag, Cu, Au, Al, Mg, Zn. Mixed powder of powder of metal 1 composed of at least one kind of metal and powder of metal 2 composed of at least one kind of element selected from group 4a, 5a and 6a, or diamond particles, alloy of metal 1 and metal 2 Step 1 of obtaining a mixed powder with a powder, Step 2 of pressing the mixed powder, and pressing of a metal 3 powder comprising at least one selected from Ag, Cu, Au, Al, Mg and Zn Step 3 of obtaining a compact by molding, and Step 4 of disposing the compact of metal 3 obtained in Step 3 on the mixed powder compact produced in Step 2, and contacting both compacts in a non-oxidizing atmosphere. While keeping A step of heating to above the melting point of group 1 and metal 3 to form carbide of metal 2 on the surface of diamond particles, and infiltrating molten metal 3 in the gap between diamond particles without load to form a dense body. A method for producing a diamond-metal composite material.
[0021]
(13) A method for producing a diamond-metal composite material comprising diamond particles, a metal and a metal carbide, wherein the diamond particles have an average particle diameter of less than 60 μm and are selected from Ag, Cu, Au, Al, Mg, and Zn. A mixed powder of a powder of metal 1 composed of at least one metal and a powder of metal 2 composed of at least one selected from elements of groups 4a, 5a and 6a, or diamond particles, and an alloy powder of metal 1 and metal 2 Step 1 of obtaining a mixed powder of the following, Step 2 of press-forming the mixed powder, and preparing a metal 3 plate or lump made of at least one selected from Ag, Cu, Au, Al, Mg and Zn. Step 3 of placing the metal 3 compact prepared in Step 3 on the mixed powder compact produced in Step 2 while maintaining both compacts in contact with each other in a non-oxidizing atmosphere. metal And a step 5 in which the carbide of the metal 2 is formed on the surface of the diamond particles by heating to a temperature higher than the melting point of the metal 3, and the molten metal 3 is infiltrated into the gaps between the diamond particles without load to form a dense body. And a method for producing a diamond-metal composite material.
[0022]
(14) The method for producing a diamond-metal composite material according to (12) or (13), wherein the diamond particles are diamond particles having an average particle diameter of 10 μm or more and less than 60 μm.
(15) The method for producing a diamond-metal composite material according to (14), wherein the average particle diameter of the diamond particles is 20 μm or more and 40 μm or less.
(16) The diamond according to any one of (12) to (15), wherein the forming in the step 2 is performed cold or warm, and the pressure at that time is in a range of 100 to 1000 MPa. Manufacturing method of metal composite material.
(17) In the step (3), the volume of the compact, plate or lump of the metal 3 is larger than the total volume of pores in the mixed powder compact produced in the step (2). (12) The method for producing a diamond-metal composite material according to any one of (16) to (16).
[0023]
(18) The melting point of the powder of the metal 1, metal 2, or an alloy thereof in the compact obtained in the above step 2 is determined by1The melting point of the metal 3 compact, plate or lump formed or prepared in step 3 is determined by Tm.2Tm1≧ Tm2The method for producing a diamond-metal composite material according to any one of the above (12) to (17), wherein
(19) In step 5, the heating temperature is T, and the melting point of metal 1 is Tm.1, The melting point of metal 3Two, T ≧ Tm1+ 200 ° C and T ≧ TmTwoThe method for producing a diamond-metal composite material according to any one of the above (12) to (18), wherein the temperature is + 200 ° C.
(20) In any one of the above (12) to (19), in the step 5, the atmosphere at the time of heating is a vacuum of 0.0133 Pa or less or a gas atmosphere containing argon, hydrogen or helium. A method for producing the diamond-metal composite material according to the above.
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
The diamond-metal composite material of the present invention has, as a matrix, a metal 1 composed of at least one selected from Ag, Cu, Au, Al, Mg, and Zn, in which diamond particles having an average particle size of less than 60 μm are dispersed. It has a structure. The diamond particles are not in contact with each other, and on the surface thereof, there is a reaction layer mainly composed of a metal 2 carbide composed of at least one element selected from the group 4a, 5a and 6a. It has a structure in which the matrix metal 1 and the diamond particles are in close contact with each other. With the above structure, the diamond-metal composite material of the present invention can have a relative density of 95% or more and a thermal conductivity at room temperature in the range of 350 W / mK to 600 W / mK.
