TW201537710A - 銅核球、焊膏、泡沫焊、銅核柱以及焊接接頭 - Google Patents

銅核球、焊膏、泡沫焊、銅核柱以及焊接接頭 Download PDF

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Publication number
TW201537710A
TW201537710A TW103138311A TW103138311A TW201537710A TW 201537710 A TW201537710 A TW 201537710A TW 103138311 A TW103138311 A TW 103138311A TW 103138311 A TW103138311 A TW 103138311A TW 201537710 A TW201537710 A TW 201537710A
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Taiwan
Prior art keywords
copper
ball
solder
core
tin
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TW103138311A
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English (en)
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TWI612633B (zh
Inventor
Takahiro Hattori
Daisuke Soma
Takahiro Roppongi
Isamu Sato
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Senju Metal Industry Co
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Publication of TW201537710A publication Critical patent/TW201537710A/zh
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Publication of TWI612633B publication Critical patent/TWI612633B/zh

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    • 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
    • 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
    • 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
    • B23K35/02—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
    • B23K35/025—Pastes, creams, slurries
    • 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
    • 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
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C23C28/02—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
    • 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
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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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    • 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
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Abstract

本發明提供可得墜落強度及對熱循環的強度的銅核球、銅核柱。 銅核球1，包括：銅球2，其係以銅或銅合金構成；及焊料層3，其係以錫與銅所組成的焊料合金所構成，披覆銅球2，焊料層3係以0.1%以上3.0%以下包含銅，殘部為錫及雜質所構成。

Description

銅核球、焊膏、泡沫焊、銅核柱以及焊接接頭
本發明係關於以焊料合金披覆銅球的銅核球、使用銅核球的焊膏、使用銅核球的泡沫焊、以及使用銅核球的焊接接頭、銅核柱、使用銅核柱的焊接接頭。
近年，由於小型資訊機器的發達，裝載的電子零件迅速的小型化。電子零件，為因應小型化的要求而為對應連接端子的狹小化或構裝面積的縮小化，使用在背面設置電極的球柵陣列(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，係將具有電極的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，係藉由將焊料作成球狀的焊料球或將焊料作成柱狀的焊料柱接合於半導體晶片的電極而形成。使用BGA的半導體封裝，係使各焊料凸塊與接觸印刷基板的導電性接點接觸地，放置於印刷基板上，藉由加熱熔融的焊料凸塊與接點接合，而裝載於印刷基板。此外，為應付更高密度構裝的要求，有將半導體封裝在高度方向堆疊的3維高密度構裝的研究。
但是，將BGA使用於3維高密度構裝的半導體封裝，則有因半導體封裝的自重將焊料球壓潰，而在電極之間發 生連接短路。此將成為進行高密度構裝的障礙。
因此，研究以銅等，以熔點較焊料高的金屬所形成的微小徑的球或柱狀的柱作為核，於其表面披覆焊料的例如利用銅核球或銅核柱的焊料凸塊。具有銅球等的焊料凸塊，在將電子零件構裝於印刷基板時，焊料凸塊即使受到半導體封裝的重量，可藉由在焊料的熔點不會熔融的銅球支持半導體封裝。因此，並不會因半導體封裝的自重而將焊料凸塊壓潰。銅核球的相關技術，可舉例如專利文獻1。
[先前技術文獻]
[專利文獻]
專利文獻1：日本特開2010-99736號公報
然而，對使用焊料球、焊料柱、銅核球或銅核柱製作的焊料凸塊，要求對墜落等的衝擊強度、及被稱為對熱循環的溫度變化的伸縮的強度。
以包含銀的焊料合金製作的焊料球，對墜落強度、熱循環的強度，均可得既定的強度。為降低焊料合金的成本，使銀的添加量為1.0%左右的低銀的焊料合金，對墜落強度、熱循環的強度，亦可得既定的強度。
另一方面，以不包含銀的合金製作的焊料球，雖然摔降強度可得既定的強度，但可觀察到對熱循環的強度的下降。
本發明的課題，係在於提供，在於銅核球，可得與焊料球或焊料柱同等以上的墜落強度及熱循環的強度，如此之銅核球、使用銅核球之焊膏、泡沫焊及焊接接頭、銅核柱、使用銅核柱的焊接接頭。
本發明者們，發現以不包含銀的焊料合金披覆銅球的銅核球、以不包含銀的焊料合金披覆的銅柱的銅核柱，與以不包含銀的焊料合金製作的焊料球或焊料柱相比，墜落強度為同程度，而可提升對熱循環的強度。
因此，本發明如下。
(1)一種銅核球，包括：核層，其係以銅、或者，將銅包含50%以上的銅合金構成；及披覆核層之焊料層，其係由錫與銅組成的焊料合金所構成。
(2)根據上述(1)之銅核球，其中焊料層，以0.1%以上3.0%以下包含銅，殘部係由錫及雜質所構成。
(3)根據上述(2)之銅核球，其中以選自由鎳及鈷之1元素以上所組成的層所披覆的上述核層，係以上述焊料層披覆。
(4)根據上述(3)之銅核球，其中α射線劑量為0.0200cph/cm2以下。
(5)一種焊膏，使用上述(1)~上述(4)中任一項之銅核球。
(6)一種泡沫焊，使用上述(1)~上述(4)中任一項之銅核球。
(7)一種焊接接頭，使用上述(1)~上述(4)是中任一項之銅核球。
(8)一種銅核柱，包括：核層，其係以銅、或者，將銅包含50%以上的銅合金構成；及披覆核層之焊料層，其係由錫與銅組成的焊料合金所構成。
(9)根據上述(8)之銅核柱，其中焊料層，以0.1%以上3.0%以下包含銅，殘部係由錫及雜質所構成。
(10)根據上述(9)之銅核柱，其中以選自由鎳及鈷之1元素以上所組成的層所披覆的上述核層，係以上述焊料層披覆。
(11)根據上述(10)之銅核柱，其中α射線劑量為0.0200cph/cm2以下。
(12)一種焊接接頭，使用上述(8)~上述(11)中任一項之銅核柱。
於本發明，墜落強度、對熱循環的強度，均可得所需之既定強度。以不包含銀的焊料合金製作的焊料球，與以包含銀的焊料合金製作的焊料球相比，雖然對熱循環的強度會下降，但在於本發明，與以包含銀的焊料合金製作的銅核球相比，加上可得所需之墜落強度，可提升對熱循環的強度。銅核柱亦同樣，與以包含銀的焊料合金製作的銅核柱相比，加上可得所需的墜落強度，可提升對熱循環的強度。
1‧‧‧銅核球
2‧‧‧銅球
