JP5158904B2 - 導電接続部材、及び導電接続部材の作製方法 - Google Patents
導電接続部材、及び導電接続部材の作製方法 Download PDFInfo
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- JP5158904B2 JP5158904B2 JP2011535810A JP2011535810A JP5158904B2 JP 5158904 B2 JP5158904 B2 JP 5158904B2 JP 2011535810 A JP2011535810 A JP 2011535810A JP 2011535810 A JP2011535810 A JP 2011535810A JP 5158904 B2 JP5158904 B2 JP 5158904B2
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Classifications
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/492—Bases or plates or solder therefor
- H01L23/4924—Bases or plates or solder therefor characterised by the materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
- H01L21/4853—Connection or disconnection of other leads to or from a metallisation, e.g. pins, wires, bumps
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- H01L21/64—Manufacture or treatment of solid state devices other than semiconductor devices, or of parts thereof, not peculiar to a single device provided for in groups H01L31/00 - H10K99/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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Description
フリップチップボンディングは半導体素子等上に形成されたバンプ(突起状物)を、回路基板等へ接合するものであるが、そのバンプの形成にはメッキ法が主に採用されている。
フリップチップボンディングにおいては、半導体素子の構成材料と半導体素子に実装する回路配線基板との間の構成材料が異なると、熱膨張係数の相異に起因してはんだバンプ電極に応力歪を発生させる。この応力歪ははんだバンプ電極を破壊させて信頼性寿命を低下させる。
特許文献2には、ナノ粒子を使用したナノハンダ先駆体と発泡剤を混合してダイに載置して発泡ハンダ先駆体を膨張させたナノ多孔性ハンダが開示されている。
特許文献3には、平均粒径が0.005〜1.0μmの金粉、銀粉またはパラジウム粉からなる金属粉と、有機溶剤とからなる、ガラスフリットを含有していない金属ペーストを200〜400℃で焼結して得られるバンプが開示されている。このようにガラスフリットを含有していない金属ペーストを用いると、半導体ウェハー上に比較的柔らかく弾力性を有する焼結体を形成できることが開示されている。
また、特許文献4には、基板上に設けたフォトレジスト層の細孔内に金メッキ層(第1バンプ層、高さ:10μm)を設け、その上に金属ペーストとして金ペーストを滴下して充填した後焼結して焼結体(第2バンプ層)を設けたバンプが開示されている。
該バンプでは、バルク状金属をバンプの主要部として、焼結体からなる弾力性を有するバンプ先端部に配して、その剛性は第1バンプ層で担保し、フリップチップ接合時のバンプの横方向の変形を抑制しピッチを維持すると共に第2バンプ層の弾力性でバンプ高さのバラつきに追従して変形し得るので低圧で平坦度の良好な接合を可能としている。この場合、基板にレジスト膜に開口を設け、該開口部内に金メッキ層等を設けて更に金属ペーストを塗布後乾燥、焼成してバンプを形成しているので工程が煩雑になり、又、特許文献3と同様に該工程において、金属ペースト中の金属粒子の分散性が良好となる有機溶剤の使用、及び、形成された多孔質体からなるバンプの空隙率や空孔サイズについては一切開示されていなく、導電性バンプの熱サイクル特性の向上についても記載されていない。
また、半導体素子とインターポーザ等との接続構造部であるダイボンド部における接着性が低いと機械的ストレス(外部応力、内部応力)や物理応力(熱ストレス)によって、半導体素子の裏面またはインターポーザ接続端子と導電性ダイボンド部との接着界面が、部分剥離したり完全剥離したりすることがある。
高性能デバイスの実現の要請から、特に、高温動作が可能なデバイスの開発が活発になっている。そのため、確保すべきヒートサイクルの温度範囲が拡大しており、耐ヒートサイクル特性に優れる接合部の開発が望まれている。また、半導体素子の高密度化に伴って電極端子のピッチおよび面積が小さくなってきているのに伴って、半導体素子を実装基板にフリップチップ実装する際に用いる導電性バンプに関しても金属多孔質体の柔軟性、弾性、延性を発揮させて、耐ヒートサイクルに優れる導電性バンプ、導電性ダイボンド部等の導電接続部材の形成が望まれている。
即ち、本発明は、以下の(1)〜(13)に記載する発明を要旨とする。
(1)半導体素子の電極端子又は回路基板の電極端子の接合面に形成された導電接続部材であって、
該導電接続部材が銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)を含む有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、前記有機溶剤(SC)を含む有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペースト、
を加熱処理して金属微粒子(P)同士が結合して形成された金属多孔質体であり、
該金属多孔質体が平均粒子径10〜500nmの金属微粒子(P)同士が結合して形成され、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、
ことを特徴とする導電接続部材(以下、「第1の態様」ということがある)。
(2)前記導電接続部材が半導体素子間を接続させるための導電性バンプである、ことを特徴とする前記(1)に記載の導電接続部材。
(3)前記導電接続部材が半導体素子と導電性基板間を接続するための導電性ダイボンド部である、ことを特徴とする前記(1)に記載の導電接続部材。
(4)導電接続部材の作製方法であって、
電子部品における半導体素子もしくは回路基板の電極端子又は導電性基板の接合面に、
銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストで、
該有機溶剤(S)が(i)少なくとも、アミド基を有する有機溶剤(SA)5〜90体積%、常圧における沸点が20〜100℃である低沸点の有機溶剤(SB)5〜45体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜90体積%含む有機溶剤(S1)、または(ii)少なくとも、アミド基を有する有機溶剤(SA)5〜95体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜95体積%含む有機溶剤(S2)、