[0025]
The diamond-metal composite material of the present invention has a relative density of at least 95% or more, and more desirably a relative density of 98% or more. If a large number of pores remain in the diamond-metal composite material, the plating solution permeates into the diamond-metal composite material when plating, and is heated and expanded during mounting to deform the diamond-metal composite material. This is not preferred.
[0026]
In order to obtain a diamond-metal composite material having excellent thermal conductivity, it is preferable to use Ag, Cu, or an alloy based on them, which has a high thermal conductivity also for the metal 1 to be composited with diamond particles. Furthermore, by alloying Ag and Cu, the melting point of metal 1 is reduced, so that the surface tension at the time of melting is reduced and the wettability is improved as compared with pure metal, so that it easily penetrates into the diamond particle gap. As a result, a dense diamond-metal composite material having few pores can be manufactured. Therefore, the ratio of Ag in the metal 1 is desirably 55 vol% to 85 vol%.
[0027]
The average particle size of the diamond particles is preferably 10 μm or more and less than 60 μm, and more preferably 20 μm or more and 40 μm or less. If the diameter of the diamond particles is too large, the workability is significantly impaired, so that the processing cost is increased and it is very difficult to obtain processing accuracy that can withstand the specification as a heat sink. On the other hand, if the diameter of the diamond particles is too small, the interface between the diamond particles and the metal increases, and the thermal conductivity loss at the interface increases, so that the thermal conductivity of the diamond-metal composite material decreases, and the high heat of the diamond increases. The conductivity is not utilized, and the thermal conductivity of the diamond-metal composite material is lower than the thermal conductivity of the metal used.
[0028]
For this reason, in the diamond-metal composite material of the present invention, the average diameter of the diamond particles is preferably 10 μm or more and less than 60 μm, and more preferably 20 μm or more and 40 μm or less.
The ratio of the diamond particles in the diamond-metal composite material is desirably 35 to 80 vol% in order to match the thermal expansion coefficient of the diamond-metal composite material with the thermal expansion coefficient of the semiconductor element when mounted.
[0029]
Further, if the interface between the diamond particles and the metal 1 is not sufficiently adhered, a diamond-metal composite material having excellent thermal conductivity cannot be obtained. In the present invention, the metal 1 melts and penetrates into the gap between the diamond particles, and at the same time, the metal 2 forms a reaction layer containing a metal carbide on the surface of the diamond particle, whereby an adhesion effect can be obtained.
The reaction layer containing the metal carbide is indispensable for obtaining the adhesion between the diamond particles and the metal. On the other hand, the reaction layer itself acts as a thermal resistance at the interface because of its low thermal conductivity.
[0030]
When thermal conduction loss occurs at the interface in the particle-dispersed composite material, the thermal conductivity is calculated by the following equation
[0031]
(Equation 1)
Here, Km is the thermal conductivity of the matrix, Kd is the thermal conductivity of the dispersed particles, Vd is the volume fraction of the dispersed particles, and a is the radius of the dispersed particles. The heat transfer coefficient at the interface is represented by hc (thermal barrier conductance), and the larger this value is, the smaller the loss of heat conductivity is. That is, as the amount of carbide formed at the interface increases, hc decreases, and the thermal conductivity of the diamond-metal composite material decreases.
[0033]
Therefore, if the reaction layer is formed in a large amount and the reaction layer becomes too thick, the thermal conductivity of the diamond-metal composite material decreases.
In addition, if the amount of carbide formed is small and the thickness of the reaction layer is too small, the reaction layer is not uniformly formed on the surface of the diamond particles, and the adhesion between the diamond and the metal decreases, and many pores are generated at the interface. In addition, the thermal conductivity of the diamond-metal composite decreases. In order to obtain a high thermal conductivity diamond-metal composite material, the thickness of the reaction layer is preferably in the range of 0.01 to 1.0 μm, and more preferably in the range of 0.05 to 0.3 μm. desirable. The thickness of the reaction layer is determined by the particle size of the diamond particles used and the amount of metal 2 added.
[0034]
The method for producing a diamond-metal composite material of the present invention includes the following steps.