3‧‧‧焊料層
4‧‧‧擴散防止層
5‧‧‧銅核柱
6‧‧‧銅柱
7‧‧‧焊料層
8‧‧‧擴散防止層
第1圖係表示本實施形態的銅核球的示意構造的剖面圖。
第2圖係表示本實施形態的銅核柱的示意構造的側剖面圖。
第3圖係表示本實施形態的銅核柱的示意構造的平面剖面圖。
更詳細說明將本發明使用於銅核球時之情形。在於本說明書，關於銅核球的組成的單位(ppm、ppb及%)，若無特別指定，係對質量的比例(質量ppm、質量ppb及質量%)。
第1圖係表示本實施的形態之銅核球的示意構造之剖面圖。本實施形態的銅核球1，係以銅球2，及披覆銅球的焊料層3所構成。
焊料層3，係以銅的添加量為0.1%以上3.0%以下，殘部為錫的不包含銀的焊料合金所構成，藉由對銅球2的表面，進行焊料鍍敷形成焊料層3。銅球2，係以銅或，包含50%以上的銅的銅合金所構成。
銅核球1，係於銅球2與焊料層3之間形成擴散防止層4。擴散防止層4，係以選自由鎳、或鈷等之1元素以上所構成，防止構成銅球2的銅擴散到焊料層3。
於銅球2的表面，以銅的添加量0.1%以上3.0%以下，殘部為錫的不包含銀的組成的焊料合金形成焊料層3的銅核球1，即使接合對象物係於銅層的表面施以預焊劑處理的銅-OSP基板，於銅層的表面施以鎳/金電鍍的鎳/金電鍍基板，對墜落等的衝擊的強度、及對被稱為熱循環的溫度變化的伸縮性 的強度，可得所需之既定強度。
以不包含銀的焊料合金製作的焊料球，與以包含銀的焊料合金製作的焊料球相比，對熱循環的強度會下降。於本實施形態的銅核球1，雖然焊料層3係以不包含銀的焊料合金形成，但與以包含銀的焊料合金製作的銅核球相比，加上可得所需之墜落強度，可提升對熱循環的強度。
利用銅核球1的焊料凸塊，即使半導體封裝的重量施加於焊料凸塊，藉由以焊料合金的熔點不會熔融的銅球支持半導體封裝。因此，不會因為半導體封裝的自重使焊料凸塊被壓潰。
然而，電子零件的小型化，可實現高密度構裝，但高密度構裝，會引起軟錯誤的問題。軟錯誤係因α射線進入半導體積體電路(以下，稱為「IC」)而有記憶胞中的記憶內容被改寫的可能性。
α射線，可認為係由於包含於焊料合金中的雜質之鈾、釷、210釙等的放射性同位素，因α衰變所放射。因此，進行可實現低α射線的組成的焊料合金的開發。
於銅核球1，銅球2以焊料層3披覆，只要構成焊料層3的焊料合金可實現低α射線，則可認為可將銅球2所放射的α射線遮蔽，但對銅球2亦要求可實現低α射線的組成。
再者，於銅核球1，表示多接近真球的程度的真球度低，則形成焊料凸塊時，會降低載置時的流動性及焊料量的均勻性。因此，期望真球度高的銅核球1。
焊料層3的組成，係以錫為主要成分的無鉛焊料 合金，由對墜落等的衝擊的強度、及對熱循環的強度的觀點，係錫-銅合金。於銅核球1，焊料層3的厚度，並無特別限制，較佳的是以100μm(單側)以下即足夠。一般以1~50μm即可。
焊料層3的組成，係使銅球2或鍍液流動而形成。藉由鍍液的流動，於鍍液中鉛、鉍、釙的元素形成鹽而沈澱。一旦形成鹽的析出物，則可穩定地存在於鍍液中。因此，關於本發明之銅核球1，析出物並不會被取入焊料層3，可減低含於焊料層3之放射性元素的含量，可減低銅核球1本身的α射線劑量。
以下，詳述關於實現低α射線的焊料層3。
．鈾：5ppb以下、釷：5ppb以下
鈾及釷係放射性元素，為抑制軟錯誤需要抑制該等的含量。鈾及釷的含量，在為使焊料層3的α射線劑量為0.0200cph/cm2以下，需要分別在5ppb以下。此外，在抑制現在或未來的高密度構裝的軟錯誤的觀點，鈾及釷的含量，分別以2ppb以下為佳。
．α射線劑量：0.0200cph/cm2以下
關於本發明的銅核球1之α射線劑量為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射線劑量。關於本發明之銅核球1的α射線劑量，可藉由構成銅核球1的焊料層3的α射線劑量為0.0200cph/cm2以下所達成。此外，銅核球1的α射線劑量，亦可如後所述，以銅球2的α射線劑量為0.0200cph/cm2以下所達成。
關於本發明之銅核球1，頂多是以100℃形成，故 很難認為可藉由鈾、釷、210釙、鉍及鉛等的放射性元素的氣化而減少放射性元素的含量。但是，使鍍液或銅球2邊流動邊進行鍍敷，則鈾、釷、鉛、鉍及210釙在鍍液中形成鹽而沈澱。沈澱的鹽係電中性，故即使鍍液流動，亦不會混入焊料鍍膜中。
因此，該等在於焊料鍍膜中的含量可顯著地減少。因此，關於本發明之銅核球1，由於係以如此之焊料層3披覆，故顯示低的α射線劑量。α射線劑量，在更高密度構裝的軟錯誤的觀點，以0.0020cph/cm2以下為佳，以0.0010cph/cm2以下更佳。