である導電性ペースト、
を載せて導電接続部材前駆体を形成する工程(工程1)と、
該導電接続部材前駆体上に接続する他方の電極端子又は導電性基板の接合面を位置合わせする工程(工程2)と、
該両電極端子、又は電極端子及び導電性基板と、導電接続部材前駆体とを150〜350℃の温度で加熱処理して、平均粒子径が10〜500nmの金属微粒子(P)同士が結合して形成された、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、金属多孔質体からなる導電接続部材を形成することにより前記接合面間を接合する工程(工程3)、
を含むことを特徴とする導電接続部材の作製方法(以下、「第2の態様」ということがある)。
(6)前記工程1における、金属微粒子(P)が、銅微粒子(P1)、
又は、銅微粒子(P1)90〜100質量%と、マグネシウム、アルミニウム、亜鉛、ガリウム、インジウム、錫、アンチモン、鉛、ビスマス、チタン、マンガン、及びゲルマニウムから選択された1種もしくは2種以上の第二の金属微粒子(P2)10〜0質量%(質量%の合計は100質量%)、からなることを特徴とする、前記(4)又は(5)に記載の導電接続部材の作製方法。
(7)前記金属微粒子(P2)が金属微粒子(P)中で、銅微粒子(P1)と合金を形成しているか、又は銅微粒子(P1)の表面で被覆層を形成していることを特徴とする、前記(6)に記載の導電接続部材の作製方法。
(9)前記有機溶剤(SA)がN−メチルアセトアミド、N−メチルホルムアミド、N−メチルプロパンアミド、ホルムアミド、N,N−ジメチルアセトアミド、1,3−ジメチル−2−イミダゾリジノン、N,N−ジメチルホルムアミド、1−メチル−2−ピロリドン、ヘキサメチルホスホリックトリアミド、2−ピロリジノン、ε−カプロラクタム、及びアセトアミドの中から選択される1種又は2種以上である、ことを特徴とする、前記(4)から(7)のいずれかに記載の導電接続部材の作製方法。
(10)前記有機溶剤(SB)が、一般式R1−O−R2(R1、R2は、それぞれ独立にアルキル基で、炭素原子数は1〜4である。)で表されるエーテル系化合物(SB1)、一般式R3−OH(R3は、アルキル基で、炭素原子数は1〜4である。)で表されるアルコール(SB2)、一般式R4−C(=O)−R5(R4、R5は、それぞれ独立にアルキル基で、炭素原子数は1〜2である。)で表されるケトン系化合物(SB3)、及び一般式R6−(N−R7)−R8(R6、R7、R8は、それぞれ独立にアルキル基、又は水素原子で、炭素原子数は0〜2である。)で表されるアミン系化合物(SB4)、の中から選択される1種又は2種以上である、ことを特徴とする前記(4)から(7)のいずれかに記載の導電接続部材の作製方法。
メタノール、エタノール、1−プロパノール、2−プロパノール、2−ブタノール、及び2−メチル2−プロパノールの中から選択される1種又は2種以上であるアルコール(SB2)、アセトン、メチルエチルケトン、及びジエチルケトンの中から選択される1種又は2種以上であるケトン系化合物(SB3)、
並びに/又はトリエチルアミン、及び/もしくはジエチルアミンであるアミン系化合物(SB4)である、ことを特徴とする前記(4)から(10)のいずれかに記載の導電接続部材の作製方法。
(12)前記有機バインダー(R)が、セルロース樹脂系バインダー、アセテート樹脂系バインダー、アクリル樹脂系バインダー、ウレタン樹脂系バインダー、ポリビニルピロリドン樹脂系バインダー、ポリアミド樹脂系バインダー、ブチラール樹脂系バインダー、及びテルペン系バインダーの中から選択される1種又は2種以上である、ことを特徴とする前記(4)から(11)のいずれかに記載の導電接続部材の作製方法。
(13)前記セルロース樹脂系バインダーがアセチルセルロース、メチルセルロース、エチルセルロース、ブチルセルロース、及びニトロセルロース;アセテート樹脂系バインダーがメチルグリコールアセテート、エチルグリコールアセテート、ブチルグリコールアセテート、エチルジグリコールアセテート、及びブチルジグリコールアセテート;アクリル樹脂系バインダーがメチルメタクリレート、エチルメタクリレート、及びブチルメタクリレート;ウレタン樹脂系バインダーが2,4−トリレンジイソシアネート、及びp−フェニレンジイソシアネート;ポリビニルピロリドン樹脂系バインダーがポリビニルピロリドン、及びN−ビニルピロリドン;ポリアミド樹脂系バインダーがポリアミド6、ポリアミド6.6、及びポリアミド11;ブチラール樹脂系バインダーがポリビニルブチラール;テルペン系バインダーがピネン、シネオール、リモネン、及びテルピネオールから選択される1種又は2種以上である、ことを特徴とする前記(12)に記載の導電接続部材の作製方法。
(ii)上記(4)に記載の第2に態様である「導電接続部材の作製方法」は、銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、又は、該金属微粒子(P)と、有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストを使用するので平均粒子径10〜500nmの金属微粒子(P)同士が結合して形成された、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲の金属多孔質体からなる導電接続部材を得ることができる。該導電接続部材は、上記第1に態様に記載した通り、熱サイクル特性に優れることから、優れた耐クラック性を有する。
〔1〕第1の態様の「導電接続部材」
本発明の第1の態様である「導電接続部材」は、半導体素子の電極端子又は回路基板の電極端子の接合面に形成された導電接続部材であって、
該導電接続部材が銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)を含む有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、前記有機溶剤(SC)を含む有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペースト、
を加熱処理して金属微粒子(P)同士が結合して形成された金属多孔質体であり、
該金属多孔質体が平均粒子径10〜500nmの金属微粒子(P)同士が結合して形成され、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、
ことを特徴とする。
第1の態様の導電接続部材として、導電性バンプ、導電性ダイボンド部等が挙げられる。導電性バンプは、例えば半導体素子間を接続させるための導電接続部材であり、導電性ダイボンド部は、通常導電性基板上に配置して半導体素子と接続させるための導電接続部材である。尚、電子部品の電極端子面上にスタッド状の導電性の接続部材を設け、該導電性の接続部材を介して更に本発明の導電接続部材を形成して電極パターンに電気的接続されるものでもよい。
本発明の第1の態様である「導電接続部材」は、半導体素子の電極端子又は回路基板の電極端子の接合面に形成された導電接続部材であって、該導電接続部材は、