{Circle around (1)} Step 1: From diamond particles having an average particle diameter of less than 60 μm, a powder of metal 1 comprising at least one selected from Ag, Cu, Au, Al, Mg, and Zn, and a 4a, 5a and 6a group element Step of obtaining a mixed powder of a metal 2 powder composed of one or more selected metals or a mixed powder of diamond particles and an alloy powder of the metal 1 and the metal 2
{Circle around (2)} Step 2: Step of pressing the mixed powder under pressure
{Circle around (3)} Step 3: A step of obtaining a compact by press-molding a metal 3 powder composed of at least one selected from Ag, Cu, Au, Al, Mg and Zn.
{Circle around (4)} Step 4: A step of arranging the metal 3 compact obtained in step 3 on the mixed powder compact produced in step 2
{Circle around (5)} Step 5: In a non-oxidizing atmosphere, the two compacts were heated to a temperature equal to or higher than the melting point of metal 3 while keeping both compacts in contact with each other to form carbides of metal 2 on the surface of the diamond particles and to melt in the gaps between the diamond particles. Step of infiltrating metal 3 with no load to form a dense body
[0035]
Here, the metal 1 and the metal 3 need not be a single substance, but may be a metal containing any of Ag, Cu, Au, Al, Mg, and Zn as a main component. Further, the metal 2 does not need to be a simple substance, and may be a substance mainly composed of one selected from the group 4a, 5a and 6a elements.
Further, the metal 1 and the metal 3 may be the same metal or different metals.
[0036]
Further, the step 3 of press-forming the powder of the metal 3 is a step of preparing a plate or lump of the metal 3, and the mixed powder compact obtained by manufacturing the plate or lump of the metal 3 in the step 4 in the step 4 May be placed on the
As the alloy powder, a powder that has been alloyed in advance, such as a commercially available active silver wax (for example, 70 wt% Ag-28 wt% Cu-2 wt% Ti), may be used.
[0037]
In the step 2, as a method of obtaining a mixed powder, a method of mixing a metal 1 powder, a metal 2 powder and diamond particles, a method of mixing a metal 1 powder and a metal 2 powder, And a method of mixing diamond particles with an alloy powder of metal 1 and metal 2.
When the mixed powder is molded, cold molding may be used. However, warm molding can provide a molded article having a higher density, and is effective when it is desired to keep the final porosity low. In addition, as the pressure at that time is higher in the range of 100 to 1000 MPa, a molded body having a lower porosity can be obtained.
[0038]
In the method for producing a diamond-metal composite material of the present invention, the final shape and performance of the diamond-metal composite material are determined by the cold or warm pressure forming step in the step 2. Therefore, in any case, it is a great feature that the pressure molding is performed after the diamond particles are mixed with the powders of the metal 1 and the metal 2 or the alloy powder thereof. By doing so, the volume at the time of molding is maintained until after the end of the process, so that material design is easier than in the conventional infiltration method. In addition, a process of processing and taking out from the container is not required, and a near net can be manufactured.
[0039]
In the step 3, a metal 3 plate or lump may be used instead of the metal 3 powder compact. Since these materials have a smaller surface area than powder materials of the same volume, the oxygen content is small and the amount of oxide formed on the surface is small. Therefore, the surface tension at the time of melting is reduced, and the wettability is improved.
[0040]
In the step 4, if the volume of the powder compact, plate, or block of the metal 3 placed on the powder compact is not larger than the total volume of the pores present in the mixed powder compact, the metal is sufficient during infiltration. And a dense diamond-metal composite material of 95% or more cannot be obtained.
[0041]
The heating temperature in the step 5 is T as the heating temperature and Tm as the melting point of the metal 1.1 ,The melting point of metal 3 is TmTwo ,In order to reduce the surface tension of the metal 1 and the metal 3 to improve the wettability, T ≧ Tm1+ 200 ° C and T ≧ TmTwoIt is desirable that the relationship be + 200 ° C. Further, the atmosphere at the time of heating is under a vacuum of 0.0133 Pa or more, or Ar, He, HTwoAnd so on. In an atmosphere in which the metal is oxidized, the wettability of the molten metal is impaired, so that it is difficult to obtain a dense diamond-metal composite material by the infiltration method.