由於構成關於本發明之銅核球1之焊料層3的純度越高，即，在於焊料層3的雜質含量越少，可減低放射性元素的含量，而減低α射線劑量，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射線劑量的觀點，以1000ppm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，焊料層3的總雜質量，係焊料層3中的錫及銅以外的雜質的含量的共計。
包含於焊料層3的雜質中，特別是以鉍與鉛的含量少為佳。鉍與鉛分別含有微量放射性同位素210鉍與210鉛。因此，可認為藉由減低鉍與鉛的含量，可顯著地減少焊料層3的α射線劑量。在於焊料層3的鉍與鉛的含量，分別以15ppm以下為佳，分別以10ppm以下更佳，分別以0ppm特別佳。
接著，詳述關於本發明之銅核球1之銅球2之組成、α射線劑量、真球度。
構成關於本發明之銅核球1之銅球2，當銅核球1使用於焊料凸塊時，由於並不會以焊接的溫度熔融，故可抑制焊接接頭的高度誤差。因此，銅球2，以真球度高且直徑誤差少為佳。此外，如上所述，銅球2的α射線劑量，亦與焊料層3同樣低為佳。以下，記載銅球2的較佳的態樣。
．鈾：5ppb以下，釷：5ppb以下
如上所述，鈾及釷係放射性同位素，在抑制軟錯誤需要抑制該等的含量。鈾及釷的含量，在為使銅球2的α射線劑量為0.0200cph/cm2以下，需要分別在5ppb以下。此外，在抑制現在或未來的高密度構裝的軟錯誤的觀點，鈾及釷的含量，分別以2ppb以下為佳。
．銅球的純度：99.9%以上99.995%以下
銅球2的純度為3N以上4N5以下。即，銅球2的雜質元素的含量為50ppm以上。在此，銅等的金屬材料的純度，係使99%為2N，99.9%為3N，99.99%為4N，99.999%為5N。所謂4N5，係表示金屬材料的純度為99.995%。
構成銅球2的銅的純度在於此範圍，則可於熔融銅中確保提高銅球2的真球度的充分的量的結晶核。提高真球度的理由詳述如下。
製造銅球時，形成為既定形狀的小片的銅材，係藉由加熱熔融，而熔融銅藉由表面張力成球形，而此凝固成銅球2。在於熔融銅由液體狀態凝固的過程，結晶粒在球形的熔融銅中成長。此時，雜質元素多，則該雜質元素成為結晶核而抑制結晶粒的成長。因此，球形的熔融銅，係藉由抑制成長的 微細結晶粒等成為真球度高的銅球2。
另一方面，雜質元素少，則成為結晶核的東西相對較少，粒成長不被抑制而以某一方向性成長，結果，球形的熔融銅的表面的一部分將突出來凝固。如此之銅球，真球度低。雜質元素，可考慮錫、銻、鉍、鋅、鐵、鋁、砷、銀、銦、鎘、銅、鉛、金、磷、硫、鈾、釷等。
純度的下限值並無特別限定，由抑制α射線劑量，抑制因純度的下降使銅球2的導電及熱傳導率的惡化的觀點，以3N以上為佳。即，銅球2除了銅的雜質元素的含量以未滿1000ppm。
．α射線劑量：0.0200cph/cm2以下
銅球2的α射線劑量為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射線劑量。於本發明，在加上通常用於製造銅球2的步驟，施以再度加熱處理。因此，使些微殘存於銅材的210釙揮發，而與銅材料相比，銅球2顯示更低的α射線劑量。α射線劑量，由抑制更高密度構裝的軟錯誤的觀點，以0.0020cph/cm2以下為佳，以0.0010cph/cm2以下更佳。
．鉛或鉍之任一之含量，或者鉛及鉍的合計含量為1ppm以上
包含於銅球2的雜質元素，可考慮錫、銻、鉍、鋅、鐵、鋁、砷、銀、銦、鎘、銅、鉛、金、磷、硫、鈾、釷等，構成關於本發明之銅核球1之銅球2，於雜質元素之中，特別是含有鉛或鉍之任一含量，或者鉛及鉍的合計含量以1ppm以上作 為雜質元素為佳。於本發明，在減少α射線劑量上，無須將鉛或鉍之任一的含量、或者，鉛及鉍的合計含量降低至極限。
其理由如下。
210鉛藉由β衰變變成210鉍，210鉍係藉由β衰變變成210釙，210釙係藉由α衰變變成206鉛。因此，為減少α射線劑量，可認為雜質元素之鉛或鉍的任一含量，或者鉛及鉍的含量盡量低為佳。
但是，包含於鉛中的210鉛及包含於鉍的210鉍的含有比很低。因此，只要將鉛及鉍的含量減低至某種程度，可認為可將210鉛及210鉍，充分去除到將α射線劑量降低到上述範圍的程度。另一方面，為提高銅球2的真球度，如上所述，雜質元素的含量較高較好。鉛與鉍均係藉由含於銅材作為雜質元素，可於銅球2的製造步驟的熔融時成為結晶核，而提升銅球2的真球度。因此，以可將α射線劑量減低至上述範圍的程度，去除210鉛及210鉍的量，含有鉛或鉍的任一，或者鉛及鉍為佳。由如此之觀點，銅球2，鉛或鉍之任一的含量，或者鉛及鉍的合計含量以1ppm以上為佳。
