TW201504459A - Ｃｕ核球 - Google Patents

Ｃｕ核球 Download PDF

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Publication number
TW201504459A
TW201504459A TW103113348A TW103113348A TW201504459A TW 201504459 A TW201504459 A TW 201504459A TW 103113348 A TW103113348 A TW 103113348A TW 103113348 A TW103113348 A TW 103113348A TW 201504459 A TW201504459 A TW 201504459A
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TW
Taiwan
Prior art keywords
ball
nucleus
solder
amount
less
Prior art date
Application number
TW103113348A
Other languages
English (en)
Other versions
TWI585220B (zh
Inventor
Hiroyoshi Kawasaki
Tomohiko Hashimoto
Atsushi Ikeda
Takahiro Roppongi
Daisuke Soma
Isamu Sato
Yuji Kawamata
Original Assignee
Senju Metal Industry Co
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Application filed by Senju Metal Industry Co filed Critical Senju Metal Industry Co
Publication of TW201504459A publication Critical patent/TW201504459A/zh
Application granted granted Critical
Publication of TWI585220B publication Critical patent/TWI585220B/zh

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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
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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    • B23K35/302—Cu as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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Abstract

本發明提供可抑制軟錯誤減低連接不良之Cu核球。 形成於Cu球表面的鍍焊料披膜，係由鍍Sn焊料披膜或以Sn為主成分的無Pb焊料合金所構成，U的含量為5ppb以下，Th的含量為5ppb以下，該Cu球的純度為99.9%以上99.995%以下，Pb及/或Bi的含量的合計量為1ppm以上，真球度為0.95以上，所得Cu核球的α射線量為0.0200cph/cm2以下。

Description

Cu核球
本發明係關於，α射線量少的Cu核球。
近年，因小型資訊機器的發達，於搭載的電子零件進行急速的小型化。電子零件，因小型化的要求為對應連接端子的狹小化或構裝面積的縮小化，使用於背面設置電極之球柵陣列(以下，稱為「BGA」。)。
於使用BGA的電子零件，例如有半導體封裝。於半導體封裝，係將具有電極之半導體晶片以樹脂密封。於半導體晶片的電極，形成有焊料凸塊。該焊料凸塊，係藉由將焊料凸塊接合於半導體晶片的電極而形成。使用BGA的半導體封裝，係藉由使加熱熔融之焊料凸塊與印刷電路板的導電性焊墊接合，而搭載於印刷電路板。此外，為對應更高密度構裝的要求，亦有將半導體封裝於高度方向疊層之3維高密度構裝的研究。