[0042]
In the method for producing a diamond-metal composite material of the present invention described above, the metal carbide of metal 2 is formed on the surface of the uniformly dispersed diamond particles, and at the same time, the metal 1 and metal 3 which melt the gaps between the diamond particles penetrate. And a dense body. Therefore, it is desirable that the alloy mixed with the diamond to form a compact has the same melting point as the metal 3 disposed thereon, and both are simultaneously in a molten state.
[0043]
Furthermore, since the shrinkage cavities may be generated due to the large shrinkage of the metal during solidification and internal defects may occur, the melting point of the metal 3 disposed on the molded body may be lower than the melting point of the alloy in the molded body. desirable. By lowering the melting point of the metal 3 disposed above, the metal 3 in the molten state penetrates into the pores formed when the alloy in the compact shrinks, and a more dense diamond-metal composite material can be obtained.
That is, the melting point of the powder of metal 1, metal 2, or an alloy thereof in the compact is Tm.1The melting point of the metal 3 compact, plate or lump formed or prepared in step 3 is determined by Tm.2Tm1≧ Tm2So that
[0044]
Since the diamond-metal composite material of the present invention has a high thermal conductivity and is easy to process as compared with a conventional diamond heat sink, it is most suitable as a heat sink used for a device having a large calorific value such as a semiconductor laser or a microwave element.
[0045]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[0046]
[Example 1]
As raw material powders, diamond particles having an average particle diameter of 40 μm, Ag-Cu alloy powder (72 wt% Ag-28 wt% Cu), and Ti powder were prepared.
As shown in Table 1 below, each of these powders was mixed so that the diamond particles were 70 vol%, the Ag-Cu alloy powder was 20.0 to 30.0 vol%, and the Ti powder was 0.0 to 10.0 vol%. Then, it was press-formed to a diameter of 10 mm and a thickness of 3 mm at a forming pressure of 800 MPa. The porosity of the molded article was around 25%.
[0047]
An Ag-Cu alloy having a diameter of 10 mm and a thickness of 1 mm was placed on the obtained molded body, and subjected to a heat treatment at a temperature shown in Table 1 below for 2 hours under a high vacuum of 0.0133 MPa or less. The melting point of the Ag-Cu alloy is about 780C. When no Ti was added, no sample was formed by this method, so the molded body was inserted into a graphite crucible and melted to produce a sample.
[0048]
[Table 1]
Each of the obtained infiltrated materials was polished to a thickness of 2 mm to measure the density, and then the thermal conductivity was measured by a laser flash method. Further, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing TiC formed on the surface of the diamond particles was measured.
[0050]
The diamond content and density of each infiltration material obtained by the measurement, the thickness of the reaction layer containing TiC formed at the interface between the diamond particles and the Ag-Cu alloy, and the numerical values of the thermal conductivity are shown in Table 2 below. . As can be seen from this result, when the thickness of the reaction layer is increased, the adhesion between the Ag-Cu alloy and the diamond particles is improved, so that the density is improved. The thermal conductivity is relatively high when the thickness of the reaction layer is in the range of 0.05 to 0.5 μm, and becomes maximum at 0.15 μm. Further, as the heating temperature is higher than the melting point, the surface tension of the molten metal is reduced and the molten metal is easily infiltrated, so that the density is improved, and the loss of heat conduction due to pores is suppressed, so that the thermal conductivity is improved.
[0051]
[Table 2]
[Example 2]
As raw material powders, diamond particles having an average particle size of 5 to 100 μm, Ag—Cu alloy powder (72 wt% Ag-28 wt% Cu), and Ti powder were prepared.
As shown in Table 3 below, each of these powders was mixed so that the diamond particles were 70 vol%, the Ag-Cu alloy powder was 17.5 to 29.4 vol%, and the Ti powder was 0.6 to 12.5 vol%. Then, it was press-formed to a diameter of 20 mm and a thickness of 10 mm at a forming pressure of 800 MPa. The porosity of the molded body was around 20 to 35%.
An Ag-Cu alloy powder molded to a diameter of 20 mm and a thickness of 10 mm was placed on the obtained molded body, and heat-treated at a heating temperature of 1000 ° C. for 2 hours under a high vacuum of 0.0133 MPa or less. The melting point of the Ag-Cu alloy is about 780C.