該導電接続部材が銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、第2の態様に記載する、常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)を含む有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、前記有機溶剤(SC)を含む有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペースト、
を加熱処理して金属微粒子(P)同士が結合して形成された金属多孔質体である。
該導電性ペーストを加熱処理して金属微粒子(P)同士が結合した金属多孔質体の形成方法については第2の態様で説明する。
第1の態様である「導電接続部材」において、銅から形成された、平均粒子径が10〜500nmの範囲の金属微粒子(P)と有機分散媒(D)とを含む導電性ペーストを加熱処理して得られる金属多孔質体は、金属微粒子(P)同士がその粒子表面で結合していて形成されたもので、金属微粒子(P)の粒子径と焼成の程度により、加熱処理前(焼結前)の金属微粒子(P)の粒子形状がほぼ維持される場合もあるが、粒子形状が相当に変化する場合も多い。
尚、加熱処理前の金属微粒子(P)の平均粒子径が10nm未満では、加熱処理(焼結)により多孔質体全体に渡って均質な粒子径と空孔を形成することが困難になるおそれがあり、かえって熱サイクル特性が低下して耐クラック性も低下する場合がある。一方、該平均粒子径が500nmを超えると金属多孔質体を構成している金属微粒子及び空孔径がミクロンサイズ近くになり、前述の通り熱サイクル特性が低下する。
加熱処理前の金属微粒子(P)の平均粒子径は、走査型電子顕微鏡(SEM)によりその直径を測定することができる。例えば、二次元形状が略円形状である場合はその円の直径、略楕円形状である場合はその楕円の短径、略正方形状である場合はその正方形の辺の長さ、略長方形状である場合はその長方形の短辺の長さを測定する。「平均粒子径」は、無作為に10〜20個選択された複数の粒子の粒子径を上記顕微鏡で観察して計測し、その平均値を計算することによって求められる。
又は(ii)銅微粒子(P1)90〜100質量%と、マグネシウム、アルミニウム、亜鉛、ガリウム、インジウム、錫、アンチモン、鉛、ビスマス、チタン、マンガン、及びゲルマニウムから選択された1種もしくは2種以上の第二の金属微粒子(P2)10〜0質量%、からなる金属微粒子を使用することができる。
金属微粒子(P)の製造の具体例、及び金属微粒子(P)における金属微粒子(P2)の結合状態等の具体例については、後述する第2の態様に記載した内容と同様である。
本発明の導電接続部材における金属多孔質体の空孔の平均空孔径は、15〜120nmの範囲である。本発明の導電接続部材は、平均一次粒子径が10〜500nmの金属微粒子(P)を含む導電性ペーストを加熱処理(焼結)して得られるので、上記平均空孔径のものが得られる。尚、平均空孔径が前記範囲の上限以下であると熱サイクル特性が一層向上して優れた耐クラック性を得ることができる。平均空孔径が前記範囲の下限未満であると均質な金属多孔質体を形成することが困難になるおそれがある。
該空孔の形状は、円形状、楕円形状、正方形状、長方形状、六角形状などのいかなる形状であってもよい。ここで「平均空孔径」は、空孔の開口形状に対する最大内接円の直径であり、例えば、空孔形状が略円形状である場合はその円の直径、略楕円形状である場合はその楕円の短径、略正方形状である場合はその正方形の辺の長さ、略長方形状である場合はその長方形の短辺の長さである。また「平均空孔径」は、走査型電子顕微鏡(SEM)を用いて無作為に選択された10〜20の空孔径の断面形状を観察して計測して得られる平均値である。
本発明の導電接続部材における金属多孔質体の空隙率は6〜9体積%である。
空隙率が前記範囲の下限未満では、導電接続部材を構成するバルク状態の金属に近似する傾向となり、弾性、柔軟性が低下するので耐サイクル特性が低下して、耐クラック性も低下するおそれがある。一方、空隙率が前記範囲の上限を超えると、機械的強度が低下すると共に金属微粒子(P)同士の接触が不十分となり導電性が低下するおそれがある。空隙率の調整は、導電性ペーストの金属微粒子(P)と有機分散媒(D)との配合割合等により行うことができる。空隙率の測定は、透過型電子顕微鏡(TEM)、走査型電子顕微鏡(SEM)等を使用して行うことができる。電子顕微鏡で測定する場合は、電子顕微鏡写真を撮り、その断面像の解析で決定することができる。また、空孔サイズが100nmより小さい場合の空隙率はウルトラミクロトーム法やイオンミリング法などにより薄片化することで、透過型電子顕微鏡で観察して測定することができる。
第1の態様の導電接続部材は、金属微粒子(P)を適度に加熱処理(焼結)して得られるものである。金属微粒子(P)を焼結することにより形成される導電接続部材では、使用する金属粉の粒度、焼結条件にもよるが、多孔質で比較的柔らかく弾力性を有するものとなる。この柔らかな導電接続部材は、基板上で電極端子間の熱膨張差によって導電接続部材内に発生する応力に対して耐久性が良好である。そして、本発明に係る導電接続部材の機械的特性は、バルクの金属(めっき法により形成されたバンプ材等)と比較すると弾力性を有し、膨張・収縮によるひずみを吸収して疲労破壊の発生が抑制される。
本発明の第2の態様である「導電接続部材の作製方法」は、導電接続部材の作製方法であって、
電子部品における半導体素子もしくは回路基板の電極端子又は導電性基板の接合面に、
銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストで、
該有機溶剤(S)が(i)少なくとも、アミド基を有する有機溶剤(SA)5〜90体積%、常圧における沸点が20〜100℃である低沸点の有機溶剤(SB)5〜45体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜90体積%含む有機溶剤(S1)、または(ii)少なくとも、アミド基を有する有機溶剤(SA)5〜95体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜95体積%含む有機溶剤(S2)、
である導電性ペースト、
を載せて導電接続部材前駆体を形成する工程(工程1)と、
該導電接続部材前駆体上に接続する他方の電極端子又は導電性基板の接合面を位置合わせする工程(工程2)と、
該両電極端子、又は電極端子及び導電性基板と、導電接続部材前駆体とを150〜350℃の温度で加熱処理して、平均粒子径が10〜500nmの金属微粒子(P)同士が結合して形成された、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、金属多孔質体からなる導電接続部材を形成することにより前記接合面間を接合する工程(工程3)、
を含むことを特徴とする。
工程1は、電子部品における半導体素子もしくは回路基板の電極端子又は導電性基板の接合面に、
銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストで、
該有機溶剤(S)が(i)少なくとも、アミド基を有する有機溶剤(SA)5〜90体積%、常圧における沸点が20〜100℃である低沸点の有機溶剤(SB)5〜45体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜90体積%含む有機溶剤(S1)、または(ii)少なくとも、アミド基を有する有機溶剤(SA)5〜95体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜95体積%含む有機溶剤(S2)、
である導電性ペースト、