但是，在3維高密度構裝的半導體封裝使用BGA，則有因半導體封裝的自重而將焊料球壓潰之情形。如果發生如此之情形，則焊料由電極溢出，可能使電極間連接，而發生短路。
因此，有由接合於電子零件的電極的Cu核球所構 成之焊料凸塊的研究。所謂Cu核球，係指於Cu球的表面形成焊料披膜者。使用Cu核球形成之焊料凸塊，在將電子零件構裝於印刷電路板時，即使半導體封裝的重量施加於焊料凸塊，藉由以焊料的熔點並不會熔融之Cu球支撐半導體封裝。因此，並不會因半導體封裝的自重而壓潰。關聯技術可舉例如專利文獻1。
於專利文獻1揭示有真球度高的Cu球的發明，亦有於Cu球披覆之Cu核球之記載。於同文獻，例示構成元素為Pb及Sn所構成的Pb-Sn焊料。此外，於同文獻，作為披膜的形成方法，揭示有鍍敷法、熔接法、焊接法等作為等價的方法。該等之中，鍍敷法，揭示有筒式電鍍等的電鍍法。
然而，電子零件的小型化雖可高密度構裝，但高密度構裝有容易引起軟錯誤的問題。軟錯誤係指因α射線射入半導體積體電路(以下，稱為「IC」。)的記憶胞中而有將記憶內如改寫的可能性者。α射線，可認為係焊料合金中的U、Th、210Po等的放射性元素因α衰變而輻射者。因此，於近年有減低放射性元素含量的低α射線焊料材料的開發的進行。關聯文獻，可舉例如專利文獻2。
於專利文獻2，揭示有α射線低的Sn晶棒的發明，記載有為減低α射線，並不單只進行電解晶練，藉由在電解液懸浮吸附劑將Pb或Bi吸附而減低α射線。
[先前技術文獻]
[專利文獻]
[專利文獻1]國際公開95/24113號
[專利文獻2]日本專利第4472752號公報
本發明的課題，係在於提供抑制軟錯誤的發生的Cu核球，具體而言係α射線少的Cu核球。
但是，於專利文獻1，完全沒有考慮減低Cu核球的α射線量的課題。此外，於同文獻，構成焊料披膜的焊料合金，唯一揭示Pb-Sn合金作為先前技術。α射線係包含於Sn的雜質之Pb的同位素210Pb，衰變210Pb→210Bi→210Po→206Pb的過程，由210Pb放射。由於同文獻所唯一揭示的Pb-Sn合金包含多量的Pb，可認為亦包含放射性元素210Pb。因此，即使將該焊料合金使用於Cu核球的焊料披膜，由於在專利文獻1，完全沒有考慮減低α射線的課題，故很難認為同文獻所揭示的Cu核球顯示低的α射線量。
於專利文獻2，如上所述，有藉由電解液或電極以靜止的狀態進行的電解精煉，去除Sn晶棒中的Pb或Bi減低α射線量的記載。但是，於同文獻，完全沒有揭示關於對Cu球進行鍍Sn，或Cu球及電解液在流動的狀態進行電鍍。此外，同文獻所記載的電解精煉，由於電解析出面僅限於一方向，故無法對如Cu球等的微小工件形成均勻的鍍層。
再者，根據專利文獻2，由於Pb或Bi與Sn的標準電極電位接近，僅以一般的電解精煉進行使Sn對平板電極的電解析出，難以減低α射線量。假如，將專利文獻2所記載 的電解精煉使用於形成Cu球的鍍敷披膜，將鍍敷液懸浮於吸附劑進行筒式電鍍，則鍍敷液或工件被攪拌，吸附劑亦同時被攪拌。此時，吸附於吸附劑的Pb離子或Bi離子有成為載體與吸附劑一起取入焊料披膜內的可能性。取入吸附劑的焊料披膜，會放射很高的α射線。此外，吸附劑的粒徑為次微米程度而非常的小，故可認為由邊流動的鍍敷液分離．回收懸浮後的吸附劑非常的難。因此，難以不使吸附Pb或Bi的吸附劑取入披膜。
加上該等，於專利文獻1雖揭示Pb-Sn合金，但係揭示鍍敷法、熔接法、焊接法等作為等價的方法，故反而是否定減低α射線的記載。專利文獻1的課題，係在於製造真球度高的Cu核球。另一方面，專利文獻2，為解決減低α射線量的課題，揭示以電解精煉盡可能去除Sn中的Pb。因此，知道專利文獻1的業者，並不會想到專利文獻2所揭示之減低Cu核球的α射線量的課題，並且，由於焊料組成亦相反，故想到減低α射線量的課題，想到進一步取代構成焊料披膜的Pb-Sn焊料合金，由無數存在的焊料合金中使用Sn系焊料，需要進行多次的嘗試錯誤。
如此地，即使是該業者，並無法組合專利文獻1與專利文獻2。更言之，即使是該業者，難以使用專利文獻2所揭示之α射線量低的Sn晶棒製作鍍敷液，藉由專利文獻1所揭示的鍍敷法形成Cu核球。
