TW201529870A - 銅核球、焊接頭、泡沫焊料以及焊膏 - Google Patents

銅核球、焊接頭、泡沫焊料以及焊膏 Download PDF

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Publication number
TW201529870A
TW201529870A TW103131719A TW103131719A TW201529870A TW 201529870 A TW201529870 A TW 201529870A TW 103131719 A TW103131719 A TW 103131719A TW 103131719 A TW103131719 A TW 103131719A TW 201529870 A TW201529870 A TW 201529870A
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Taiwan
Prior art keywords
solder
ball
less
metal layer
solder ball
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TW103131719A
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English (en)
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TWI589712B (zh
Inventor
Hiroyoshi Kawasaki
Shigeki KONDOH
Takahiro Roppongi
Daisuke Soma
Isamu Sato
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Senju Metal Industry Co
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Publication of TW201529870A publication Critical patent/TW201529870A/zh
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Publication of TWI589712B publication Critical patent/TWI589712B/zh

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    • 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
    • B23K35/0233—Sheets, foils
    • B23K35/0238—Sheets, foils layered
    • 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
    • B23K35/22—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
    • 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
    • B23K35/302—Cu as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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Abstract

確保銅核球安裝於電極上時的對準性，且抑制軟錯誤發生。 銅核球11係包括：Cu焊球1、與被覆該Cu焊球1表面的金屬層2。金屬層2係由從Ni、Co、Fe之中選擇1以上的元素構成。Cu焊球1係純度99.9%以上且99.995%以下、U含量在5ppb以下、Th含量在5ppb以下、Pb及Bi中之至少其中一者的含量合計量達1ppm以上、真球度達0.95以上、α線量在0.0200cph/cm2以下。

Description