を載せて導電接続部材前駆体を形成する工程である。
(1)金属微粒子(P)
金属微粒子(P)の平均一次粒子径が10〜500nmの範囲が好ましい理由、及び該粒子径の測定法は、第1の態様に記載した内容と同様である。
金属多孔質体を構成している金属微粒子(P)としては、導電性、加熱処理の際の焼結性、製造の容易性から、(i)銅微粒子(P1)、
又は(ii)前記銅微粒子(P1)90〜100質量%と、マグネシウム、アルミニウム、亜鉛、ガリウム、インジウム、錫、アンチモン、鉛、ビスマス、チタン、マンガン、及びゲルマニウムから選択された1種もしくは2種以上の金属微粒子(P2)10〜0質量%(質量%の合計は100質量%)、からなる粒子であることが好ましい。
前記銅微粒子(P1)は相対的に導電性の高い金属であり、一方、金属微粒子(P2)は相対的に融点が低い金属である。銅微粒子(P1)に第二の金属微粒子(P2)を併用する場合には、金属微粒子(P2)が金属微粒子(P)中で銅微粒子(P1)と合金を形成しているか、又は前記金属微粒子(P2)が金属微粒子(P)中で銅微粒子(P1)の表面で被覆層を形成していることが好ましい。
前記銅微粒子(P1)及び金属微粒子(P2)を併用することにより、加熱処理温度を低下でき、又金属微粒子間の結合をより容易にすることができる。
本発明において、平均一次粒子径10〜500nmの金属微粒子(P1)の製造方法は、具体的には特開2008−231564号公報に開示された方法を採用することができる。該公報に開示された製造方法を採用すると、平均一次粒子径が10〜500nmの金属微粒子を容易に得ることが可能であり、また該公報に開示された金属微粒子の製造方法において、金属イオンの還元反応終了後に還元反応水溶液に凝集剤を添加して遠心分離等により回収される、反応液中の不純物が除去された金属微粒子(P)に有機分散媒(D)を添加して混練して、本発明の導電性ペーストを製造することができる。
本発明において、導電性ペースト中に金属微粒子(P)を均一に分散させるためには分散性、加熱処理の際の焼結性等に優れる特定の有機分散媒(D)を選択することが重要である。
有機分散媒(D)は、導電性ペースト中で金属微粒子(P)を分散させ、導電性ペーストの粘度の調節、及び導電性バンプ前躯体、導電性ダイボンド部前躯体等の導電接続部材前躯体の形状を維持し、かつ加熱処理の際に液状及びガス状で還元剤としての機能を発揮することができる。有機分散媒(D)は、有機溶剤(S)、又は有機溶剤(S)と有機バインダー(R)からなる。
有機溶剤(S)は、
(i)少なくとも、アミド基を有する有機溶剤(SA)5〜90体積%、常圧における沸点が20〜100℃である低沸点の有機溶剤(SB)5〜45体積%、及び常圧における沸点が100℃以上で、かつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜90体積%含む有機溶剤(S1)、並びに
(ii)少なくとも、アミド基を有する有機溶剤(SA)5〜95体積%、及び常圧における沸点が100℃以上で、かつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜95体積%含む有機溶剤(S2)、
の中から選択される1種である。
上記以外の他の有機溶剤成分を配合する場合には、テトラヒドロフラン、ジグライム、エチレンカルボナート、プロピレンカルボナート、スルホラン、ジメチルスルホキシド等の極性有機溶剤を使用することができる。
有機溶剤(S)は、導電性ペースト中で主に金属微粒子(P)を均一に分散させ、適度な粘度の調節、及び印刷(塗布)された導電接続部材前駆体が加熱処理される際に乾燥、焼成速度を調節する機能を発揮し、また金属微粒子(P)が通常の焼結温度より低い温度で焼結することを可能とする溶媒調整機能を発揮することも期待できる。
有機溶剤(S1)は、少なくとも、アミド基を有する有機溶剤(SA)5〜90体積%、常圧における沸点が20〜100℃である低沸点の有機溶剤(SB)5〜45体積%、並びに常圧における沸点が100℃以上で、かつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜90体積%含む有機溶剤である。
有機溶剤(SA)は、有機溶剤(S1)中に5〜90体積%含まれ、導電性ペースト中で分散性と保存安定性を向上し、更に前記接合面上の導電性ペーストを加熱処理して金属多孔質体を形成する際に接合面での密着性を向上する作用を有している。有機溶剤(SB)は、有機溶剤(S1)中に5〜45体積%以上含まれ、導電性ペースト中で溶媒分子間の相互作用を低下させ、分散している金属微粒子(P)の有機溶剤(S1)に対する親和性を向上する作用を有している。
有機溶剤(SC)は、有機溶剤(S1)中に5〜90体積%以上含まれ、導電性ペースト中で分散性と、分散性の一層の長期安定化を図ることが可能になる。また有機溶剤(SC)を混合有機溶剤中に存在させると、その導電性ペーストを電極端子接合面に印刷(塗布)して加熱処理すると金属多孔質体の均一性が向上し、また有機溶剤(SC)の有する酸化被膜の還元促進効果も働き、導電性の高い導電接続部材を得ることが出来る。
「有機溶剤(S1)は、少なくとも、有機溶剤(SA)5〜90体積%、有機溶剤(SB)5〜45体積%、並びに有機溶剤(SC)5〜90体積%含む有機溶剤である。」とは、有機溶剤(S1)が有機溶剤(SA)、有機溶剤(SB)、及び有機溶剤(SC)から前記配合割合で100体積%となるように配合されていてもよく、また前記配合割合の範囲内で、更に本発明の効果を損なわない範囲で他の有機溶剤成分を配合してもよいことを意味するが、この場合、有機溶剤(SA)、有機溶剤(SB)、及び有機溶剤(SC)からなる成分が90体積%以上含まれていることが好ましく、95体積%以上がより好ましい。
有機溶剤(S2)は、少なくとも、アミド基を有する有機溶剤(SA)5〜95体積%、及び常圧における沸点が100℃以上で、かつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜95体積%含む有機溶剤である。
有機溶剤(SA)は、有機溶剤(S2)中に5〜95体積%含まれ、該混合有機溶剤中で分散性と保存安定性を向上し、更に導電性ペーストを加熱処理して金属多孔質体を形成する際に接合面での密着性を向上する作用を有している。
有機溶剤(SC)は、有機溶剤(S2)中に5〜95体積%含まれ、導電性ペースト中で分散性を一層向上させる。また有機溶剤(SA)と有機溶剤(SC)とを有機溶剤(S2)中に存在させると、導電性ペーストを半導体素子の電極端子又は回路基板の電極端子の接合面上に印刷(塗布)後、加熱処理する際に、比較的低い加熱処理温度でも焼結を進行させることができる。
「有機溶剤(S2)は、少なくとも、有機溶剤(SA)5〜95体積%、及び有機溶剤(SC)5〜95体積%含む有機溶剤である。」とは、有機溶剤(S2)が有機溶剤(SA)、及び有機溶剤(SC)から前記配合割合で100体積%となるように配合されていてもよく、また前記配合割合の範囲内で更に、本発明の効果を損なわない範囲で他の有機溶剤成分を配合してもよいことを意味するが、この場合、有機溶剤(SA)、及び有機溶剤(SC)からなる成分が90体積%以上含まれることが好ましく、95体積%以上がより好ましい。
以下に上記した有機溶剤(SC)、有機溶剤(SA)、及び有機溶剤(SB)の具体例を示す。
(a)有機溶剤(SC)