如此地，使用專利文獻1或專利文獻2所記載的先前技術製造的Cu核球，用於形成接點，則存在於Cu核球的 焊料披膜中的放射線元素擴散至接點的電極，而射出α射線的可能性高。因此，即使組合先前的技術，並無法減低Cu核球的α射線量，故藉由高密度構裝而無法避免成為新問題的軟錯誤。
本發明者們，首先進行使用於Cu核球之Cu球之選定。結果，發現只要在Cu球不含有一定量的Pb及/或Bi，則會使Cu球的真球度降低，進行焊料鍍敷時對Cu球的焊料鍍敷不均勻，結果，所得Cu核球的真球度會降低。
其次，為減低構成Cu核球之焊料披膜的α射線，著眼於使用鍍敷法形成焊料鍍敷披膜之點進行銳意研究。本發明者們，為減低鍍敷液中的Pb、Bi，或由該等元素的衰變所生成之Po，使Cu球或鍍敷液流動於Cu球形成鍍敷披膜時，意外地，即使不懸浮吸附劑該等Pb、Bi、Po元素形成鹽。因此，該鹽由於係電中性，故並不會在鍍敷披膜取入該等元素，而得到可減低構成Cu核球之鍍敷披膜之α射線量之見識。
在此，本發明如下。
(1)一種Cu核球，包括：Cu球；及披覆於該Cu球的表面之焊料鍍敷披膜之Cu核球，其特徵在於：上述焊料鍍敷披膜，係Sn焊料鍍敷披膜或以Sn為主成分的無Pb焊料合金所構成之焊料鍍敷披膜，U的含量為5ppb以下，Th的含量為5ppb以下，該Cu球的純度為99.9%以上99.995%以下，Pb及/或Bi 的含量的合計量為1ppm以上，真球度為0.95以上，然後，Cu核球的α射線量為0.0200cph/cm2以下。
在此，所謂「以Sn為主成分」係指焊料鍍敷披膜中的Sn含量對披膜質量為40質量%以上。因此，構成本發明之焊料鍍敷披膜包含Sn焊料鍍敷披膜。
(2)根據上述(1)之Cu核球，其中上述Cu核球的α射線量為0.0020cph/cm2以下。
(3)根據上述(1)之Cu核球，其中上述Cu核球的α射線量為0.0010cph/cm2以下。
(4)根據上述(1)至(3)中任一項之Cu核球，其中上述Cu球中的Pb及Bi的含量合計為1ppm以上。
(5)根據上述(1)至(4)中任一項之Cu核球，其直徑為1~1000μm。
(6)根據上述(1)至(5)中任一項之Cu核球，其中上述Cu球，在以上述焊料鍍敷披膜披覆之前預先以選自由Ni及Co之1元素以上所組成的鍍敷層披覆。
(7)一種接點，使用上述(1)至(6)中任一項之Cu核球所形成。
第1圖係使用純度為99.9%的Cu錠所製造的Cu球之SEM照片。
第2圖係使用純度為99.995%以下的Cu線所製造的Cu球之SEM照片。
第3圖係使用純度超過99.995%的Cu板所製造的Cu球之SEM照片。
以下，更詳細地說明本發明。在於本說明書，關於Cu核球之鍍敷披膜的組成之單位(ppm、ppb、及%)，若無特別指定係表示對鍍敷披膜之質量之比例(質量ppm、質量ppb、及質量%)。此外，關於Cu球的組成之單位(ppm、ppb、及%)，若無特別指定係表示對Cu球之質量之比例(質量ppm、質量ppb、及質量%)。
關於本發明之Cu核球，包括：Cu球；及披覆於該Cu球的表面之焊料鍍敷披膜。本發明之焊料鍍敷披膜，係主要對工件之Cu球，使鍍敷液流動而形成。藉由鍍敷液的流動於鍍敷液中Pb、Bi、Po的元素形成鹽而沉澱。一旦形成鹽之析出物，則會穩定地存在於鍍敷液中。因此，關於本發明之Cu核球並不會被取入鍍敷披膜，可減低包含於鍍敷披膜之放射性元素的含量，可減低Cu核球本身的α射線量。
以下，詳述關於Cu核球之構成要素之焊料鍍敷披膜及Cu球。
1.焊料鍍敷披膜
．焊料鍍敷披膜的組成
焊料鍍敷披膜的組成，以合金之情形，只要是以Sn為主成分的無Pb焊料合金之合金組合，並無特別限定。此外，焊料鍍敷披膜，可為Sn鍍敷披膜。可舉例如，Sn、Sn-Ag合金、Sn-Cu合金、Sn-Ag-Cu合金、Sn-In合金、即對該等添加既定 的合金元素者。均為Sn含量為40質量%以上。添加的合金元素，例如有Ag、Cu、In、Ni、Co、Sb、Ge、P、Fe等。該等之中，焊料鍍敷披膜的合金組成，由落下衝擊特性的觀點，以Sn-3Ag-0.5Cu為佳。
焊料鍍敷披膜的厚度，並無特別限定，以100μm(單邊)以下即充分。一般以20~50μm即可。
．U：5ppb以下，Th：5ppb以下
U及Th係放射性元素，為抑制軟錯誤需要抑制該等的含量。U及Th的含量，在為使焊料鍍敷披膜的α射線量在0.0200cph/cm2以下，需要各為5ppb以下。此外，於現在或未來的高密度構裝抑制軟錯誤的觀點，U及Th的含量，各以2ppb以下為佳。