銅核球、焊接頭、泡沫焊料以及焊膏
本發明係關於α線量少、且具有磁性的銅核球、焊接頭、泡沫焊料以及焊膏。
近年，隨小型資訊機器的發達，所搭載電子零件正朝急速小型化發展。電子零件為因應小型化要求而導致連接端子狹小化與安裝面積縮小化，便有採用在背面設置電極的球柵陣列封裝(以下稱「BGA」)。
適用BGA的電子零件係有如半導體封裝。半導體封裝係將設有電極的半導體晶片利用樹脂密封。在半導體晶片的電極上形成焊料凸塊。該焊料凸塊係藉由將焊球接合於半導體晶片的電極而形成。適用BGA的半導體封裝便藉由將經加熱而熔融的焊料凸塊、與印刷電路基板的導電性島進行接合，而搭載於印刷電路基板上。又，為因應更進一步的高密度安裝要求，半導體封裝有就朝高度方向重疊的3次元高密度安裝進行檢討。
但是，若經3次元高密度安裝的半導體封裝適用BGA，便會有因半導體封裝的自重而導致焊球崩潰的情形。若發生此種情況，焊料便會從電極滲出，導致電極間相連接，亦判斷會發生短路。
此處針對使用焊膏在電子零件的電極上，電氣式耦接Cu焊球的焊料凸塊進行檢討。使用Cu焊球形成的焊料凸塊係當電子零件安裝於印刷電路基板時，即便半導體封裝的重量施加於焊料凸塊，仍可利用在焊料熔點下不會熔融的Cu焊球支撐著半導體封裝。所以，不會因半導體封裝的自重而導致焊料凸塊崩潰。
將Cu焊球配置於電極上的方法，係有實施對印刷電路基板上所配置的遮罩構件開口部饋入(feeding)Cu焊球的方法。該饋入方法係利用饋入手段使Cu焊球朝電極掉落後，使Cu焊球在遮罩上進行機械式移動，而將Cu焊球饋入於遮罩的開口部內。饋入方法係針對隨Cu焊球微小化，高精度將Cu焊球配置於電極上的方法而言屬有效。
但是，習知當使Cu焊球朝開口部移動時，因為伴隨使用刮刀或刷毛使Cu焊球移動的機械式移動，因而會有因刮刀而導致焊球發生損傷或變形、或者從刷毛混入異物的問題。
此處，有提案藉由使焊球具磁性，俾迴避焊球安裝時遭損傷等情形的饋入方法。例如專利文獻1所記載的焊球之配置裝置，係使焊球表面經覆被覆Ni等強磁性材料而使帶磁性的焊料核球，散佈於基板上之後，藉由使在平台內設置的磁石移動，而將焊料核球利用磁力作用饋入於遮罩開口部中。
再者，專利文獻2所記載的銅核球，係在防止Cu焊球的Cu擴散於焊料中之目的下，於Cu焊球表面上被覆著Ni。專利文獻3所記載的金屬焊球，係在抑制Cu與焊料間之 反應目的下，於核球與電鍍層之間，設置由Ni、NiP合金、NiB合金、Co及Pt中之任一元素構成的反應抑制層。
但是，近年雖隨電子零件的小型化已然實現高密度安裝，但隨高密度安裝的演進會引發軟錯誤的問題。軟錯誤係因α線進入半導體積體電路(以下稱「IC」)的記憶單元中，導致記憶內容會有被覆寫的可能性。α線可認為係因焊料合金中的U、Th、Po等放射性元素出現α崩壞而放射出的。此處，近年有進行減輕放射性元素含量的低α線焊料材料開發。
為減少α線量，一般係降低含放射性同位素的U、Th、Pb、Bi含量。例如相關文獻的專利文獻4。專利文獻4係揭示α線量低的Sn鑄錠發明，為減少α線量，不僅施行電解精煉，亦藉由使電解液中懸浮吸附劑，而吸附Pb、Bi俾降低α線量。專利文獻5有記載α線量低的Ag及Ag合金。專利文獻6有記載α線量低的Cu及Cu合金。
先前技術文獻
專利文獻
專利文獻1：日本專利特開2009-32813號公報
專利文獻2：日本專利特開2010-99736號公報
專利文獻3：日本專利特開2007-46087號公報
專利文獻4：日本專利第4472752號公報
專利文獻5：日本專利特開2011-214040號公報
專利文獻6：國際公開第2012/120982號公報
然而，上述專利文獻4~6雖為製造低α線量的銅核球，藉由使用高純度Cu便可實現銅核球的低α線量，但另一方面會有導致銅核球的真球度降低之問題。又，相關安裝時的銅核球損傷等並無沒有任何考慮在內。
再者，上述專利文獻1~3就降低焊料核球與銅核球之α線量的課題完全沒有考量在內，於高密度安裝時會有無法抑制軟錯誤發生的問題。
於是，本發明為解決上述課題，目的在於提供：防止當銅核球安裝於電極上時發生焊球損傷等，能抑制軟錯誤發生的銅核球、焊接頭、泡沫焊料以及焊膏。
本發明者等首先針對銅核球所使用的Cu焊球進行篩選。結果，發現若Cu焊球一定量含有Pb及Bi中之至少其中一者，便會造成Cu焊球的真球度降低，即便施行鍍Ni等，但仍被依低真球度狀態施行電鍍，結果導致所獲得銅核球的真球度降低。