鉛或鉍之任一的含量，或者鉛及鉍的合計含量，以10ppm以上更佳。上限值以可減低α射線劑量的範圍，並無限定，由抑制銅球2的導電度的惡化的觀點，鉛或鉍之任一的含量，或者鉛及鉍的合計的含量，以未滿1000ppm更佳。鉛的含量，以10ppm~50ppm更佳，鉍的含量，以10ppm~50ppm更佳。
．銅球的真球度：0.95以上
銅球2的形狀，在抑制腳高高度的觀點，真球度以0.95以上為佳。銅球2的真球度在0.95以下，則銅球會成為不定形狀，而在形成凸塊時形成高度不均勻的凸塊，提高發生接合不良的可能性。真球度，以0.990以上為佳。在於本發明，所謂真球度，係表示由真球的偏離。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)、最小外切中心法(MCC法)等各種方法求得。詳言之，所謂真球度，係將各500個銅球2的直徑以長徑商除時所算出的算術平均值，其值越接近上限的1.00表示越接近真球。於本發明之長徑的長度、及直徑的長度，係以MITSUTOYO公司製的ULTRA QUICK VISION，ULTRA QV350-PRO測定裝置所測定的長度。
．銅球的直徑：1~1000μm
銅球2的直徑，以1~1000μm為佳。在於此範圍，則可穩定地製造球狀的銅球2，此外，端子間為窄間距時可抑制連接短路。
說明關於本發明之銅核球1之適用例，則銅核球1，係使用於混練焊料粉末、銅核球1，及助焊劑之焊膏。在此，關於本發明之銅核球1使用於焊膏時，「銅核球」亦可稱為「銅核粉」。
「銅核粉」，係包括上述特性的各個銅核球1，以多數銅核球1的集合體。例如，調和作為焊膏中的粉末等，與單一的銅核球，在於使用形態區別。同樣地，使用於焊料凸塊的形成時，通常亦係以集合體使用，故在如此的形態使用的「銅 核粉」，係與單一的銅核球有所區別。將「銅核球」以「銅核粉」的形態使用時，一般，銅核球的直徑為1~300μm。
此外，關於本發明之銅核球1，使用於銅核球1分散在焊料中的泡沫焊。於焊膏及泡沫焊，例如使用組成為錫-3銀-0.5銅(各數值為質量%)之焊料合金。再者，本發明不應限定於焊料合金。再者，關於本發明之銅核球1，可使用於電子零件的焊接接頭。此外，本發明，亦可應用在以銅為核之柱、桿或錠的形態。
說明關於本發明之銅核球1之製造方法之一例。成為材料之銅材，係放置在如陶瓷之耐熱性的板子之耐熱板，與耐熱板一起在爐中加熱。於耐熱板設有底部成半球狀的多數圓形的溝。溝的直徑及深度，可按照銅球的粒徑適宜設定，例如直徑為0.8mm，深度為0.88mm。此外，將銅細線切斷而得的小片形狀的銅材(以下，稱為「小片材」。)，一個一個投入耐熱板的溝內。
小片材投入溝內的耐熱板，在充填氨分解氣體的爐內升溫至1100~1300℃，進行30~60分鐘加熱處理。此時，爐內溫度呈銅的熔點以上，則小片材將會熔融成球狀。之後，於爐內冷卻，於耐熱板的溝內形成銅球2。冷卻後，成形的銅球2，以未滿銅的熔點的溫度800~1000℃再度進行加熱處理。
此外，作為其他的方法，由設於坩堝底部的小孔滴下熔融銅的液滴，該液滴被冷卻而將銅球2造粒之噴霧法，或以熱電漿將切銅金屬加熱為1000℃以上而造粒的方法。如此造粒的銅球2，可分別以800~1000℃的溫度再度進行加熱處理 30~60分鐘。
在關於本發明之銅核球1之製造方法，於造粒銅球2之前，亦可將作為銅球2的原料的銅材，以800~1000℃加熱處理。
銅球2的原料之銅材，可使用例如，錠、線、桿等。銅材的純度，在不過度降低銅球的純度的觀點，可為99.9~99.99%。
使用更高純度的銅材時，亦可不進行上述加熱處理，將熔融銅的持溫與先前同樣地降至1000℃左右。如此，上述加熱處理，可按照銅材的純度、α射線劑量為適宜省略或變更。此外，製造α射線劑量高的銅球或異形的銅球時，亦可將該等銅球作為原料再利用，可進一步降低α射線劑量。
此外，使如上所述地製作的銅球2與鍍液流動，於銅球2形成焊料層3的方法，有以習知之滾鍍等的電鍍法、連接於鍍敷槽之幫浦使鍍敷槽中的鍍液產生高速渦流，藉由鍍液的渦流，於銅球2形成鍍膜的方法、於鍍敷槽設置振動板，以既定的頻率振動，使鍍液被高速渦流攪拌，藉由鍍液的渦流，於銅球2，形成鍍膜的方法等。
於直徑100μm的銅球，披覆膜厚(單側)2μm的鍍鎳，進一步於鍍鎳上形成18μm的錫-銅焊料鍍膜，作成直徑大約140μm的銅核球為一例進行說明。
本發明之一實施形態之含有錫-銅之鍍液，係在以水為主體之媒體，含有磺酸類及金屬成分之錫及銅作為必要成分。
金屬成分係於鍍液中，以錫離子(Sn2+及/或Sn4+)及銅離子(Cu+/Cu2+)存在。鍍液，係藉由將主要以水與磺酸類所組成之鍍母液與金屬化合物混合而得，為金屬離子的穩定性，含有有機錯化劑為佳。
鍍液中的金屬化合物，例如可例示如下者。