．α射線量：0.0200cph/cm2以下
關於本發明之Cu核球的α射線量為0.0200cph/cm2以下。此係，在於電子零件的高密度構裝軟錯誤不會成為問題的程度的α射線量。關於本發明之Cu核球之α射線量，可藉由構成Cu核球的焊料鍍敷披膜的α射線量在0.0200cph/cm2以下而達成。本發明之焊料鍍敷披膜頂多以100℃形成，故難以認為可藉由U、Th、210Po、Bi及Pb等的放射性元素的汽化而減低放射性元素的減低。但是，邊使鍍敷液或Cu球流動進行鍍敷，則U、Th、Pb、Bi、及210Po會在鍍敷液中形成鹽而沉澱。由於沉澱的鹽係電中性，即使鍍敷液流動，並不會混入焊料鍍敷披膜中。可顯著地減低該等在焊料鍍敷披膜中的含量。因此，關於本發明之Cu核球，由於係以如此之焊料鍍敷披膜批覆， 故顯示較低的α射線量。α射線量，在更進一步的高密度構裝抑制軟錯誤的觀點，以0.0020cph/cm2以下為佳，以0.0010cph/cm2以下更佳。
構成本發明之焊料鍍敷披膜的純度越高，即雜質的含量越少，可減低放射性元素的含量，減低α射線量，故雜質量的下限值並無特別限定。另一方面，上限值，由減低α射線量的觀點，以150ppm以下為佳，以100ppm以下更佳，進一步以50ppm以下為佳，以10ppm以下特別佳。
再者，焊料鍍敷披膜為Sn焊料時，焊料鍍敷披膜的純度，係焊料鍍敷披膜中的Sn以外的雜質的合計量。此外，焊料鍍敷披膜為Sn-3Ag-0.5Cu的焊料合金時，焊料鍍敷披膜的純度，係焊料鍍敷披膜中的Sn、Ag、及Cu以外的雜質的含量的合計。
包含於焊料鍍敷披膜的雜質，於Sn焊料鍍敷披膜之情形，可舉Ag、Ni、Pb、Au、U、Th等。由Sn-Ag-Cu合金所構成的焊料鍍敷披膜時，可舉Sn、Fe、As、In、Ni、Pb、Au、U、Th等。於雜質，特別是以Bi的含量較少為佳。一般而言，於Bi的原料包含微量的放射性同位素之210Bi。因此，藉由減低Bi的含量，可認為可顯著地減低焊料鍍敷披膜的α射線量。Bi的含量，以15ppm以下為佳，以10ppm以下更佳，以0ppm特別佳。
2.Cu球
其次，詳述關於構成本發明之Cu球。
構成本發明之Cu球，係於Cu核球用於焊料凸塊 時，由於並不會在焊接的溫度熔融，可抑制焊料接點的高度的離散。因此，Cu球以真球度高而直徑的離散少者為佳。此外，如上所述，Cu球的α射線量亦與焊料披膜Cu樣地低為佳。以下記載Cu球的較佳的態樣。
．Cu球的純度：99.9%以上99.995%以下
構成本發明之Cu球以99.9%以上99.995%以下為佳。Cu球的純度在此範圍，則可於熔融Cu中確保充分量可提高Cu球的真球度的結晶核。提高真球度的理由，詳述如下。
製造Cu球時，形成為既定形狀的小片的Cu材，係藉由加熱熔融，熔融Cu藉由表面張力而成為球形，此凝固成為Cu球。在於熔融Cu由液體狀態凝固的過程，結晶粒在球形的熔融Cu中成長。此時，雜質多，則該雜質元素成為結晶核而抑制結晶粒的成長。因此，球形的熔融Cu，藉由抑制成長的細微結晶粒成為真球度高的Cu球。另一方面，雜質元素少，則相對地成為結晶核者少，無法抑制粒成長而帶著方向性成長。結果，球形的熔融Cu在表面的一部分凸出凝固。如此的Cu球真球度低。雜質元素，可考慮Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、U、Th等。
純度的下限值並無特別限定，由抑制α射線量，抑制因純度的降低而使Cu球的導電度或熱傳導率的惡化的觀點，以99.9%以上為佳。
在此，相對於焊料鍍敷披膜純度越高越可減低α射線量，於Cu球即使不使純度提高到必要以上，亦可減低α射線量。Cu熔點較Sn高，於製造時的加熱溫度Cu較高。於 本發明，製造Cu球時，由於如後所述對Cu球進行先前並未對Cu材進行之加熱處理，故210Pb、210Bi等的放射線元素會揮發。另一方面，使用以Sn為主成分之焊料形成焊料鍍敷披膜時，焊料合金僅加熱至100℃左右的溫度。由於在焊料鍍敷處理，上述放射性元素幾乎不會揮發而殘存於鍍敷液，故需要降低Pb或Bi等的雜質濃度，提高焊料鍍敷披膜的純度。
．α射線量：0.0200cph/cm2以下