其次，為降低構成銅核球之含Ni、Co、Fe的金屬層α線量，便著眼於使用電鍍法形成金屬層之事進行深入鑽研。結果，本發明者等為降低電鍍液中的Pb、Bi，以及減輕因該等元素崩壞所生成的Po，而一邊使Cu焊球、電鍍液流動，一邊在Cu焊球上形成電鍍被膜時，意外發現即便未懸浮吸附劑，該等Pb、Bi、Po元素仍會形成鹽。結果，在Ni等金屬層中不會取入該等元素，發現便會降低α線量。又，發現藉由構 成金屬層的金屬係使用高純度Ni、Co、Fe，且使用離子交換水等雜質較少的水生成電鍍液，便可減少所獲得金屬層的α線量。
在此，本發明係如下。
(1)一種銅核球，包括：Cu焊球；以及金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，U含量係5ppb以下，Th含量係5ppb以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上，α線量係0.0200cph/cm2以下。
(2)一種銅核球，包括：Cu焊球；以及金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述金屬層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
(3)一種銅核球，包括： Cu焊球；金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；以及第2金屬層，其乃被覆著上述金屬層的表面，且由從上述金屬層中未含有的Ni、Co、Fe之中選擇1以上的元素構成；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述第2金屬層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
(4)一種銅核球，包括：Cu焊球；金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；以及焊料層，其乃被覆著上述金屬層的表面；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述焊料層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
(5)一種銅核球，包括：Cu焊球； 金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；以及第2金屬層，其乃被覆著上述金屬層的表面，且由從上述金屬層中未含有的Ni、Co、Fe之中選擇1以上的元素構成；以及焊料層，其乃被覆著上述第2金屬層的表面；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述焊料層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
(6)如上述(1)~(5)所記載的銅核球，其特徵在於：α線量係0.0200cph/cm2以下。
(7)如上述(1)~(5)所記載的銅核球，其特徵在於：α線量係0.0010cph/cm2以下。
(8)如上述(1)~(5)中任一項所記載的銅核球，其特徵在於：更進一步包括被覆著上述金屬層、上述第2金屬層或上述焊料層表面的助焊劑層。
(9)一種焊接頭，其特徵在於：使用上述(1)~(8)中任一項所記載的銅核球。
(10)一種泡沫焊料，其特徵在於：使用上述(1)~(8)中任一項所記載的銅核球。
(11)一種焊膏，其特徵在於：使用上述(1)~(8)中任一項所記載的銅核球。
根據本發明，因為將Cu焊球的α線量設定在0.0200cph/cm2以下，因而當使用本發明銅核球形成焊接頭時，能抑制軟錯誤發生。又，因為Cu焊球表面利用Ni等金屬層被覆，因而可使銅核球帶有磁性。藉此，可防止銅核球安裝於電極上時發生損傷等情形，且可確保對準性。
1‧‧‧Cu焊球
2‧‧‧金屬層
11‧‧‧銅核球
圖1係本發明銅核球的構成例圖。
以下針對本發明進行更詳細說明。本說明書中，相關銅核球的金屬層組成單位(ppm、ppb、及%)，在無特別聲明之前提下，係表示相對於金屬層質量的比例(質量ppm、質量ppb、及質量%)。又，相關Cu焊球組成的單位(ppm、ppb、及%)，在無特別聲明之前提下，係表示相對於Cu焊球質量的比例(質量ppm、質量ppb、及質量%)。