[0053]
[Table 3]
Each of the obtained infiltrated materials was cut into a piece having a diameter of 10 mm and a thickness of 2 mm, and the thermal conductivity was measured by a laser flash method. After processing to a diameter of 5 mm and a thickness of 10 mm to measure the density, the coefficient of thermal expansion was measured by a working transformer type coefficient of thermal expansion measuring device. Further, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing TiC formed on the surface of the diamond particles was measured.
[0055]
The following table shows the diamond particle size, diamond content, density, thickness of the reaction layer containing TiC formed at the interface between the diamond particles and the Ag-Cu alloy, and numerical values of the thermal conductivity of each infiltration material obtained by the measurement. The results are shown in FIG. As can be seen from this result, the thermal conductivity increases in proportion to the diameter of the diamond particles used. Ag: 410 W / mK and Cu: 390 W / mK as compared with the thermal conductivity of the plain metal, and a high-performance heat sink exceeding these was the case where diamond particles of 20 μm or more were used.
[0056]
[Table 4]
[Example 3]
Samples 11 to 18 prepared in Example 2 were processed to 10 mm × 10 mm × 1 mm, and Au—Sn was vacuum-deposited to a thickness of 3 μm as a metal bonding layer to enable brazing to the surface, and the surface roughness (Ra ) Was measured. Then, a GaAs semiconductor laser element of 0.3 × 0.3 × 0.1 mm was joined thereon with an Au—Sn alloy brazing material.
[0058]
Table 5 shows the results of measuring the saturation light output of each of the obtained laser elements. The smaller the particle size of the diamond particles used for the heat sink, the higher the surface quality after plating, and the more uniform the Au-Sn alloy layer is formed during brazing. As a result, good adhesion to the semiconductor element and good heat uniformity of the semiconductor element are maintained, so that stability during operation is improved and a high saturated light output is obtained. On the other hand, if the particle size is reduced to 5 μm, the thermal conductivity falls below 300, and the heat dissipation is reduced, so that the saturated light output is reduced.
[0059]
[Table 5]
[Example 4]
As raw material powders, diamond particles having an average particle diameter of 40 μm and Ag, Cu, and Ti powders were prepared.
As shown in Table 6 below, each of these powders was mixed such that 70 vol% of diamond particles, 19.3 vol% of Ag powder, 9.1 vol% of Cu powder, and 1.6 vol% of Ti powder were formed. A compact was formed by pressure molding at a pressure of 800 MPa to a diameter of 10 mm and a thickness of 3 mm. The porosity of the molded article was around 25%.
[0061]
Next, Ag-Cu alloy plates having different mixing ratios as shown in Table 6 were prepared, processed into a disk having a diameter of 10 mm and a thickness of 1 mm, and placed on a compact, under a high vacuum of 0.0133 MPa or less. Was heated at a heating temperature of 1000 ° C. for 2 hours. The melting point of the metal component of the molded body is 780 ° C, and the melting point of the metal disk is about 780 ° C to 973 ° C.
[0062]
[Table 6]
Each of the obtained infiltrated materials was polished to a thickness of 2 mm to measure the density, and then the thermal conductivity was measured by a laser flash method. Further, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing TiC formed on the surface of the diamond particles was measured.
[0064]
Table 7 below shows the diamond content obtained by the measurement, the density of each infiltration material, the thickness of the reaction layer containing TiC formed at the interface between the diamond particles and the Ag-Cu alloy, and the thermal conductivity. . From these results, the relative density after infiltration becomes higher as the melting point of the Ag-Cu alloy disk placed thereon becomes lower. In particular, when the Ag concentration in the Ag-Cu alloy disk is 550 to 85 vol%, the density becomes 95%. It can be seen that the above is relatively high.
[0065]
[Table 7]
[Example 5]
As raw material powders, diamond particles having an average particle diameter of 40 μm, Ag-Cu alloy powder (72 wt% Ag-28 wt% Cu), and Ti powder were prepared.
A sample having a diameter of 20 mm and a thickness of 10 mm was prepared from each of these powders by the method described in Example 1 under the conditions of Sample 7. The sample after infiltration had a diamond content of about 55 vol%.