構成本發明之Cu球的α射線量，較佳的是0.0200cph/cm2以下。此係，在於電子零件的高密度構裝軟錯誤不會成為問題的程度的α射線量。於本發明，加上用於製造Cu球通常進行的步驟，施以再度加熱處理。因此，些微殘存於Cu的原材料的210Po揮發，與Cu的原材料相比Cu球顯示更低的α射線量。α射線量，在更進一步的高密度構裝抑制軟錯誤的觀點，以0.0020cph/cm2以下為佳，以0.0010cph/cm2以下更佳。
．Pb及Bi的含量以合計為1ppm以上
構成本發明之Cu球，含有Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、U、Th等，特別是Pb及/或Bi的含量合計以含有1ppm以上為佳。於本發明，即使是在於焊料接點的形成時露出Cu球時，於減低α射線量上並沒有需要將Cu球的Pb及/或Bi的含量減低至極限。此係根據以下的理由。
210Pb及210Bi係藉由β衰變變化為210Po。為減低α射線量，雜質元素的Pb及Bi的含量盡量低為佳。
但是，包含於Pb及Bi的210Pb及210Bi的含有比低。只要某種程度減低Pb或Bi的含量，則可認為幾乎去除210Pb 及210Bi。關於本發明的Cu球，Cu的溶解溫度設定較先前稍高，或對Cu材及/或造粒後的Cu球施以加熱處理而製造。此溫度，由於即使是較Pb或Bi的沸點低之情形亦未發生氣化故可減低雜質元素量。此外，為提高Cu球的真球度雜質元素的含量高較佳。因此，本發明的Cu球，Pb及/或Bi的含量以合計為1ppm以上。Pb及Bi均包含時，Pb及Bi的合計含量為1ppm以上。
如此地，Pb及/或Bi由於在製造Cu球之後亦有某種程度的殘存而含量的測定誤差少。再者如前所述Bi及Pb在於Cu球的製造步驟之熔融時會成為結晶核，故藉由添加一定量的Bi或Pb可製造真球度高的Cu球。因此，Pb或Bi，係用於推測雜質元素的含量的重要的元素。由如此的觀點，Pb及/或Bi的含量以合計為1ppm以上為佳。Pb及/或Bi的含量，合計以10ppm以上更佳。上限值，並無特別限定，由抑制Cu球的導電度惡化的觀點，Pb及/或Bi的含量的含量合計以未滿1000ppm更佳，進一步以100ppm以下為佳。Pb的含量，以10ppm~50ppm為佳，Bi的含量，以10ppm~50ppm更佳。
．Cu球的真球度：0.95以上
構成本發明之Cu球，由控制站立高度的觀點真球度為0.95以上。Cu球的真球度未滿0.95，則由於Cu球將成不定形狀，而於凸塊形成時形成高度不均勻的凸塊，提高發生接合不良的可能性。再者，對Cu球的鍍敷成為不均勻，將Cu核球搭載於電極進行回焊時，發生Cu核球的位移，而使自我對準性惡化。真球度，以0.990以上更佳。在於本發明，真球度係表 示由真球的偏移。真球度，可例如，以最小平方中心法(LSC法)、最小區域中心法(MZC法)、最大內接中心法(MIC法)、最小外接中心法(MCC法)等各種方法求得。
．Cu球的直徑：1~1000μm
構成本發明之Cu球的直徑以1~1000μm為佳。在於該範圍，則可穩定地製造球狀的Cu球，此外，端子間為窄間距時可抑制連接之短路。
在此，例如，關於本發明的Cu核球的直徑為1~300μm程度時，「Cu核球」的集合體亦可稱為「Cu核球粉」。在此，「Cu核球粉」，係將包括上述特性的各個Cu核球，多數Cu核球的集合體。例如，調合於焊膏中的粉末等，與使用單一Cu核球的形態有所區別。同樣地，用於形成焊料凸塊時，通常作為集合體使用，與以如此之形態使用之「Cu核球粉末」與單一的Cu核球有所區別。
關於本發明的Cu核球，可於形成焊料鍍敷披膜之前，預先於Cu球的表面以其他的金屬鍍敷層披覆。特別是，於Cu球表面預先披覆鍍Ni層或鍍Co層等，由於可減低Cu對焊料鍍敷披膜中的溶出，故可抑制Cu球的Cu蝕。此外，使用於鍍敷層之金屬並不限於單一金屬，亦可使用由Ni、Co等之中組合2元素以上的合金。
此外，關於本發明之Cu核球的真球度以0.95以上為佳。Cu核球的真球度低時，將Cu核球搭在於電極進行回焊時，引起Cu核球的位移，使自我對準性惡化。真球度，以0.990以上更佳。再者，關於本發明之Cu核球，亦可使用於形成將 電子零件的端子相互接合之焊料接點。
說明關於本發明之Cu核球之製造方法之一例。