圖1所示係本發明銅核球11的構成一例。如圖1所示，本發明的銅核球11係包括：Cu焊球1、以及被覆著Cu焊球1的表面且由從Ni、Co、Fe之中選擇1以上元素構成的金屬層。Cu焊球1係純度99.9%以上且99.995%以下、U含量在5ppb以下、Th含量在5ppb以下、Pb及/或Bi之含量合計量達1ppm以上、真球度達0.95以上、α線量在0.0200cph/cm2 以下。根據本發明的銅核球11，可降低焊接頭的α線量，且能使銅核球11全體帶有磁性。
1.金屬層
首先，針對本發明的金屬層2進行詳細說明。金屬層2係由例如：鍍Ni層、Co電鍍層、Fe電鍍層、或含有Ni、Co、Fe元素中之2以上的電鍍層構成。金屬層2係當銅核球11使用為焊料凸塊時，在焊接溫度下不會熔融而殘留，對焊接頭高度具有貢獻，因而構成真球度高、直徑變動少、且α線量低狀態。
．銅核球之α線量：0.0200cph/cm2以下
本發明銅核球11的α線量係0.0200cph/cm2以下。此係電子零件高密度安裝時，軟錯誤不會構成問題之程度的α線量。本發明銅核球11的α線量係藉由構成銅核球11的金屬層2之α線量在0.0200cph/cm2以下便可達成。所以，本發明的銅核球11因為被此種金屬層2被覆，因而呈較低的α線量。α線量就從更進一步抑制高密度安裝的軟錯誤觀點，較佳係0.0020cph/cm2以下、更佳係0.0010cph/cm2以下。金屬層2的U及Th含量係為能將Cu焊球1的α線量設為0.0200cph/cm2以下，便分別設為5ppb以下。又，就從抑制目前或未來高密度安裝的軟錯誤觀點，U及Th含量較佳係分別在2ppb以下。
．金屬層之磁性功能
因為銅核球11係Cu焊球1的表面利用由強磁性體構成的金屬層2被覆，因而焊球全體具有磁性。依此，藉由對銅核球11賦予磁性，便可獲得如下述效果。即，當利用饋入方法將銅 核球11安裝於電極上時，可利用在平台內所設置磁石的磁力，將在基板上所載置遮罩上散佈的銅核球11，明確地饋入於遮罩的開口部。藉此，因為不會有如習知饋入手段般的使刮刀、刷毛直接性接觸銅核球11，便可防止因饋入手段而造成銅核球11遭損傷與變形，並可防止異物混入。又，因為利用磁石的作用可調整銅核球11的位置，因而亦可確保銅核球11安裝於電極上時的對準性。
．金屬層之阻障功能
在迴焊時，若在為將銅核球11與電極間予以接合而使用的焊料(膏)中，有擴散Cu焊球1的Cu，焊料中及連接界面便會大量形成硬脆的Cu6Sn5、Cu3Sn介金屬化合物，當受衝擊時龜裂便會進展，導致連接部遭破壞。所以，為能獲得充分的連接強度，便必需抑制(阻障)Cu從Cu焊球1朝焊料的擴散。本實施例中，因為發揮阻障層功能的金屬層2形成於Cu焊球1的表面上，因而可抑制Cu焊球1的Cu擴散於糊膏狀焊料中。
．金屬層之組成及膜厚
金屬層2的組成係當由單一的Ni、Co或Fe構成金屬層2的情況，若排除不可避免的雜質外，Ni、Co、Fe便為100%。又，金屬層2所使用的金屬並不僅侷限於單一金屬，亦可使用從Ni、Co或Fe之中組合2元素以上的合金。又，亦可將由金屬層2所選擇元素以外的Ni、Co、Fe構成之單體金屬或合金構成的第2金屬層，被覆著金屬層2的表面。在金屬層2或第2金屬層中，在不致對Ni、Co、Fe所具有阻障功能與磁性功能構成影響的程度內，亦可既定量添加其他元素。所添加的元 素係可例如：Sn、Ag、Cu、In、Sb、Ge、P等。金屬層2或第2金屬層的膜厚T係例如1μm~20μm。
2. Cu焊球
其次，針對構成本發明的Cu焊球1進行詳細說明。Cu焊球1係構成當銅核球11使用為焊料凸塊時，在焊接溫度下不會熔融而殘留，對焊接頭高度具有貢獻，因而構成真球度高、直徑變動少、且α線量低狀態。
．U：5ppb以下、Th：5ppb以下
U及Th係屬於放射性同位元素，為能抑制軟錯誤便必需抑低該等的含量。U及Th含量係為能將Cu焊球1的α線量設為0.0200cph/cm2以下，便必需分別設在5ppb以下。又，就從抑制目前或未來高密度安裝的軟錯誤觀點，U及Th含量較佳分別係2ppb以下。
．Cu焊球的純度：99.9%以上99.995%以下
構成本發明的Cu焊球1較佳係純度99.9%以上且99.995%以下。若Cu焊球1的純度在該範圍內，熔融Cu中便可確保為提高Cu焊球1之真球度的足夠量結晶核。真球度提高的理由詳述如下。