有機溶剤(SC)は、常圧における沸点が100℃以上で、分子中に1又は2以上のヒドロキシル基を有するアルコール及び/又は多価アルコールからなり、還元性を有する有機化合物である。また、炭素数が5以上のアルコール、及び炭素数が2以上の多価アルコールが好ましく、常温で液状であり、比誘電率が高いもの、例えば10以上のものが好ましい。
平均一次粒子径10〜500nmの金属微粒子(P)は微粒子の表面積が大きいので酸化の影響を考慮する必要があるが、以下に挙げる有機溶剤(SC)は加熱処理(焼結)の際に液状及びガス状で還元剤としての機能を発揮するので、加熱処理の際に金属微粒子の酸化を抑制して焼結を促進する。
有機溶剤(SC)の具体例として、エチレングリコール、ジエチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、2−ブテン−1,4−ジオール、2,3−ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、グリセロール、1,1,1−トリスヒドロキシメチルエタン、2−エチル−2−ヒドロキシメチル−1,3−プロパンジオール、1,2,6−ヘキサントリオール、1,2,3−ヘキサントリオール、1,2,4−ブタントリオール等が例示できる。
上記アルコール類のなかでは、分子中に2個以上のヒドロキシル基を有する多価アルコールがより好ましく、エチレングリコール及びグリセロールが特に好ましい。
有機溶剤(SA)は、アミド基(−CONH−)を有する化合物であり、特に比誘電率が高いものが好ましい。有機溶剤(A)として、N−メチルアセトアミド(191.3 at 32℃)、N−メチルホルムアミド(182.4 at 20℃)、N−メチルプロパンアミド(172.2 at 25℃)、ホルムアミド(111.0 at 20℃)、N,N−ジメチルアセトアミド(37.78 at 25℃)、1,3−ジメチル−2−イミダゾリジノン(37.6 at 25℃)、N,N−ジメチルホルムアミド(36.7 at 25℃)、1−メチル−2−ピロリドン(32.58 at 25℃)、ヘキサメチルホスホリックトリアミド(29.0 at 20℃)、2−ピロリジノン、ε−カプロラクタム、アセトアミド等が挙げられるが、これらを混合して使用することもできる。尚、上記アミド基を有する化合物名の後の括弧中の数字は各溶媒の測定温度における比誘電率を示す。これらの中でも比誘電率が100以上である、N−メチルアセトアミド、N−メチルホルムアミド、ホルムアミド、アセトアミドなどが好適に使用できる。尚、N−メチルアセトアミド(融点:26〜28℃)のように常温で固体の場合には他の溶剤と混合して処理温度で液状として使用することができる。
有機溶剤(SB)は、常圧における沸点が20〜100℃の範囲にある有機化合物である。
常圧における沸点が20℃未満であると、有機溶剤(SB)を含む粒子分散液を常温で保存した際、有機溶剤(SB)の成分が揮発し、ペースト組成が変化してしまうおそれがある。また常圧における沸点が100℃以下の場合に、該溶媒添加による溶媒分子間の相互引力を低下させ、微粒子の分散性を更に向上させる効果が有効に発揮されることが期待できる。
有機溶剤(SB)として、一般式R1−O−R2(R1、R2は、それぞれ独立にアルキル基で、炭素原子数は1〜4である。)で表されるエーテル系化合物(SB1)、一般式R3−OH(R3は、アルキル基で、炭素原子数は1〜4である。)で表されるアルコール(SB2)、一般式R4−C(=O)−R5(R4、R5は、それぞれ独立にアルキル基で、炭素原子数は1〜2である。)で表されるケトン系化合物(SB3)、及び一般式R6−(N−R7)−R8(R6、R7、R8は、それぞれ独立にアルキル基、又は水素原子で、炭素原子数は0〜2である。)で表されるアミン系化合物(SB4)が例示できる。
前記エーテル系化合物(SB1)としては、ジエチルエーテル(35℃)、メチルプロピルエーテル(31℃)、ジプロピルエーテル(89℃)、ジイソプロピルエーテル(68℃)、メチル−t−ブチルエーテル(55.3℃)、t−アミルメチルエーテル(85℃)、ジビニルエーテル(28.5℃)、エチルビニルエーテル(36℃)、アリルエーテル(94℃)等が例示できる。
前記アルコール(SB2)としては、メタノール(64.7℃)、エタノール(78.0℃)、1−プロパノール(97.15℃)、2−プロパノール(82.4℃)、2−ブタノール(100℃)、2−メチル2−プロパノール(83℃)等が例示できる。
前記ケトン系化合物(SB3)としては、アセトン(56.5℃)、メチルエチルケトン(79.5℃)、ジエチルケトン(100℃)等が例示できる。
また、前記アミン系化合物(SB4)としては、トリエチルアミン(89.7℃)、ジエチルアミン(55.5℃)等が例示できる。
有機バインダー(R)は、導電性ペースト中で金属微粒子(P)の凝集の抑制、導電性ペーストの粘度の調節、及び導電接続部材前駆体の形状を維持する機能を発揮する。
前記有機バインダー(R)は、セルロース樹脂系バインダー、アセテート樹脂系バインダー、アクリル樹脂系バインダー、ウレタン樹脂系バインダー、ポリビニルピロリドン樹脂系バインダー、ポリアミド樹脂系バインダー、ブチラール樹脂系バインダー、及びテルペン系バインダーの中から選択される1種又は2種以上が好ましい。
具体的には、前記セルロース樹脂系バインダーがアセチルセルロース、メチルセルロース、エチルセルロース、ブチルセルロース、及びニトロセルロース;アセテート樹脂系バインダーがメチルグリコールアセテート、エチルグリコールアセテート、ブチルグリコールアセテート、エチルジグリコールアセテート、及びブチルジグリコールアセテート;アクリル樹脂系バインダーがメチルメタクリレート、エチルメタクリレート、及びブチルメタクリレート;ウレタン樹脂系バインダーが2,4−トリレンジイソシアネート、及びp−フェニレンジイソシアネート;ポリビニルピロリドン樹脂系バインダーがポリビニルピロリドン、及びN−ビニルピロリドン;ポリアミド樹脂系バインダーがポリアミド6、ポリアミド66、及びポリアミド11;ブチラール樹脂系バインダーがポリビニルブチラール;テルペン系バインダーがピネン、シネオール、リモネン、及びテルピネオール、の中から選択される1種又は2種以上であることが好ましい。
導電性ペーストは、銅から形成された、均一次粒子径10〜500nmの金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストである。
これに加熱処理すると、ある温度に達すると有機溶剤(S)の蒸発、又は有機溶剤(S)の蒸発と有機バインダー(R)の熱分解が進行して、金属微粒子(P)の表面が現れ、互いに表面で結合(焼結)する原理を利用して接合材として機能するものである。
前記導電性ペースト中の、金属微粒子(P)と有機分散媒(D)との配合割合(P/D)は50〜85質量%/50〜15質量%(質量%の合計は100質量%)であることが好ましい。
尚、本発明の効果を損なわない範囲で、本発明の導電性ペーストに他の金属微粒子、有機分散媒等を配合することができる。
有機溶剤(S)の選択により、該溶剤のみで金属微粒子(P)を均一に分散させ、導電性ペーストの粘度の調節、及び導電接続部材前駆体の形状を維持できる機能を発揮できる場合には、有機分散媒(D)として有機溶剤(S)のみからなる成分を使用できる。
導電性ペーストには、前記した成分に必要に応じて消泡剤、分散剤、可塑剤、界面活性剤、増粘剤など公知の添加物を加えることができる。導電性ペーストを製造する際に、各成分を混合した後にボールミル等を用いて混練することができる。