成為材料之Cu材係置於如陶瓷等之耐熱性的板(以下，稱為「耐熱板」。)，與耐熱板一起於爐中加熱。於耐熱板設有多數底部呈半球狀的圓形的溝。溝的直徑或深度，可按照Cu球的粒徑適宜設定，例如，直徑為0.8mm、深度為0.88mm。此外，切斷Cu細線而得之薄片形狀的Cu材(以下，稱為「薄片材」。)，於耐熱板的溝內各投入一個。於構內投入薄片材之耐熱板，係於充填氨分解氣體的爐內升溫至1100~1300℃，進行30~60分鐘的加熱處理。此時，爐內溫度成為Cu的熔點以上，則薄片材熔融成球狀。之後，爐內被冷卻，於耐熱板的溝內將Cu球成形。冷卻後，成形之Cu球，係以未滿Cu的熔點的溫度之800~1000℃再度進行加熱處理。
此外，作為別的方法，由設於坩鍋的低部的孔滴下熔融Cu的液滴，該液滴被冷卻將Cu球造粒之噴霧法，或熱電漿將切Cu金屬加熱為1000℃以上而造粒的方法。如此地造粒之Cu球，亦可分別以800~1000℃的溫度施以30~60分鐘再加熱處理。
本發明的Cu核球的製造方法，亦可於Cu球的造粒之前將Cu球的原料之Cu材以800~1000℃加熱處理。
Cu球的原料的Cu材，例如可使用錠、線、柱等。Cu材的純度，由不過度降低純度的觀點，可為99.9~99.99%。
使用更高純度的Cu材時，亦可不進行上述加熱處理，將熔融Cu的保持溫度與先前Cu樣地降至1000℃左右。 如此地，上述加熱處理，亦可按照Cu材的純度或α射線量適宜省略或變更。此外，即使製造α射線量高的Cu球或異形的Cu球時，亦可將該等Cu球作為原料再利用，可進一步降低α射線量。
此外，如上所述地製作的Cu球或使鍍敷液流動於Cu球形成鍍敷披膜的方法，有習知之筒式鍍敷等的電鍍法、連接於鍍敷槽的幫浦使鍍敷槽中的鍍敷液發生高速亂流，藉由鍍敷液的亂流於Cu球形成鍍敷披膜的方法，於鍍敷槽設振動板以既定的頻率振動使鍍敷液高速亂流攪拌，藉由鍍敷液的亂流於Cu球形成鍍敷披膜的方法等。
於直徑100μm的Cu球形成膜厚(單測)20μm的Sn-Ag-Cu焊料鍍敷披膜，作成直徑約140μm的Cu核球作為一例說明之。
關於本發明之一實施形態之含有Sn-Ag-Cu之鍍敷液，係以水為主體之媒體，含有磺酸類及金屬成分之Sn、Ag及Cu作為必要成分。
金屬成分係於鍍敷液中以Sn離子(Sn2+及/或Sn4+)，Ag離子(Ag+)及Cu離子(Cu+/Cu2+)存在。鍍敷液，主要係藉由由水與磺酸類所組成的鍍敷母液與金屬化合物混合而得，為金屬離子的穩定性，含有有機錯合劑為佳。
鍍敷液中的金屬化合物，例如可例示如下者。
Sn化合物的具體例，可舉甲基磺酸、乙基磺酸、2-丙醇磺酸、對酚磺酸等的有機磺酸之錫鹽、硫酸錫、氧化錫、硝酸錫、氯化錫、嗅化錫、碘化錫、磷酸錫、焦磷酸錫、醋酸錫、蟻酸 錫、檸檬酸錫、葡糖酸錫、酒石酸錫、乳酸錫、琥珀酸錫、磺胺酸、硼氟化錫、矽氟化錫等的亞Sn化合物。該等的Sn化合物，可以一種單獨或混合兩種以上使用。
銅化合物，可舉上述有機磺酸之銅鹽、硫酸銅、氧化銅、硝酸銅、氯化銅、嗅化銅、碘化銅、磷酸銅、焦磷酸銅、醋酸銅、蟻酸銅、檸檬酸銅、葡糖酸銅、酒石酸銅、乳酸銅、琥珀酸銅、磺胺酸銅、硼氟化銅、矽氟化銅等。該等Cu化合物，可以一種單獨或混合兩種以上使用。
Ag化合物，可舉上述有機磺酸之銀鹽、硫酸銀、氧化銀、氯化銀、硝酸銀、嗅化銀、碘化銀、磷酸銀、焦磷酸銀、醋酸銀、蟻酸銀、檸檬酸銀、葡糖酸銀、酒石酸銀、乳酸銀、琥珀酸銀、磺胺酸銀、硼氟化銀、矽氟化銀等。該等Ag化合物，可以一種單獨或混合兩種以上使用。
此外，對直徑100μm的Cu球形成膜厚(單側)20μm的Sn-Ag-Cu焊料鍍敷披膜時，需要約0.0108庫倫的電量。
鍍敷液中的各金屬的調合量，Sn2+為0.21~2mol/L，以0.25~1mol/L為佳，Ag為0.01~0.1mol/L，以0.02~0.05mol/L為佳，Cu為0.002~0.02mol/L，以0.003~0.01mol/L為佳。在此，由於參與鍍敷的是Sn2+，故於本發明只要調整Sn2+的量即可。
此外，Ag離子濃度對Cu離子濃度(Ag/Cu莫耳比)，以4.5~5.58的範圍為佳，於該範圍，則可形成如Sn-3Ag-0.5Cu合金等的熔點低的Sn-Ag-Cu鍍敷披膜。
再者，根據法拉第的電解法則，根據下式(1)估計所期望的 焊料鍍敷的析出量，算出電量，對鍍敷液通電流成算出之電量，使Cu球及鍍敷液流動進行鍍敷處理。鍍敷槽的容量可按照Cu球及鍍敷液的總投入量決定。
w(g)=(I×t×M)/(Z×F)...式(1)