製造Cu焊球1時，形成既定形狀小片的Cu材會因加熱而熔融，而熔融Cu則利用表面張力成為球形，其凝固便成為Cu焊球1。在熔融Cu從液體狀態進行凝固的過程中，結晶粒會在球形熔融Cu中成長。此時，若雜質元素偏多，該雜質元素便會成為結晶核而抑制結晶粒成長。所以，球形熔融Cu為因成長受抑制的微細結晶粒而成為高真球度的Cu焊球 1。另一方面，若雜質元素偏少，則相對性成為結晶核者亦會變少，便朝晶粒成長未受抑制的某方向性成長。結果，球形熔融Cu的表面其中一部分會突出並凝固。此種Cu焊球1的真球度低。雜質元素可考慮例如：Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、U、Th等。
純度下限值並無特別的限定，就從抑制α線量、抑制因純度低下而導致Cu焊球1的導電率與熱導率劣化觀點，較佳係99.9%以上。
此處，鍍Ni層等金屬層2係純度越高則越能降低α線量，相對的Cu焊球1係即便純度未提高至必要以上，仍可降低α線量。Cu的熔點較高於Sn，製造時的加熱溫度則Cu較高。本發明中，當製造Cu焊球1時，如後述，因為對Cu材施行習知未採行的加熱處理，便會使210Po、210Pb、210Bi所代表的放射性元素揮發。該等放射性元素中特別係210Po較容易揮發。
．α線量：0.0200cph/cm2以下
構成本發明的Cu焊球1之α線量較佳係0.0200cph/cm2以下。此係電子零件高密度安裝時，軟錯誤不會構成問題之程度的α線量。本發明中，追加為製造Cu焊球1而通常採行的步驟，並再度施行加熱處理。所以，在Cu的原材料中極些微殘存的210Po會揮發，相較於Cu的原材料之下，Cu焊球1呈現更低的α線量。α線量就從更加抑制高密度安裝下的軟錯誤觀點，較佳係0.0020cph/cm2以下、更佳係0.0010cph/cm2以下。
．Pb及Bi中之至少其中一者的含量合計達1ppm 以上
構成本發明的Cu焊球1係含有雜質元素之Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、U、Th等，特別係Pb及Bi中之至少其中一者的含量合計含有達1ppm以上。本發明中，即便在焊接頭形成時有露出Cu焊球1的情況，在降低α線量前提下，未必需要將Cu焊球1的Pb及Bi中之至少其中一者含量降低至極限。理由如下。
210Pb及210Bi會因β崩壞而轉變為210Po。為能降低α線量，最好亦盡量降低屬於雜質元素的Pb及Bi含量。
但是，Pb及Bi中所含210Pb、210Bi的含有比較低。若Pb、Bi的含量降低至某程度，便可認為210Pb、210Bi幾乎被除去。本發明的Cu焊球1係將Cu的熔解溫度設定為略高於習知，或者對Cu材及/或造球後的Cu焊球1施行加熱處理而製造。該溫度係即便較低於Pb、Bi沸點的情況，仍會發生氣化，因而可減少雜質元素量。又，為提高Cu焊球1的真球度，雜質元素含量越高越好。所以，本發明的Cu焊球1係Pb及Bi中之至少其中一者的含量合計達1ppm以上。當Pb及Bi均有含的情況，Pb及Bi之合計含量係1ppm以上。
依此，Pb及Bi中之至少其中一者即便在製造Cu焊球1後仍殘存某程度的量，因而含量的測定誤差較小。又，如前述，因為Bi及Pb在Cu焊球1製造步驟的熔融時會成為結晶核，因而若在Cu中含有一定量的Bi、Pb，便可製造高真球度的Cu焊球1。所以，Pb與Bi係供推定雜質元素含量的重要元素。就從此項觀點，Pb及Bi中之至少其中一者的含量合 計較佳係1ppm以上。Pb及Bi中之至少其中一者的含量更佳係合計達10ppm以上。上限值並無特別的限定，就從抑制Cu焊球1的導電率劣化觀點，較佳係Pb與Bi中之至少其中一者的含量合計未滿1000ppm、特佳係100ppm以下。Pb含量更佳係10ppm~50ppm，Bi含量更佳係10ppm~50ppm。
．Cu焊球之真球度：0.95以上