[0067]
After filling the mixed powder in a quartz container and heating at 1000 ° C. for 2 hours under a high vacuum of 0.0133 MPa or less to confirm that the sample was completely formed, the sample was further heated in vacuum to form a metal. Most of the components were volatilized to form a porous body having a diameter of 20 mm and a thickness of 10 mm. The porosity of the porous body was about 45%.
The obtained porous body was again inserted into the quartz container, and a product obtained by molding the Ag-Cu alloy to a diameter of 20 mm x a thickness of 5 mm was placed thereon, and heat-treated at 1000 ° C for 2 hours to put the Ag-Cu alloy into the porous body. Infiltrated. The melting point of the Ag-Cu alloy is about 780C. The sample after infiltration had a diamond content of about 55 vol%.
[0068]
As a result of measuring the densities of the samples obtained by the two methods, the former was 96% and the latter was 92%. Also, as a result of examining the density distribution in the plate thickness direction shown in Table 8, the former was almost constant at about 96%, while the density fluctuated in the latter sample, Density tended to decrease. From this result, it is understood that it is difficult to infiltrate the Ag-Cu alloy into the gap between the porous bodies to form a dense body.
[0069]
[Example 6]
As raw material powders, diamond particles having an average particle diameter of 40 μm and Ag, Cu, and Ti powders were prepared.
As shown in Table 8 below, each of these powders was mixed to form 70 vol% of diamond particles, 19.3 vol% of Ag powder, 9.1 vol% of Cu powder, and 1.6 vol% of Ti powder, and formed. While changing the pressure and the molding temperature, a compact was formed by pressure molding to a diameter of 20 mm and a thickness of 10 mm.
[0070]
An Ag-Cu mixed powder (72 wt% Ag-28 wt% Cu) formed into a shape having a diameter of 20 mm and a thickness of 4 mm is placed on the obtained molded body, and heated at a temperature of 1000 ° C. for 2 hours under a high vacuum of 0.0133 MPa or less. Heat treated. The melting point of the Ag-Cu alloy is about 780C.
[0071]
[Table 8]
Each of the obtained infiltrated materials was cut into a piece having a diameter of 10 mm and a thickness of 2 mm, and the thermal conductivity was measured by a laser flash method. After processing to a diameter of 5 mm and a thickness of 10 mm to measure the density, the coefficient of thermal expansion was measured by a working transformer type coefficient of thermal expansion measuring device. Further, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing TiC formed on the surface of the diamond particles was measured.
[0073]
The following table shows the diamond content, density, thickness of the reaction layer containing TiC formed at the interface between diamond particles and the Ag-Cu alloy, thermal conductivity, and coefficient of thermal expansion of each infiltration material obtained by the measurement. The results are shown in FIG. As can be seen from these results, a forming pressure of 100 MPa or more is required for forming a sample, and the higher the forming pressure, the higher the density of the obtained sample. This indicates that the density of the sample after infiltration depends on the density of the compact. Further, the density after infiltration is improved to 98% by warm forming. Since the diamond content of the infiltration material is determined by the molding density, when it is desired to keep the coefficient of thermal expansion low, warm molding is advantageous.
[0074]
[Table 9]
[Example 7]
As raw material powders, diamond particles having an average particle diameter of 40 μm and Ag, Cu, and Ti powders were prepared.
As shown in Table 10 below, each of these powders was mixed with powder having a different content of diamond particles, and was press-formed to a diameter of 20 mm and a thickness of 10 mm while changing the forming pressure and forming temperature to obtain a formed body.
[0076]
An Ag-Cu mixed powder (72 wt% Ag-28 wt% Cu) formed into a piece having a diameter of 20 mm and a thickness of 4 mm is placed on the obtained compact, and is heated at a heating temperature of 1000 ° C. for 2 hours under a high vacuum of 0.0133 MPa or less. Heat treated. The melting point of the Ag-Cu alloy is about 780C. In Sample 33, the metal melted during the heat treatment leached, and a sound infiltration material could not be formed.
[0077]
[Table 10]
Each of the obtained infiltrated materials was cut into a piece having a diameter of 10 mm and a thickness of 2 mm, and the thermal conductivity was measured by a laser flash method. After processing to a diameter of 5 mm and a thickness of 10 mm to measure the density, the coefficient of thermal expansion was measured by a working transformer type coefficient of thermal expansion measuring device. Further, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing TiC formed on the surface of the diamond particles was measured.