式(1)中，w係電解析出量(g)，I係電流(A)，t係通電時間(秒)，M係析出元素之原子量(Sn為118.71)，z係原子價(Sn為2價)，F係法拉第常數(96500庫倫)，電量Q(A．秒)係以(I×t)表示。
於本發明，使Cu球及鍍敷液流動進行鍍敷，關於使之流動的方法，並無特別限定。例如，如筒式電鍍法，藉由筒的旋轉使Cu球及鍍敷液流動。
鍍敷處理後，於大氣中或N2氣氛中乾燥可得關於本發明之Cu核球。
此外，本發明，亦可應用於以Cu為管柱、柱或錠的形狀。
[實施例]
以下說明本發明之實施例，惟本發明並非限定於該等。於本實施例製作真球度高的Cu球，於該Cu球的比面形成焊料鍍敷披膜測定α射線量。
．Cu球的製作
調查製作真球度高的Cu球的條件。準備純度為99.9%的Cu錠、純度為99.995%以下的Cu線、及純度超過99.995%的銅板。分別投入坩鍋中之後，將坩鍋的溫度升溫至1200℃，進行45分鐘加熱處理，由設於坩鍋底部的孔使熔融Cu之液滴 滴下，將滴液冷卻將Cu球造粒。藉此，製作平均粒徑為250μm的Cu球。將製作之Cu球的元素分析結果及真球度示於第1表。以下，詳述真球度的測定方法。
．真球度
真球度係以CNC影像測定系統測定。裝置，係MITSUTOYO公司製之ULTRA QUICK VISION，ULTRA QV350-PRO。
此外，製作之各個Cu球的SEM照片示於第1~3圖。第1圖，係使用純度為99.9%的Cu錠製作之Cu球之SEM照片。第2圖係使用純度為99.995%以下的Cu線所製造的Cu球之SEM照片。第3圖係使用純度超過99.995%的Cu板所製造的Cu球之SEM照片。SEN照片的倍率為100倍。
α射線量的測定方法如下。
．α射線量
α射線量的測定係使用氣流比例計數器的α射線測定裝置。測定樣品係於300mm×300mm的平面淺底容器鋪滿Cu球者。將該測定樣品放入α射線測定裝置內，以PR-10氣流放置24小時後，測定α射線量。
再者，使用於測定之PR-10氣體(氬90%-甲烷10%)，係將PR-10氣體填充於氣瓶經過3週以上者。經過3週以上的氣瓶，為不使進入氣瓶的大氣中的氡產生α射線，遵照JEDEC(Joint Electron Device Engineering Council)所訂定的α射線測定方法之指針。
將製作之Cu球之元素分析結果、α射線量示於第 1表。
如第1表、第1圖及第2圖所示，使用純度為99.9%的Cu錠及99.995%以下的Cu線之Cu球，均表示真球度為0.990以上。另一方面，如第1表及第3圖所示，使用純度超過99.995%的Cu板的Cu球，真球度低過0.95。因此，於以下所示實施例及比較例，均係使用99.9%的Cu錠製造之Cu球製作Cu核球。
實施例1
關於以純度99.9%的Cu錠所製造的Cu球，以如下條件形成Sn焊料鍍敷披膜製作Cu核球。
Cu核球，係以約0.17庫倫的電量，使用以下的鍍敷液進行鍍敷處理，於直徑250μm的Cu球披覆膜厚(單側)為50μm的焊料鍍敷。以SEM照片觀察以焊料鍍敷披膜披覆的Cu核球的剖面，膜厚約為50μm。
處理後，於大氣中乾燥，得到Cu核球。
焊料鍍敷液，係如下製作。
於攪拌容器，對調製鍍敷液所需的水的1/3，放入54重量%的甲基磺酸水溶液的全容作為敷液。其次，放入錯化劑之硫醇化合物之一例之乙醯半胱胺酸確認溶解後，放入其他的錯化劑之芳香族胺基化合物之一例之2,2’-二硫代二苯胺。變成薄淡藍色的凝膠狀的液體迅速地放入甲基磺酸亞錫。其次對鍍敷液加入必要的2/3，最後放入介面活性劑之一例之α-萘酚聚氧乙烯醚(EO10莫耳)3g/L，完成鍍敷液的調製。製作鍍敷液中的甲基磺酸的濃度為2.64mol/L，錫離子濃度為0.337mol/L之鍍敷液。使用於本例之甲基磺酸亞錫，係以下述Sn板片材作為 原料調製者。
焊料鍍敷液之原料之Sn板片材的元素分析，及形成於Cu核球的表面的焊料鍍敷披膜的元素分析，關於U及Th係以高頻耦合電漿質譜分析(ICP-MS分析)，關於其他的元素係以高頻耦合電漿發射光譜分析(ICP-AES分析)進行。Sn板片材的α射線量，係於300mm×300mm的平面淺底容器鋪Sn板片材以外與Cu球做同樣的測定。Cu核球的α射線量，亦與上述Cu球做同樣的測定。此外，關於Cu核球的真球度，亦以與Cu球相同的條件進行測定。將該等的測定結果示於第2表。
實施例2