構成本發明的Cu焊球1就從控制基板間的適當空間(間隙器高度)觀點，真球度達0.95以上。若Cu焊球1的真球度未滿0.95，則因為Cu焊球1呈不定形狀，因而在凸塊形成時會形成高度不均勻的凸塊，導致發生接合不良的可能性提高。又，當將銅核球11搭載於電極上並施行迴焊時，會引發銅核球11出現位置偏移，導致自對準性惡化。真球度更佳係0.990以上。本發明中，所謂「真球度」係表示偏離正球的偏差。真球度係利用例如最小平方圓法(LSC法)、最小區域圓法(MZC法)、最大內切圓法(MIC法)、最小外接圓法(MCC法)等各種方法求取。詳言之，所謂「真球度」係表示500個Cu焊球的各直徑除以長徑時計算出的算術平均值，值越接近上限的1.00，便表示越接近正球。本發明中所謂「長徑的長度」、及「直徑的長度」係指利用MITUTOYO公司製Ultra Qucik版、ULTRA QV350-PRO測定裝置測定的長度。
．Cu焊球之直徑：1~1000μm
構成本發明的Cu焊球1之直徑較佳係1~1000μm。若在此範圍內，便可安定地製造球狀Cu焊球1，且可抑制當端子間屬於窄間距時的連接短路情形。
此處，例如當本發明的銅核球11之直徑係1~300μm程度的情況，「銅核球」集合體亦可稱為「Cu核粉末」。其中，「Cu核粉末」係包括分別具有上述特性的銅核球11之多數銅核球11的集合體。例如焊膏中依粉末形式摻合等，在使用形態上與單一銅核球11有所區分。同樣的，使用於焊料凸塊形成時，亦是通常依集合體形式處置，因而依此種形態使用的「Cu核粉末」係與單一銅核球11有所區分。
再者，本發明銅核球11的真球度較佳係0.95以上。當銅核球11的真球度偏低時，在將銅核球11搭載於電極上並施行迴焊時，會引發銅核球11出現位置偏移，導致自對準性惡化。真球度更佳係0.990以上。
再者，構成本發明銅核球11的金屬層2之表面或第2金屬層，亦可利用助焊劑層被覆。又，構成銅核球11的金屬層2或第2金屬層的表面亦可利用焊料層被覆。此時，亦可將焊料層表面更進一步利用助焊劑層被覆。
本發明中，除將Cu焊球1自體設為低α線量之外，藉由在銅核球11構成中成為最外殼的金屬層2、第2金屬層或焊料層的α線量設定在0.0200cph/cm2以下，便可達成本發明。所以，因為本發明的銅核球11係被此種最外殼被覆，因而呈低α線量。α線量就從更進一步抑制高密度安裝時的軟錯誤觀點，較佳係0.0020cph/cm2以下、更佳係0.0010cph/cm2以下。為能將銅核球11的α線量設在0.0200cph/cm2以下，金屬層2、第2金屬層或焊料層的U及Th含量分別設為5ppb以下。又，就從抑制目前或未來高密度安裝的軟錯誤觀點，U及Th含量 較佳分別係2ppb以下。
再者，藉由使本發明銅核球11分散於焊料中，便可使用為泡沫焊料。又，藉由使含有本發明的銅核球11，亦可使用為焊膏。又，本發明的銅核球11亦可使用於將電子零件的端子彼此間予以接合的焊接頭形成。
針對本發明銅核球11之製造方法一例進行說明。材料的Cu材放置於如陶瓷之類的耐熱性板(以下稱「耐熱板」)上，再與耐熱板一起在爐中加熱。耐熱板中設有底部呈半球狀的多數圓形溝渠。溝渠的直徑與深度係配合Cu焊球1的粒徑再行適當設定，例如直徑0.8mm、深度0.88mm。又，經切斷Cu細線而獲得的晶片形狀Cu材(以下稱「晶片材」)，係每次1個投入於耐熱板的溝渠內。在溝渠內已投入晶片材的耐熱板，在經填充氨分解氣體的爐內升溫至1100~1300℃，並施行30~60分鐘的加熱處理。此時若爐內溫度成為Cu的熔點以上，晶片材便會熔融而成為球狀。然後，冷卻爐內，並在耐熱板的溝渠內成形為Cu焊球1。經冷卻後，所成形的Cu焊球1依未滿Cu熔點的溫度800~1000℃再度施行加熱處理。
再者，其他方法尚有如：從在坩堝底部設置的節流孔滴下熔融Cu，冷卻該液滴而造球Cu焊球1的霧化法；以及由熱電漿將Cu切割金屬(cut metal)加熱至1000℃以上並造球的方法。依此造球的Cu焊球1亦可分別依800~1000℃溫度施行30~60分鐘的再加熱處理。
本發明銅核球11的製造方法，在造球出Cu焊球1之前，亦可將屬於Cu焊球1原料的Cu材依800~1000℃施行 加熱處理。
屬於Cu焊球1原料的Cu材係可使用例如顆粒、焊線、柱等。Cu材的純度就從Cu焊球1的純度不會過度降低的觀點，較佳係99.9~99.99%。
再者，使用高純度Cu材的情況，亦可未施行前述加熱處理，而將熔融Cu的保持溫度與習知同樣地下降至1000℃程度。依此前述加熱處理亦可配合Cu材純度與α線量而適當省略與變更。又，當製造α線量高的Cu焊球1、或異形Cu焊球1的情況，該等Cu焊球1亦可再利用為原料，可使α線量更降低。