[0079]
Relative density of each infiltration material obtained by measurement, diamond content after infiltration, thickness of reaction layer containing TiC formed at interface between diamond particles and Ag-Cu alloy, thermal conductivity, thermal expansion coefficient Are shown in Table 11 below. As can be seen from the results, the diamond content capable of producing a sound infiltration material was in the range of 35 to 80 vol% in the diamond-metal composite material. In addition, it can be seen that the higher the diamond content, the higher the thermal conductivity and the lower the thermal expansion coefficient.
[0080]
[Table 11]
Example 8
Diamond powder having an average particle size of 40 μm, Ag-Cu alloy powder (72 wt% Ag-28 wt% Cu), Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W powders are prepared as raw material powders. did.
Each of these powders was mixed at a ratio as shown in Table 12 below, and pressed under a molding pressure of 800 MPa to a size of 10 mm in diameter × 3 mm in thickness to obtain a molded body. The porosity of the molded article was around 25%.
[0082]
A product obtained by molding an Ag-Cu mixed powder (72 wt% Ag-28 wt% Cu) to a diameter of 10 mm × a thickness of 1 mm on the obtained molded body is placed under a high vacuum of 0.0133 MPa or less at a heating temperature of 1000 ° C. for 2 hours. Heat treated. The melting point of the Ag-Cu alloy is about 780C.
[0083]
[Table 12]
Each of the obtained infiltrated materials was polished to a thickness of 2 mm to measure the density, and then the thermal conductivity was measured by a laser flash method. In addition, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing metal carbide formed on the surface of the diamond particles was measured.
[0085]
The relative density of each infiltration material, the thickness of the reaction layer containing the metal carbide formed at the interface between the diamond particles and the Ag-Cu alloy, and the thermal conductivity obtained by the measurement are shown in Table 13 below. The analysis confirmed the presence of metal carbide on the surface of each diamond particle. In each case, sufficient adhesion between the diamond particles and the metal was obtained by the metal carbide, and higher thermal conductivity was obtained as compared with the plain metal.
[0086]
[Table 13]
[Example 9]
As raw material powders, diamond particles having an average particle diameter of 40 μm and Ag, Cu, and Ti powders were prepared. As shown in Table 14 below, each of these powders was mixed such that 70 vol% of diamond particles, 19.3 vol% of Ag powder, 9.1 vol% of Cu powder, and 1.6 vol% of Ti powder were formed. A compact was formed by pressure molding at a pressure of 800 MPa to a diameter of 10 mm and a thickness of 3 mm. The porosity of the molded article was around 25%.
[0088]
Next, as shown in Table 14, a plate material of Ag-Cu alloy (72 wt% Ag-28 wt% Cu), Ag, Cu, Au, Al, Mg, and Zn was prepared and processed into a disk shape having a diameter of 10 mm and a thickness of 1 mm. The samples 50 to 53 were heated at 1090 ° C. for 2 hours and the samples 54 to 57 were heated at 900 ° C. for 2 hours under a high vacuum of 0.0133 MPa or less.
[0089]
[Table 14]
Each of the obtained infiltrated materials was polished to a thickness of 2 mm to measure the density, and then the thermal conductivity was measured by a laser flash method. Further, the interface between the diamond particles and the metal was observed with a transmission electron microscope, and the thickness of the reaction layer containing TiC formed on the surface of the diamond particles was measured.
[0091]
Table 15 below shows the diamond content, the density of each infiltration material, the thickness of the reaction layer containing TiC formed at the interface between the diamond particles and the Ag-Cu alloy, and the thermal conductivity values obtained by the measurement. . From this result, it is possible to form a sample even when a metal other than Ag, Cu and its alloy is used as the metal disk to be placed thereon, but since the low thermal conductivity of the metal part is lowered, the obtained diamond- It can be seen that the thermal conductivity of the metal composite material is also relatively low.
[0092]
[Table 15]
[Example 10]
Au-Sn was vacuum-deposited on the surface of the sample 32 manufactured in Example 5 to a thickness of 3 µm as a metal bonding layer for enabling brazing. Then, a GaAs semiconductor laser element of 0.3 × 0.3 × 0.1 mm was joined thereon with an Au—Sn alloy brazing material.