錫化合物的具體例，可舉甲基磺酸、乙基磺酸、2-丙醇磺酸、對苯基磺酸等的有機磺酸的錫鹽、磺酸錫、氧錫銀、硝酸錫、氯化錫、溴化錫、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、磺胺酸錫、硼氟化錫、矽氟化錫等的亞錫化合物。該等錫化合物，可以一種單獨或混合二種以上使用。
銅化合物，可舉上述有機磺酸的銅鹽、磺酸銅、氧化銅、硝酸銅、氯化銅、溴化銅、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、硼氟化銅等。該等銅化合物可以一種單獨或混合二種以上使用。
此外，對披覆直徑104μm的鍍鎳的銅球形成膜厚(單側)18μm的錫-銅焊料鍍膜時，需要約0.0101庫侖的電量。
鍍液中的各金屬的調合量，Sn2+以0.05~2mol/L，以0.25~1mol/L為佳，銅以0.002~0.02mol/L，以0.003~0.01mol/L為佳。在此，參與鍍敷的係Sn2+，故在本發明調整Sn2+的量即可。
再者，根據法拉第的電解定律，以下式(1)估計鍍敷所期望的焊料的析出量，算出電量，對鍍敷液通入所算出之 電量的電流，邊使銅球及鍍液流動邊進行鍍敷處理。鍍敷槽的容量，可按照銅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係析出元素的原子量(錫為118.71)，Z係原子價(錫為2價)，F係法拉第常數(96500庫侖)，電量Q(A．秒)係以(I×t)表示。
於本發明，雖然係邊使銅球及鍍液流動而進行鍍敷，但是關於使之流動的方法，並無特別限定。例如，滾電鍍法，藉由滾桶的轉動，使銅球及鍍液流動。
鍍敷處理之後，於大氣中或N2氣氛中乾燥得到關於本發明的銅核球。
實施例
以下說明本發明之銅核球1之實施例，惟本發明不應限定於該等。
<墜落強度及熱循環試驗>
製作，形成有不包含銀的焊料合金所形成的焊料層的銅核球、形成有包含銀的焊料合金形成焊料層的銅核球、以不包含銀的焊料合金形成的焊球、及以包含銀的焊料合金形成的焊料球，進行對墜落等的衝擊強度的墜落強度試驗，及測定對熱循環的伸縮性的強度的熱循環試驗。
作為第1圖所示的銅核球1，於實施例1，製作直徑300μm的銅核球1。實施例1的銅核球1，係於直徑250μm的銅球2，以鎳形成膜厚在單側為2μm的擴散防止層4，以錫- 銅合金形成焊料層3。錫-銅合金的組成係錫-0.7銅，在於焊料層3的銅的添加量為0.7%。
作為比較例，於比較例1，製作將焊料層以錫-銀-銅合金形成之銅核球。錫-銀-銅合金之組成為錫-1.0銀-0.7銅。於比較例2，以與實施例1相同組成的錫-銅合金製作焊料球。於比較例3，以與比較例1相同組成的錫-銀-銅合金製作焊料球。
熱循環試驗，係使用上述實施例與各比較例的銅核球與焊料球，將15個半導體封裝基板(PKG)接合於1張的印刷電路板(PCB)上，製作評估基板。印刷電路板，使用於銅層的表面，施以預焊劑處理的尺寸174mm×120mm，厚度0.8mm的銅-OSP基板。半導體封裝基板，使用尺寸12×12mm之銅-OSP基板。
墜落強度試驗，係使用上述實施例與各比較例之銅核球與焊料球，將3個半導體封裝基板接合於1張印刷電路板上，製作評估基板。印刷電路板，使用於銅層的表面上進行預焊劑處理之尺寸30×120mm、厚度0.8mm的銅-OSP基板。半導體封裝基板使用銅-OSP基板。
在使用於對熱循環試驗及墜落強度試驗的半導體封裝基板，形成膜厚為15μm的抗蝕膜，於抗蝕膜上形成開口徑240μm的開口部，以回焊爐將實施例或比較例之銅核球或焊料球接合。回焊條件，在熱循環試驗墜落強度試驗均係以N2氣氛，頂峰溫度為245℃，預備加熱為140~160℃ 20秒，本加熱以220℃以上進行40秒。
如此地，將接合銅核球或焊料球的半導體封裝基板，分別構裝於熱循環試驗用的印刷電路板與墜落強度試驗用的印刷電路板。於印刷電路板，在熱循環試驗用與墜落強度試驗用，均係將焊料合金的組成為錫-3.0銀-0.5銅的焊膏，以厚度100μm，直徑240μm印刷，將接合實施例或比較例的銅核球或焊料球的半導體封裝基板，以回焊爐與印刷電路板連接。回焊條件，係於大氣，頂峰溫度為245℃，預備加熱為140~160℃70秒，本加熱以220℃以上進行40秒。
墜落強度試驗，係將製作的評估基板，於舉離載台10mm的位置，使用專用的夾具固定基板的兩端。遵照JEDEC規範，反覆施加加速度1500G的衝擊，由初期電阻值上升1.5倍時視作斷裂，記錄墜落次數。
熱循環試驗，係將製作的評估基板，以串聯電路常時測定電阻。使用ESPEC製冷熱衝擊裝置TSA101LA，分別以-40℃與+125℃各保持10分鐘的處理作為1個循環，以電阻值超過15Ω時視為斷裂，記錄印刷電路板上的15個半導體封裝基板的所有焊料接合部被破壞時的熱疲勞循環次數。對每1個組成製作10組評估基板，進行10次試驗，以其平均值作為結果。