導電性ペーストを半導体素子の電極端子等の上に塗布して、導電性バンプ前駆体、導電性ダイボンド部前駆体等の導電接続部材前駆体を形成する手段としては、特に制限されないが例えば公知のスクリーン印刷、後述するレジスト等により開口部を形成して該開口部に導電性ペーストを塗布する方法等が挙げられる。
スクリーン印刷を使用する場合には、例えば半導体素子の電極端子等の上に版膜(レジスト)が設けられたスクリーン版を配置して、その上に導電性ペーストを載せてスキージで該ペーストを摺動すると、導電性ペーストはレジストのない部分のスクリーンを通過して、電極端子等の上に転移して、導電接続部材前駆体が形成される。導電性ペーストを充填するための開口部形成方法としては、露光・現像工程を経て感光性樹脂層にパターンを形成するフォトリソグラフィー方法、レーザー光、電子線、イオンビーム等の高エネルギー線を素子上に設けた絶縁樹脂層に照射して、加熱による溶融もしくは樹脂の分子結合を切断するアブレーションにより該樹脂層に開口部を形成する方法がある。これらの方法の中で、実用性の点からフォトリソグラフィー法、又はレーザー光を用いた開口部形成方法が好ましい。
本発明の工程2は、前記導電接続部材前駆体上に接続する他の電極端子とを位置合わせする工程である。該他の電極端子との位置合わせは、例えば半導体素子の電極端子上に形成された複数の導電接続部材前駆体と、該電極端子と対となって接合される部分との位置合わせを行い、加熱処理後に、半導体素子の電極端子と、回路基板の電極端子とが電気的接続を確保できるように接触させる工程である。具体例としては、半導体素子上の電極と、テープリール等で搬送されてきた基板の接続端子部とを光学装置等で位置合わせすることができる。
工程3は、前記導電接続部材前駆体を150〜350℃度の温度で加熱処理して、平均粒子径が10〜500nmの金属微粒子(P)同士が結合して形成された、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、金属多孔質体からなる導電接続部材を形成することにより前記接合面間を接合する工程である。
(1)加熱処理
半導体素子の電極端子上等の上に形成され、相対する端子電極と接している状態の導電接続部材前駆体は、150〜350℃度の温度で加熱処理して、半導体素子の電極端子等と相対する端子電極等を電気的、機械的に接合する。導電接続部材前駆体中に有機分散媒(D)として比較的低沸点の有機溶剤(S)が含有されている場合には、加熱処理に先立ち、予め乾燥工程を設けて有機溶剤(S)の少なくとも一部を蒸発、除去しておくことができる。
金属微粒子(P)として平均一次粒子径が10〜500nmの範粒子を使用するので、加熱により有機分散媒(D)が除去されれば、その表面のエネルギーによってバルク状態の金属の融点より低温で凝集して、金属微粒子表面間での結合(焼結)が進み、金属多孔質体からなる導電接続部材が形成される。加熱処理の際に有機溶剤(S)中に、有機溶剤(SC)が含有されていると、該溶剤が液状及び気体状で還元機能を発揮するので、金属微粒子(P)の酸化が抑制されて焼結が促進される。
このようにして得られる金属多孔質体からなる導電性バンプ、ダイボンド部等の導電接続部材における金属多孔質体の空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である。尚、導電接続部材における、空隙率、金属微粒子の平均粒子径、及び平均空孔径の測定方法は第1の態様に記載したのと同様である。
本発明の導電接続部材は、金属微粒子(P)同士が面接触し、結合(焼結)して形成された金属多孔質体であるので、適度な弾力性と柔らかさを有し、かつ、導電性も損なわれることがない。
(1)金属微粒子の平均粒子径の測定方法
金属微粒子を走査型電子顕微鏡(SEM)によって、無作為に10個選択された粒子の断面を観察し、その断面の二次元形状に対する最大内接円の直径を測定し、その平均値を求めた。尚、電子顕微鏡の断面写真において、二次元形状が略円形状である場合はその円の直径、略楕円形状である場合はその楕円の短径、略正方形状である場合はその正方形の辺の長さ、略長方形状である場合はその長方形の短辺の長さを測定した。
(2)平均空孔径の測定方法
「平均空孔径」は、走査型電子顕微鏡(SEM)を用いて無作為に選択された10〜20の空孔径の断面形状を観察して計測し、その平均値とした。
(3)空隙率の測定方法
空隙率の測定は、透過型電子顕微鏡(TEM)により、電子顕微鏡写真を撮り、その断面像の解析で決定することができる。また、空孔サイズが100nmより小さい場合の空隙率はウルトラミクロトーム法により薄片化することで、透過型電子顕微鏡(TEM)で観察して測定した。
平均一次粒子径150nmの銅微粒子と、有機溶剤と有機バインダーからなる有機分散媒から導電性ペーストを調製して、該導電性ペーストを導電性基板上に塗布して導電性バンプ前駆体を形成し、次に該前駆体上に、電子部品のリードを載せた後加熱処理(焼結)して導電性バンプ接合体を形成した。得られた導電性バンプ接合体の耐熱サイクル試験を行った。
(1)導電性ペーストの調製
表1に示す通り、水溶液中で銅イオンからの無電解還元により調製された、平均一次粒子径150nmの銅微粒子70質量%と、
有機溶剤としてグリセロール40体積%、N−メチルアセトアミド55体積%、及びトリエチルアミン5体積%からなる混合溶剤(本発明の有機溶剤(S1)に相当する)95質量%と有機バインダーとしてエチルセルロース(平均分子量1000,000)5質量%からなる有機分散媒30質量%とを混錬して、導電性ペーストを調製した。
(2)基板上にバンプ前駆体の形成と、該前駆体の焼結による導電性バンプ接合体の形成
前記導電性ペーストをセラミック基板上に設けた4個(1辺が4mmの正方形の頂点に対応する位置の100μmφ×9μm厚みのパッドに、それぞれ70μmφ×70μmの厚さにスクリーン印刷することで、導電性バンプ前駆体を形成した。
該バンプ前駆体上に、チップ型電子部品のリードを載せた後、不活性ガス雰囲気下、200℃で20分間加熱して焼結し、金属多孔質体からなる導電性バンプ接合体を形成した。
(i)空孔の観察
バンプにより接続された、回路基板とチップ型電子部品をエポキシ樹脂に埋め込めこんだ。続いて、埋め込んだ樹脂ともに電子部品・回路基板を研磨してバンプ部分の断面を露出させた。
バンプの断面を、走査型電子顕微鏡により観察を行ったところ、表1に示す通り、空隙率は7体積%で、平均空孔径は18nmであった。
(ii)耐熱サイクル試験
上記導電性バンプにより部品が接合された回路基板(導電性バンプ接合体)を、1サイクルの温度変化を下記4つの条件を順に1000回繰り返すことにより、冷熱サイクルによる耐熱サイクル試験を行った。
条件:−55℃で30分間、25℃で5分間、125℃で30分間、25℃で5分間の順
その結果、冷熱サイクル試験後の接続部の抵抗が、初期の電気抵抗の2倍以上になった場合を不良とする評価基準で評価を行ったところ、10サンプル測定しても、不良発生数は見られなかった。導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表1に示す。
実施例2において、有機溶剤として表1に示す通り、グリセロール45体積%、及びN−メチルアセトアミド55体積%からなる混合溶剤(本発明の有機溶剤(S2)に相当する)を使用した以外は、実施例1と同様にして、バンプ前駆体を形成後に加熱処理して導電性バンプ接合体を形成した。
次に、実施例2で得られた導電性バンプ接合体について、実施例1に記載したと同様に耐熱サイクル試験を行った。実施例2の導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表1に示す。