在所製作Cu焊球1上形成金屬層2的方法，係可採用公知的電解電鍍法等方法。例如形成鍍Ni層的情況，針對鍍Ni的浴種，藉由使用Ni基底金屬調整Ni鍍液，再於該經調整過的Ni鍍液中浸漬Cu焊球1並進行電析，便在Cu焊球1的表面上形成鍍Ni層。又，形成鍍Ni層等金屬層2的其他方法亦可採用公知的無電解電鍍法等。
再者，本發明亦可應用於以Cu為核的管柱、柱、顆粒形態。
實施例1
以下，對本發明實施例進行說明，惟本發明並不僅侷限於該等。本實施例係製作真球度高的Cu焊球，在該Cu焊球的表面上形成金屬層的鍍Ni層，並測定α線量。
．Cu焊球之製作
調查高真球度的Cu焊球之製作條件。準備純度99.9%的 Cu顆粒、純度99.995%以下的Cu焊線、及純度超過99.995%的Cu板。分別投入於坩堝中，然後將坩堝溫度升溫至1200℃，施行45分鐘的加熱處理。接著，從在坩堝底部設置的節流孔滴下熔融Cu，冷卻生成的液滴而造球出Cu焊球，製得平均粒徑250μm的Cu焊球。就元素分析，針對U及Th係利用感應耦合電漿質量分析(ICP-MS分析)實施，針對其他元素係利用感應耦合電漿發光分光分析(ICP-AES分析)實施。
．真球度
真球度係利用CNC影像測定系統進行測定。裝置係使用MITUTOYO公司製的Ultra Qucik版、ULTRA QV350-PRO。
．α線量
α線量的測定方法係如下。α線量的測定係使用氣體流動比例計數器的α線測定裝置。測定樣品係在300mm×300mm的平面淺底容器中墊底鋪設Cu焊球。將該測定樣品放入α線測定裝置內，依PR-10氣體流動放置24小時後，測定α線量。
另外，測定所使用的PR-10氣體(氬90%-甲烷10%)係在PR-10氣體填充於氣體鋼瓶中之後經3週以上者。使用經3週以上鋼瓶的理由係為不會因進入氣體鋼瓶的大氣中之氡而產生α線，而依照JEDEC(Joint Electron Device Engineering Council)所規定的JEDEC STANDARD-Alpha Radiation Measurement In Electronic Materials JESD221。所製作Cu焊球的元素分析結果、α線量係如表1所示。
如表1所示，使用純度99.9%Cu顆粒、及純度99.995%以下Cu焊線的Cu焊球，均呈真球度達0.990以上。另一方面，如表1所示，使用純度超過99.995%Cu板的Cu焊球，真球度低於0.95。
其次，在利用純度99.9%Cu顆粒製造的Cu焊球表面上，使用純度99.99%以上的Ni基底金屬形成鍍Ni層，而製作銅核球。本實施例中，因為使用瓦特浴電析出鍍Ni層，因而電鍍液的調整係依如下述實施。首先，利用鹽酸溶解Ni基底金屬，使水分及多餘的鹽酸氣體蒸發而製作氯化Ni的結晶。又，利用硫酸溶解Ni基底金屬，使水分及多餘的硫酸氣體蒸發而製作硫酸Ni的結晶。利用建浴時所使用離子交換水的1/3使氯化Ni與硫酸Ni溶解。剩餘的2/3離子交換水加熱至60℃，使硼酸溶解後，添加氯化Ni與硫酸Ni的混合溶液，充分攪拌，藉由使氯化Ni、硫酸Ni及硼酸完全溶解，而結束Ni鍍液的調整。
其次，在電鍍裝置的電鍍槽中，裝滿依上述方法建浴的Ni鍍液，投入Cu焊球，使Cu焊球浸漬於Ni鍍液中。然後，施加電流而進行電析，便對Cu焊球表面施行鍍Ni。本 實施例中，一邊使Cu焊球及電鍍液流動一邊施行電鍍，但相關使流動的方法並無特別的限定。例如桶式電解電鍍法的情況，藉由使桶依特定旋轉數進行旋轉，在可使Cu焊球及電鍍液流動。此時，Ni鍍液的液溫維持於40~60℃。又，電量設為0.0019庫倫，例如在直徑100μm的Cu焊球1個之單側形成2μm(參照圖1的T)鍍Ni層。若Ni膜厚已成長至目標球徑，便停止電鍍裝置，回收在Cu焊球表面上已形成鍍Ni層的銅核球。
銅核球的α線量係使用與前述Cu焊球同樣的裝置，並依照同樣方法進行測定。又，相關銅核球的真球度亦使依照與Cu焊球相同的條件進行測定。該等的測定結果係如表2所示。
實施例2
實施例2中，採用使用表1所示純度99.995%以下Cu焊線製成的Cu焊球，依照與實施例1同樣的方法施行鍍Ni處理，製作在Cu焊球表面上形成鍍Ni層的銅核球，施行與實施例1同樣的評價。針對所製作的銅核球依照與實施例1同樣地測定α線量、真球度。測定結果如表2所示。
實施例3
實施例3中，採用使用表1所示純度超過99.995%的Cu板製成的Cu焊球，依照與實施例1同樣的方法施行鍍Ni處理，製作在Cu焊球表面上形成鍍Ni層的銅核球，施行與實施例1同樣的評價。針對所製作的銅核球依照與實施例1同樣地測定α線量、真球度。測定結果如表2所示。