於第一表表示半導體封裝基板，係於銅層的表面進行預焊劑處理的銅-OSP基板之情形之試驗結果。
半導體封裝基板，係於銅層的表面進行預焊劑處理的銅-OSP基板之情形，如第1表所示，焊料層以錫-銅合金形成的實施例1的銅核球，提升墜落強度的同時，對熱循環的強度亦得到超過所需的1500次。
半導體封裝基板為銅-OSP基板時，將焊料層以錫-銀-銅合金形成的比較例1的銅核球，雖墜落強度得到既定的強度，但看到對熱循環強度的下降。
半導體封裝基板為銅-OSP基板時，以錫-銅合金形成的比較例2的焊料球，雖墜落強度提升，但可看到對熱循環強度的下降。以錫-銀-銅合金形成的比較例3的焊料球，墜落強度、對熱循環的強度均得到所需之值。
如此，於實施例1的銅核球，接合對象物為銅-OSP基板時，可得充分的墜落強度及對熱循環的強度。
在此，在於實施例1的銅核球，在於焊料層的銅的添加量以0.1%以上3.0%以下的範圍進行墜落強度試驗、熱循環試驗，結果墜落強度、對熱循環的強度均得到所需以上之值。但是，銅的添加量為3.0%左右，則焊料合金的熔點會變高。因此，在以錫-銅合金形成的焊料層的銅的添加量，以0.1%以上2.0%以下為佳。
<α射線劑量的測定>
接著，製作真球度高的銅球，測定於該銅球表面形成焊料層的銅核球的α射線劑量。
．銅球的製作
調查真球度高的銅球的製作條件。準備純度99.9%銅錠、 純度99.995%以下的銅線及純度超過99.995%的銅板。將各個投入坩鍋之後，將坩鍋溫度升溫至1200℃，進行加熱處理45分鐘，由設在坩堝底部的孔滴落熔融銅的液滴，將液滴冷卻將銅球造粒。藉此，製作平均粒徑為250μm的銅球。將製作的銅球的元素分析結果及真球度示於第3表。
．真球度
以下，詳述真球度的測定方法。真球度，係以CNC影像測定系統測定。裝置係MITSUTOYO公司製的ULTRA QUICK VISION，ULTRA QV350-PRO。
．α射線劑量
α射線劑量的測定方法表示如下。於α射線劑量的測定，使用氣流比例計數器的α線測定裝置。測定樣品係於300mm×300mm的平面淺底容器鋪滿銅球者。將該測定樣品放入α射線測定裝置內，以PR-10氣流放置24小時之後，測定α射線劑量。
再者，使用於測定之PR-10氣體(氬90%-甲烷10%)，係將PR-10氣體充填於氣瓶後經過3週以上者。使用經過3週以上的氣瓶，係為避免進入氣瓶的大氣中的氡所產生的α射線，遵照JEDEC(Joint Electron Device Engineering Council)所制定的α射線測定方法的方針。
於第2表表示製作之銅球的元素分析結果、α射線劑量。
第2表係表示使用純度99.9%的銅錠及99.995%以下的銅線的銅球，真球度均為0.990以上。另一方面，如第3表所示，使用純度超過99.995%的銅板的銅球真球度低於0.95。因此，於以下所示實施例及比較例均係使用99.995%以下的銅線所製造的銅球製作銅核球。
關於以純度99.995%以下的銅線製造的銅球，以如下條件形成錫焊料鍍膜，製作實施例2的銅核球。
實施例2的銅核球，係對直徑250μm的銅球，使用約0.17庫侖的電量使用如下鍍液進行鍍敷處理，披覆膜厚(單側)50μm的焊料層。以SEM照片觀察以焊料鍍膜披覆的銅核球的剖面，結果膜厚約為50μm。處理後，於大氣中乾燥，得到銅核球。
焊料鍍液，係如下製作。於攪拌容器，對調製鍍液所需的水的1/3，放入54重量%的甲基磺酸水溶液的全容作為敷水。接著，放入作為錯化劑的硫醇化合物之一例之乙醯半胱胺酸，確認溶解之後，放入別的錯化劑的芳香族胺基化合物之一例之2,2'-二硫代二苯胺。變成淺藍色的凝膠狀的液體則迅速放入甲基磺酸亞錫。接著，對鍍液加入所需水的2/3，最後 加入作為界面活性劑之一例之α-萘酚聚氧乙烯醚(EO10莫耳)3g/L，完成鍍液的調製。製作鍍液中的甲基磺酸的濃度為2.64mol/L，錫離子濃度為0.337mol/L的鍍液。
於本例使用的甲基磺酸亞錫，係以下述錫片材作為原料調製。
焊料鍍液的原料之錫片材的元素分析，及形成於銅核球表面的焊料鍍膜的元素分析，關於鈾及釷，係以感應耦合電漿質量分析(ICP-MS分析)，其他的元素係以感應耦合電漿發光光譜分析(ICP-AES分析)進行。錫片材的α射線劑量，係於300mm×300mm的平面淺底容器鋪錫片材以外，以與銅球同樣地測定。銅核球的α射線劑量，係與上述銅球同樣地測定。此外，關於銅核球的真球度，亦使用與銅球同樣的條件進行測定。於第3表表示該等的測定結果。再者，作為比較例，測定錫片材的α射線劑量。
根據第3表，於錫片材的階段，α射線劑量超過0.2000cph/cm2，但是使用該錫片材，於銅球形成錫-銅合金焊料層的實施例2，α射線劑量顯示未滿0.0010cph/cm2。實施例2的銅核球，證明藉由鍍敷法形成焊料鍍膜，可減低α射線劑量。