金属微粒子として、平均一次粒子径1.5μmの銅微粒子(水溶液中で銅イオンからの無電解還元により調製された銅微粒子)を用いた以外は、実施例1と同様にして、バンプ前駆体を形成後に加熱処理して、部品との導電性バンプ接合体を形成した。
次に、実施例1に記載したと同様に耐熱サイクル試験を行った。
比較例1の導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表1に示す。
実施例1で使用したと同様の平均一次粒子径150nmの銅微粒子60質量%と、
有機溶剤として表2に示す通り、グリセロール40体積%、N−メチルアセトアミド55体積%、及びトリエチルアミン5体積%からなる混合溶剤(本発明の有機溶剤(S1)に相当する)95質量%と、有機バインダーとしてエチルセルロース(平均分子量1000,000)5質量%からなる有機分散媒40質量%とを混錬して、導電性ペーストを調製した以外は、実施例1と同様にして、バンプ前駆体を形成後に加熱処理して部品との導電性バンプ接合体を形成した。
次に、実施例1に記載したと同様に耐熱サイクル試験を行った。
実施例3の導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表2に示す。
実施例4において、有機溶剤としてグリセロール45体積%、及びN−メチルアセトアミド55体積%からなる混合溶剤(本発明の有機溶剤(S2)に相当する)を表2に示す通り使用した以外は、実施例1と同様にして、バンプ前駆体を形成後に加熱処理して導電性バンプ接合体を形成した。
次に、実施例4で得られた導電性バンプ接合体について、実施例1に記載したと同様に耐熱サイクル試験を行った。実施例4の導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表2に示す。
金属微粒子として、平均一次粒子径1.5μmの銅微粒子(水溶液中で銅イオンからの無電解還元により調製された銅微粒子)を用いた以外は、実施例4と同様にして、バンプ前駆体を形成後に加熱処理して導電性バンプ接合体を形成した。
次に、実施例1に記載したと同様に耐熱サイクル試験を行った。
比較例1の導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表2に示す。
平均一次粒子径150nmの銅微粒子と、有機溶剤および有機バインダーとを表3に示す割合にそれぞれ混合して実施例5、6に用いる導電ペーストを調製した。該導電性ペーストを導電性基板上に塗布して角状のダイボンド材を形成し、次にその上に、電子部品のリードを載せた後加熱処理(焼結)して接合体を形成した。得られた接合体の空隙率、平均空孔径の測定、および耐熱サイクル試験を行った。
(1)導電性ペーストの調製
実施例5、6において、水溶液中で銅イオンからの無電解還元により調製された、平均一次粒子径150nmの銅微粒子70質量%と、
表3に示す有機溶剤(本発明の有機溶剤(S1)、(S2)にそれぞれ相当する)95質量%と、有機バインダーとしてエチルセルロース(平均分子量1000000)5質量%からなる有機分散媒30質量%とを混錬して、導電性ペーストを調製した。
(2)電子部品の接合
アルミ基板(電気化学工業(株)製、商品名:ヒットプレートK−1、アルミ板厚1.5mm上に、厚さ0.075mmの絶縁層が形成され、さらに該絶縁層上に厚さ0.038mmの回路用銅箔が積層されている)を用い、前記銅箔をエッチングによって5.5×5.5mmにパターニングしてパッドを形成した。導電性ペーストを用いてメタルマスクを5×5×0.15mmのパターンを形成し、更にその上にスパッタ処理面と加熱接合用細片が接するように4×4×0.35(厚)mmのシリコンチップ(スパッタ処理Ti/Au=35/150nm)を配置した。フリップチップボンダーによりシリコンチップの上面から5MPaの圧力を加えながら300℃で、10分の加熱をすることでアルミ基板上にシリコンチップを実装した。
(i)空孔の観察
接続されたアルミ基板とシリコンチップをエポキシ樹脂に埋め込めこんだ。続いて、埋め込んだ樹脂ともに接続体を研磨してペースト接続部の断面を露出させた。
接続部の断面を、走査型電子顕微鏡により観察を行ったところ、空隙率は5体積%であった。平均空孔径は50nmの範囲であった。
(ii)耐熱サイクル試験
前記アルミ基板とシリコンチップを接合した部材を、1サイクルの温度変化を下記4つの条件を順に1000回繰り返すことにより、冷熱サイクルによる耐熱サイクル試験を行った。
条件:−55℃で30分間、25℃で5分間、125℃で30分間、25℃で5分間の順
その結果、冷熱サイクル試験後、接続部において超音波顕微鏡を用いて、剥離部の有無の観察を行った。超音波顕微鏡観察では、剥離部は、超音波の反射信号が高く観察される。10サンプル測定しても、接続面全体で接続部位における超音波反射信号がほとんどなく、剥離が発生したサンプルは見られなかった。導電性ペーストの成分と組成、及び評価結果をまとめて表3に示す。
金属微粒子として、平均一次粒子径1.5μmの銅微粒子(水溶液中で銅イオンからの無電解還元により調製された銅微粒子)を用いた以外は、実施例7と同様にして、該導電性ペーストを導電性基板上に塗布して角状のダイボンド材を形成し、次にその上に、電子部品のリードを載せた後加熱処理(焼結)して接合体を形成した。得られた接合体の耐熱サイクル試験を行った。次に、実施例1に記載したと同様に、得られた接合体の空隙率、平均空孔径の測定、および耐熱サイクル試験を行った。
比較例1の導電性ペーストの成分と組成、及び導電性バンプの評価結果をまとめて表3に示す。
Claims (13)
- 半導体素子の電極端子又は回路基板の電極端子の接合面に形成された導電接続部材であって、
該導電接続部材が銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)を含む有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、前記有機溶剤(SC)を含む有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペースト、
を加熱処理して金属微粒子(P)同士が結合して形成された金属多孔質体であり、
該金属多孔質体が平均粒子径10〜500nmの金属微粒子(P)同士が結合して形成され、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、
ことを特徴とする導電接続部材。 - 前記導電接続部材が半導体素子間を接続させるための導電性バンプである、ことを特徴とする請求項1に記載の導電接続部材。
- 前記導電接続部材が半導体素子と導電性基板間を接続するための導電性ダイボンド部である、ことを特徴とする請求項1に記載の導電接続部材。
- 導電接続部材の作製方法であって、
電子部品における半導体素子もしくは回路基板の電極端子又は導電性基板の接合面に、
銅から形成された、平均一次粒子径10〜500nmの金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、
又は、前記金属微粒子(P)と、有機溶剤(S)及び有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストで、