Table 16 shows the results of measuring the saturation light output of each of the obtained laser elements. For comparison, the results when a diamond heat sink and a Cu-W heat sink were used are also shown in Table 16. The diamond-metal composite material comprising the diamond particles and the metal of the present invention obtained a high saturated light output. This is because the diamond-metal composite material has high heat conductivity due to its high thermal conductivity, it has a low Young's modulus compared to diamond, and its thermal expansion coefficient is close to that of semiconductors. This is probably because the laser generation efficiency is increased by the fact that it is unlikely to occur.
[0094]
[Table 16]
[Example 11]
Au-Sn was vacuum-deposited on the surface of the sample 32 manufactured in Example 5 to a thickness of 3 µm as a metal bonding layer for enabling brazing. Then, a GaAs semiconductor laser element of 0.3 × 0.3 × 0.1 mm was joined thereon with an Au—Sn alloy brazing material.
Each of the obtained laser elements was continuously oscillated at a power of 150 mW, and the oscillation state was evaluated from the temperature fluctuation of the semiconductor laser. Table 17 shows the results. For comparison, the results when a diamond heat sink and a Cu-W heat sink were used are also shown in Table 17.
[0096]
By using the diamond-metal composite material comprising the metal and the diamond of the present invention, a stable oscillation state was obtained. This is because the diamond-metal composite material has high heat conductivity due to its high thermal conductivity, it has a low Young's modulus compared to diamond, and its thermal expansion coefficient is close to that of semiconductors. It is considered that, because it is difficult to generate, distortion due to thermal stress hardly occurs in the semiconductor element, and a stable laser oscillation state is obtained.
[0097]
[Table 17]
[Example 12]
As raw material powders, diamond particles having an average particle diameter of 40 μm, Ag-Cu alloy powder (72 wt% Ag-28 wt% Cu), and Ti powder were prepared.
A sample having a diameter of 20 mm and a thickness of 10 mm was prepared from each of these powders under the conditions of Sample 7 by the method described in Example 1 (referred to as Production Method 1). The sample after infiltration had a diamond content of about 55 vol%.
[0099]
After filling the mixed powder in a quartz container and heating at 1000 ° C. for 2 hours under a high vacuum of 0.0133 MPa or less to confirm that the sample was completely formed, the sample was further heated in vacuum to form a metal. The components were completely evaporated to give a porous body having a diameter of 20 mm and a thickness of 10 mm. The porous body had a structure in which diamond particles were connected by TiC, and had a porosity of about 45%.
[0100]
The obtained porous body was again inserted into the quartz container, and a product obtained by molding the Ag-Cu alloy to a diameter of 20 mm x a thickness of 5 mm was placed thereon, and heat-treated at 1000 ° C for 2 hours to put the Ag-Cu alloy into the porous body. Infiltrated. The melting point of the Ag-Cu alloy is about 780C. The sample after infiltration had a diamond content of about 55 vol%. (The above is the manufacturing method 2)
[0101]
Au-Sn was vacuum-deposited to a thickness of 3 μm as a metal bonding layer to enable brazing to the surfaces of the samples obtained by the two types of manufacturing methods, and the surface roughness was measured. Then, a GaAs semiconductor laser element of 0.3 × 0.3 × 0.1 mm was joined thereon with an Au—Sn alloy brazing material.
[0102]
Each of the obtained laser elements was continuously oscillated at a power of 150 mW, and the oscillation state was evaluated from the temperature fluctuation of the semiconductor laser. The results are shown in Table 18. A stable oscillation state was obtained in the diamond-metal composite material produced by Production Method 1. This is because the surface precision after processing is good because it does not have a structure in which diamond particles are connected, the adhesion to the semiconductor element is good, and the low Young's modulus causes distortion in the semiconductor element due to thermal stress. This is considered to be due to the fact that stable laser oscillation is obtained.
[0103]
[Table 18]
【The invention's effect】
According to the present invention, a diamond-metal composite material having high density and high thermal conductivity can be provided. By using this high-performance diamond-metal composite material as a heat sink, the performance of a semiconductor laser, a microwave device, and the like can be maximized.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a microstructure of a diamond-metal composite material of the present invention.
Claims (20)
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