根據表2所示，實施例1的銅核球之α線量係未滿0.0010cph/cm2。根據實施例1的銅核球，驗證到即便在Cu焊球表面上形成鍍Ni層的情況仍可降低α線量。又，實施例1所製成銅核球的α線量在表1雖無記載，但即在製成後經1年，仍未發現α線上升。
同樣的，實施例2及實施例3亦是銅核球的α線量未滿0.0010cph/cm2。根據實施例2、3的銅核球，驗證到即便在Cu焊球表面上形成鍍Ni層的情況仍可降低α線量。又，實施例2及實施例3所製成銅核球的α線量在表1雖無記載，但即在製成後經1年，仍未發現α線上升。
另外，本發明的技術範圍並不僅侷限於上述實施形態，涵蓋在不脫逸本發明主旨的範疇內對上述實施形態所追加的各種變更。例如上述實施例中，針對金屬層係採用鍍Ni層的例子進行說明，惟當金屬層係採用Co電鍍層、Fe電鍍層的情況，仍與鍍Ni層同樣的，可獲得低α線量、且高真球度的銅核球。
1‧‧‧Cu焊球
2‧‧‧金屬層
11‧‧‧銅核球

Claims (11)

  1. 一種銅核球，包括：Cu焊球；以及金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，U含量係5ppb以下，Th含量係5ppb以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上，α線量係0.0200cph/cm2以下。
  2. 一種銅核球，包括：Cu焊球；以及金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述金屬層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
  3. 一種銅核球，包括：Cu焊球；金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；以及 第2金屬層，其乃被覆著上述金屬層的表面，且由從上述金屬層中未含有的Ni、Co、Fe之中選擇1以上的元素構成；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述第2金屬層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
  4. 一種銅核球，包括：Cu焊球；金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；以及焊料層，其乃被覆著上述金屬層的表面；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述焊料層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
  5. 一種銅核球，包括：Cu焊球；金屬層，其乃被覆著上述Cu焊球的表面且由從Ni、Co、Fe之中選擇1以上的元素構成；以及第2金屬層，其乃被覆著上述金屬層的表面，且由從上述 金屬層中未含有的Ni、Co、Fe之中選擇1以上的元素構成；以及焊料層，其乃被覆著上述第2金屬層的表面；其特徵在於：上述Cu焊球係純度99.9%以上且99.995%以下，Pb及Bi中之至少其中一者的含量合計量係1ppm以上，真球度係0.95以上；上述焊料層係U含量在5ppb以下、Th含量在5ppb以下、α線量在0.0200cph/cm2以下。
  6. 如申請專利範圍第1至5項中任一項之銅核球，其中，α線量係0.0200cph/cm2以下。
  7. 如申請專利範圍第1至5項中任一項之銅核球，其中，α線量係0.0010cph/cm2以下。
  8. 如申請專利範圍第1至5項中任一項之銅核球，其中，更進一步包括被覆著上述金屬層、上述第2金屬層或上述焊料層表面的助焊劑層。
  9. 一種焊接頭，其特徵在於：使用申請專利範圍第1至8項中任一項之銅核球。
  10. 一種泡沫焊料，其特徵在於：使用申請專利範圍第1至8項中任一項之銅核球。
  11. 一種焊膏，其特徵在於：使用申請專利範圍第1至8項中任一項之銅核球。
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