此外，實施例2的銅核球，即使在製作後經過2 年，亦沒有看到α射線劑量的上升。
再者，以上係說明關於本發明之銅核球，惟本發明的形狀只要可達成防止因半導體封裝的自重使焊料凸塊被壓潰的目標，並不限於球狀，亦可使用上述之銅核柱。具體而言，亦可使用圓柱、三角柱或四角柱等的對基板直接接觸的上下面係以3邊以上構成的柱體。成核的銅柱可按照習知的方法形成，披覆銅柱表面的鍍敷亦可以使用於上述銅核球的方法形成鍍敷披覆。
第2圖係表示本實施形態的銅核柱的示意構造的剖面圖，第3圖係表示本實施形態之銅核柱之示意構造之平面剖面圖。本實施形態的銅核柱5，係以銅柱6，披覆銅柱6的焊料層7構成。
構成關於本發明之銅核柱5之銅柱6的上面及底面的直徑以1~1000μm為佳，特別是使用於窄間距時，以1~300μ更佳，進一步以1~200μm為佳，以1~100μm最佳。然後銅柱6的高度L，以1~3000μm為佳，特別是使用於窄間距時1~300μm更佳，進一步以1~200μm為佳，以1~100μm最佳。銅柱6的直徑及高度L在於上述範圍時，可將端子間以窄間距構裝，故可抑制連接短路的同時，可謀求半導體封裝的小型化及高積集化。
構成上述銅柱6的大小以外的關於本發明的銅核柱5的銅柱6的純度、α射線劑量、及含有的雜質等的較佳的條件，與關於本發明之銅球2的條件相同。再者，於銅柱6，由於並沒有要求真球度，故無需純度為4N5以下，即雜質元素 的含量為50ppm以上。但是，只要可減低α射線劑量的範圍，則無需將雜質的含量減至極限，在減低α射線劑量上，只要使鈾及釷的含量在既定之值以下，無須使鉛或鉍之任一的含量，或者，鉛及鉍的含量減至極限。即使不將雜質的含量減至極限，並不會影響墜落強度及對熱循環的強度。
此外，構成關於本發明之銅核柱5之焊料層7的焊料組成或α射線劑量、含有之雜質等的較佳的條件，與關於本發明之焊料層3的條件相同。
再者，關於本發明的銅核柱5的α射線劑量等的較佳的條件，與關於本發明的銅核球1的條件相同。
關於本發明的銅核柱5，亦可於銅柱6與焊料層7之間，形成擴散防止層8。擴散防止層8，係選自由鎳、或鈷等的1元素以上所構成，防止構成銅柱6的銅擴散至焊料層7。
關於本發明的銅核柱5，可使用於連接層積半導體晶片間的電極的矽貫通電極(through-silicon via：TSV)。TSV，係對矽以蝕刻開洞，於孔中依序形成絕緣層、於其上形成貫通導體，將矽的上下面研磨，使貫通導體露出上下面而製造。此步驟之中貫通導體，先前，將銅等藉由鍍敷法在孔中填充形成的方法，惟以此方法，由於將矽全面浸漬於鍍液，故有雜質的吸附及吸濕之虞。因此，可將關於本發明的銅核柱5，直接對形成於矽的孔向高度方向插入，使用作為貫通導體。將銅核柱5插入矽時，亦可藉由焊膏等的焊料材料接合，此外，將銅核柱5插入矽時，亦可僅以助焊劑接合。藉此可防止雜質的吸附及吸濕等的不良，藉由省略鍍敷步驟，可減低製造成本 及製造時間。
上述關於本發明的銅核柱5，可得與焊料柱同等以上的墜落強度及對熱循環的強度。
1‧‧‧銅核球
2‧‧‧銅球
3‧‧‧焊料層
4‧‧‧擴散防止層

Claims (12)

  1. 一種銅核球，包括：核層，其係以銅、或者，將銅包含50%以上的銅合金構成；及披覆上述核層之焊料層，其係由錫與銅組成的焊料合金所構成。
  2. 根據申請專利範圍第1項之銅核球，其中焊料層，以0.1%以上3.0%以下包含銅，殘部係由錫及雜質所構成。
  3. 根據申請專利範圍第2項之銅核球，其中以選自由鎳及鈷之1元素以上所組成的層所披覆的上述核層，係以上述焊料層披覆。
  4. 根據申請專利範圍第3項之銅核球，其中α射線劑量為0.0200cph/cm2以下。
  5. 一種焊膏，使用申請專利範圍第1至4項中任一項之銅核球。
  6. 一種泡沫焊，使用申請專利範圍第1至4項中任一項之銅核球。
  7. 一種焊接接頭，使用申請專利範圍第1至4項之中任一項之銅核球。
  8. 一種銅核柱，包括：核層，其係以銅、或者，將銅包含50%以上的銅合金構成；及披覆上述核層之焊料層，其係由錫與銅組成的焊料合金所構成。
  9. 根據申請專利範圍第8項之銅核柱，其中焊料層，以0.1%以上3.0%以下包含銅，殘部係由錫及雜質所構成。
  10. 根據申請專利範圍第9項之銅核柱，其中以選自由鎳及鈷之1元素以上所組成的層所披覆的上述核層，係以上述焊料層披覆。
  11. 根據申請專利範圍第10項之銅核柱，其中α射線劑量為0.0200cph/cm2以下。
  12. 一種焊接接頭，使用申請專利範圍第8至11項中任一項之銅核柱。
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