關於以純度99.9%的銅錠所製造的Cu球，形成膜厚(單側)為50μm的Sn-Ag-Cu焊料鍍敷披膜製作Cu核球。
於實施例2，焊料鍍敷液，係如下製作。
於攪拌容器，對調製鍍敷液所需的水的1/3，放入54重量%的甲基磺酸水溶液的全容作為敷液。其次，邊攪拌放入所需量的氧化銀之全容確認完全沒有黑沉而成為透明後，迅速地放入氫氧化銅的全容完全溶解，放入錯化劑之硫醇化合物之一例之乙醯半胱胺酸確認溶解後，放入其他的錯化劑之芳香族胺基化合物之一例之2,2’-二硫代二苯胺。變成薄淡藍色的凝膠狀的液體迅速地放入甲基磺酸亞錫。液變成黃色透明。其次對鍍敷液加入必要的2/3，最後放入介面活性劑之一例之α-萘酚聚氧乙烯醚(EO10莫耳)3g/L，完成鍍敷液的調製。製作鍍敷液中的甲基磺酸的濃度為2.64mol/L，錫離子濃度為0.337mol/L、銅離子濃度為0.005mol/L、銀離子濃度為0.0237mol/L、之鍍 敷液。
如此地製作鍍敷液之後，使用於實施例1使用之α射線量為0.203cph/cm2的Sn板片材，α射線量為<0.0010cph/cm2，純度為6N的Cu板材及α射線量為<0.0010cph/cm2，純度為5N之Ag薄片材之外，以與實施例1同樣地製作鍍敷液製作Cu核球，進行元素分析及α射線量、真球度的測定。將測定結果，示於第2表。
於本例錫離子亦係來自上述Sn板片材者，關於銀離子、銅離子，係分別來自上述Ag薄片材、Cu板材者。
比較例1
關於以純度99.9%的Cu錠所製造的Cu球，使用熔接法以如下條件形成Sn焊料披膜製作Cu核球。具體而言，於難以焊接的鋁板的既定的位置設置多數研缽狀的凹陷。此外，使用上述Sn板片材，藉由已知的噴霧法預先製作直徑為300μm的Sn球。於設於鋁基板的各凹陷，各放1個Cu球及Sn球，將助熔劑噴霧。之後，將鋁板於加熱爐中加熱為270℃使Sn球熔融。熔融Sn於Cu球的周圍沾濕，藉由表面張力披覆Cu球。如此地製作比較例1之Cu核球。焊料披膜的膜厚(單側)為50μm。關於製作的Cu核球，與實施例1同樣地，測定元素分析、α射線量及真球度。將測定結果示於第2表。
[第2表]
根據第2表，於實施例1，α射線量顯示未滿0.0010cph/cm2。實施例1之Cu核球，證明可藉由鍍敷法形成焊料鍍敷披膜可減低α射線量。
於實施例2，使焊料鍍敷披膜的組成為Sn-2.95Ag-0.29Cu時，α射線量顯示未滿0.0010cph/cm2。實施例2之Cu核球，與實施例1同樣地，證明可藉由鍍敷法形成焊料鍍敷披膜可減低α射線量。
此外於實施例1、實施例2所製作之Cu核球之α射線量，即使於製作後經過1年，並沒有看到α射線的上昇。另一方面，於比較例1，α射線量顯示0.183cph/cm2，顯示與Sn板片材同程度的α射線量。因此，比較例1的Cu核球，並沒有達至可迴避軟錯誤的程度的α射線量。

Claims (8)

  1. 一種Cu核球，包括：Cu球；及披覆於該Cu球的表面之焊料鍍敷披膜之Cu核球，其特徵在於：上述焊料鍍敷披膜，係Sn焊料鍍敷披膜或以Sn為主成分的無Pb焊料合金所構成之焊料鍍敷披膜，U的含量為5ppb以下，Th的含量為5ppb以下，該Cu球的純度為99.9%以上99.995%以下，Pb及/或Bi的含量的合計量為1ppm以上，真球度為0.95以上，然後，Cu核球的α射線量為0.0200cph/cm2以下。
  2. 根據申請專利範圍第1項之Cu核球，其中上述Cu核球的α射線量為0.0020cph/cm2以下。
  3. 根據申請專利範圍第1項之Cu核球，其中上述Cu核球的α射線量為0.0010cph/cm2以下。
  4. 根據申請專利範圍第1至3項中任一項之Cu核球，其中上述Cu球中的Pb及Bi的含量合計為1ppm以上。
  5. 根據申請專利範圍第1至4項中任一項之Cu核球，其直徑為1~1000μm。
  6. 根據申請專利範圍第1至5項中任一項之Cu核球，其中上述Cu球，在以上述焊料鍍敷披膜披覆之前預先以選自由Ni及Co之1元素以上所組成的鍍敷層披覆。
  7. 根據申請專利範圍第1至6項中任一項之Cu核球，其中上述Cu核球的真球度為0.95以上。
  8. 一種接點，使用申請專利範圍第1至7項中任一項之Cu核 球所形成。
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