該有機溶剤(S)が(i)少なくとも、アミド基を有する有機溶剤(SA)5〜90体積%、常圧における沸点が20〜100℃である低沸点の有機溶剤(SB)5〜45体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜90体積%含む有機溶剤(S1)、または(ii)少なくとも、アミド基を有する有機溶剤(SA)5〜95体積%、及び常圧における沸点が100℃以上でかつ分子中に1又は2以上のヒドロキシル基を有するアルコール及び/もしくは多価アルコールからなる有機溶剤(SC)5〜95体積%含む有機溶剤(S2)、
である導電性ペースト、
を載せて導電接続部材前駆体を形成する工程(工程1)と、
該導電接続部材前駆体上に接続する他方の電極端子又は導電性基板の接合面を位置合わせする工程(工程2)と、
該両電極端子、又は電極端子及び導電性基板と、導電接続部材前駆体とを150〜350℃の温度で加熱処理して、平均粒子径が10〜500nmの金属微粒子(P)同士が結合して形成された、空隙率が6〜9体積%で、平均空孔径が15〜120nmの範囲である、金属多孔質体からなる導電接続部材を形成することにより前記接合面間を接合する工程(工程3)、
を含むことを特徴とする導電接続部材の作製方法。 - 前記工程1における、導電性ペースト中の、金属微粒子(P)と有機分散媒(D)との配合割合(P/D)が50〜85質量%/50〜15質量%であり、該有機分散媒(D)中の有機溶剤(S)と有機バインダー(R)との配合割合(S/R)が80〜100質量%/20〜0質量%(質量%の合計はいずれも100質量%)である、ことを特徴とする請求項4に記載の導電接続部材の作製方法。
- 前記工程1における、金属微粒子(P)が、銅微粒子(P1)、
又は、銅微粒子(P1)90〜100質量%と、マグネシウム、アルミニウム、亜鉛、ガリウム、インジウム、錫、アンチモン、鉛、ビスマス、チタン、マンガン、及びゲルマニウムから選択された1種もしくは2種以上の金属微粒子(P2)10〜0質量%(質量%の合計は100質量%)からなる、ことを特徴とする請求項4又は5に記載の導電接続部材の作製方法。 - 前記金属微粒子(P2)が金属微粒子(P)中で、銅微粒子(P1)と合金を形成しているか、又は銅微粒子(P1)の表面で被覆層を形成している、ことを特徴とする請求項6に記載の導電接続部材の作製方法。
- 前記有機溶剤(SC)がエチレングリコール、ジエチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、2−ブテン−1,4−ジオール、2,3−ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、グリセロール、1,1,1−トリスヒドロキシメチルエタン、2−エチル−2−ヒドロキシメチル−1,3−プロパンジオール、1,2,6−ヘキサントリオール、1,2,3−ヘキサントリオール、1,2,4−ブタントリオール、トレイトール、エリトリトール、ペンタエリスリトール、ペンチトール、及びヘキシトールの中から選択される1種又は2種以上である、ことを特徴とする請求項4から7のいずれかに記載の導電接続部材の作製方法。
- 前記有機溶剤(SA)がN−メチルアセトアミド、N−メチルホルムアミド、N−メチルプロパンアミド、ホルムアミド、N,N−ジメチルアセトアミド、1,3−ジメチル−2−イミダゾリジノン、N,N−ジメチルホルムアミド、1−メチル−2−ピロリドン、ヘキサメチルホスホリックトリアミド、2−ピロリジノン、ε−カプロラクタム、及びアセトアミドの中から選択される1種又は2種以上である、ことを特徴とする請求項4から7のいずれかに記載の導電接続部材の作製方法。
- 前記有機溶剤(SB)が、一般式R1−O−R2(R1、R2は、それぞれ独立にアルキル基で、炭素原子数は1〜4である。)で表されるエーテル系化合物(SB1)、一般式R3−OH(R3は、アルキル基で、炭素原子数は1〜4である。)で表されるアルコール(SB2)、一般式R4−C(=O)−R5(R4、R5は、それぞれ独立にアルキル基で、炭素原子数は1〜2である。)で表されるケトン系化合物(SB3)、及び一般式R6−(N−R7)−R8(R6、R7、R8は、それぞれ独立にアルキル基、又は水素原子で、炭素原子数は0〜2である。)で表されるアミン系化合物(SB4)、の中から選択される1種又は2種以上である、ことを特徴とする請求項4から7のいずれかに記載の導電接続部材の作製方法。
- 前記有機溶剤(SB)が、ジエチルエーテル、メチルプロピルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、メチル−t−ブチルエーテル、t−アミルメチルエーテル、ジビニルエーテル、エチルビニルエーテル、及びアリルエーテルの中から選択される1種又は2種以上であるエーテル系化合物(SB1)、
メタノール、エタノール、1−プロパノール、2−プロパノール、2−ブタノール、及び2−メチル2−プロパノールの中から選択される1種又は2種以上であるアルコール(SB2)、アセトン、メチルエチルケトン、及びジエチルケトンの中から選択される1種又は2種以上であるケトン系化合物(SB3)、
並びに/又はトリエチルアミン、及び/もしくはジエチルアミンであるアミン系化合物(SB4)である、ことを特徴とする請求項4から10のいずれかに記載の導電接続部材の作製方法。 - 前記有機バインダー(R)が、セルロース樹脂系バインダー、アセテート樹脂系バインダー、アクリル樹脂系バインダー、ウレタン樹脂系バインダー、ポリビニルピロリドン樹脂系バインダー、ポリアミド樹脂系バインダー、ブチラール樹脂系バインダー、及びテルペン系バインダーの中から選択される1種又は2種以上である、ことを特徴とする請求項4から11のいずれかに記載の導電接続部材の作製方法。
- 前記セルロース樹脂系バインダーがアセチルセルロース、メチルセルロース、エチルセルロース、ブチルセルロース、及びニトロセルロース;アセテート樹脂系バインダーがメチルグリコールアセテート、エチルグリコールアセテート、ブチルグリコールアセテート、エチルジグリコールアセテート、及びブチルジグリコールアセテート;アクリル樹脂系バインダーがメチルメタクリレート、エチルメタクリレート、及びブチルメタクリレート;ウレタン樹脂系バインダーが2,4−トリレンジイソシアネート、及びp−フェニレンジイソシアネート;ポリビニルピロリドン樹脂系バインダーがポリビニルピロリドン、及びN−ビニルピロリドン;ポリアミド樹脂系バインダーがポリアミド6、ポリアミド6.6、及びポリアミド11;ブチラール樹脂系バインダーがポリビニルブチラール;テルペン系バインダーがピネン、シネオール、リモネン、及びテルピネオールから選択される1種又は2種以上である、ことを特徴とする請求項12に記載の導電接続部材の作製方法。
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CN102812543B (zh) | 2016-03-30 |
WO2011114751A1 (ja) | 2011-09-22 |
CN102812543A (zh) | 2012-12-05 |
US20130001775A1 (en) | 2013-01-03 |
EP2560197A4 (en) | 2016-04-27 |
KR101755749B1 (ko) | 2017-07-07 |
EP2560197A1 (en) | 2013-02-20 |
KR20130053400A (ko) | 2013-05-23 |
JPWO2011114751A1 (ja) | 2013-06-27 |
US10177079B2 (en) | 2019-01-08 |
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