TWI648416B - 核材料和半導體封裝以及形成凸塊電極的方法 - Google Patents

核材料和半導體封裝以及形成凸塊電極的方法 Download PDF

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TWI648416B
TWI648416B TW106138292A TW106138292A TWI648416B TW I648416 B TWI648416 B TW I648416B TW 106138292 A TW106138292 A TW 106138292A TW 106138292 A TW106138292 A TW 106138292A TW I648416 B TWI648416 B TW I648416B
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mass
concentration ratio
nuclear material
plating layer
nuclear
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TW106138292A
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TW201823482A (zh
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西野友朗
近藤茂喜
服部貴洋
川浩由
六本木貴弘
相馬大輔
佐藤勇
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日商千住金屬工業股份有限公司
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    • 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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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
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Abstract

本發明的核材料係在核12的表面上，將由Sn與Bi所構成(Sn-Bi)系焊料合金施行鍍敷被膜的核材料，其中，鍍焊層16中的Bi係在鍍焊層中依既定範圍濃度比分佈的核材料，在鍍焊層中依Bi濃度比91.7~106.7%既定範圍內分佈的核材料。因為鍍焊層中的Bi呈均質，因而包括鍍焊層中的內周側、外周側在內橫跨全區域的Bi濃度比均在既定範圍內。所以，不會發生內周側較外周側更早熔融，導致內周側與外周側出現體積膨脹差，造成核材料發生爆裂飛散等狀況。又，因為鍍焊層全體幾乎均勻熔融，因而不會有因熔融時序落差而發生的核材料位置偏移，故不會有因位置偏移等所衍生的電極間短路等可能性。

Description

核材料和半導體封裝以及形成凸塊電極的方法
本發明係關於核材料、具有使用該核材料之焊料凸塊的半導體封裝、以及形成凸塊電極的方法。
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(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而構成。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。近年為因應更高密度安裝的要求，半導體封裝亦有開發出朝高度方向重疊的三次元高密度安裝。
形成三次元高密度安裝的半導體封裝為BGA，當在半導體晶片的電極上載置焊料球並施行迴焊處理時，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，焊料會從電極滲出導致電極間相接處，會有發生短路的可能 性。
為防止此種短路事故，有提案焊料球不會因自重而崩潰、或在焊料熔融時不會變形的焊料凸塊。具體而言，提案將由金屬或樹脂成形的球使用為核，再將利用焊料被覆該核的核材料使用為焊料凸塊。
被覆著核的鍍焊層大多使用以Sn為主成分的無鉛焊料。較佳例係可例如由Sn與Bi構成的Sn系焊料合金(參照專利文獻1與專利文獻2)。
專利文獻1所揭示的核材料，金屬係使用Cu球，將其當作核，並在其表面上形成由Sn與Bi所構成Sn系焊料合金的鍍焊層。含Bi的Sn系焊料合金，因為熔融溫度係130~140℃的較低溫，因而為了對半導體封裝賦予的熱應力較少等理由被使用為鍍敷組成。
專利文獻1，鍍焊層中所含的Bi含有量係依內側(內周側)較少，且朝外側(外周側)逐漸提高的濃度斜率施行鍍敷處理。
專利文獻2所揭示的焊料凸塊，亦是出於與專利文獻1同樣的理由，將Cu球使用為核，並在其上面形成由Sn與Bi所構成Sn系焊料合金的鍍敷被膜。專利文獻2的鍍焊層中所含Bi含有量，係依內側(內周側)高，並朝外側(外周側)逐漸降低的濃度斜率施行鍍敷處理。
專利文獻2的技術係形成與專利文獻1完全相反的濃度斜率。理由係考慮由專利文獻2提案的濃度控制，較由專利文獻1所提案情況更為簡單，較容易形成的緣故。
[先行技術文獻] [專利文獻]
[專利文獻1]日本專利特開2007-44718號公報
[專利文獻2]日本專利第5367924號公報
但是，若所使用核材料係在Cu球表面上由Sn與Bi所構成Sn系焊料合金的鍍敷被膜，並將該核材料載置於半導體晶片的電極上並施行迴焊處理時，專利文獻1與2會發生如下述問題。
專利文獻1所揭示的技術，依此設有Bi濃度在內周側較低、在外周側則較高之濃度斜率的鍍焊層，但當此種濃度斜率(內側較低、外側較高)的情況，Bi熔融的時序會有內周側與外周側出現些微落差的可能性。
若熔融時序發生落差，即便核材料的外表面已開始熔融，但內周面側的區域卻仍未出現熔融，呈現混雜部分溶解情形，結果造成核材料出現朝熔融側些微位置偏移情形。若窄間距的高密度安裝，在此種位置偏移情況下進行的焊料處理會有成為致命性缺陷的可能性。
專利文獻2的Bi濃度斜率恰與專利文獻1相反。即便此種情況，在將半導體封裝予以連接時仍是採行利用迴焊進行加熱處理。如專利文獻2所示，若依鍍焊層中的Bi濃度在內周側較高、外周側較低的狀態施行加熱熔融，則因為內周側的Bi密度較高，因而焊料會從內周側的Bi區域開始熔融。 因為即便內周側的Bi區域已熔融，但外周側的Bi區域卻仍未開始熔融，因而內周側的Bi區域側便提早出現體積膨脹。
因此種體積膨脹在內外周側的快慢差異，導致在Bi的內周側與外周側(外氣)出現壓力差，若Bi的外周側開始熔融，則因內周側的體積膨脹所造成壓力差，會造成成為核的Cu球發生爆裂飛散之類的狀況。此種狀況的發生係無法迴避的。
依此設有由Sn與Bi所構成Sn系焊料合金之鍍焊層的Cu核球，當鍍焊層中的Bi有濃度斜率的情況會發生不良情形。
緣是，本發明有鑑於上述課題而完成，目的在於提供：特別係核表面設有由Sn與Bi所構成(Sn-Bi)系焊料合金施行電鍍，形成之電鍍焊層的核材料，鍍焊層中所含Bi係依91.4~106.7%既定範圍的濃度比分佈於鍍焊層中之核材料。換言之，藉由將Bi的濃度比收束於既定範圍內，鍍焊層中的Bi濃度成為均質(均等)，在鍍焊層中包含內層、中間層及外層在內的全區域，Bi濃度比均在既定範圍內的核材料及使用該核材料的半導體封裝。
但，當在核與(Sn-Bi)系焊料合金鍍焊層間，施行Ni電鍍等基底鍍敷層的情況，便提供鍍焊層中除基底鍍敷層外其餘均形成Bi呈均質分佈的核材料。
又，亦提供具有使用此種核材料之凸塊的半導體封裝。
另外，本案所使用的「Bi濃度比(%)」係指鍍焊層既定區域中，Bi測量值(質量%)相對於目標Bi含有量(質量%)的比(%)、或Bi測量值的平均值(質量%)相對於目標Bi含有量(質 量%)的比(%)。
再者，因為既定區域的Bi含有量亦可換說為該既定區域的Bi濃度，因而本案所採用的「Bi濃度比(%)」便指鍍焊層既定區域中，所計測Bi濃度相對於目標Bi濃度的比(%)、或所計測Bi濃度的平均相對於目標Bi濃度的比(%)。
另外，鍍焊層的Bi含有量計測亦可採取針對核材料使用氧酸等溶解鍍焊層，再施行ICP-AES、ICP-MS等公知分析手法。
為解決上述課題，申請專利範圍第1項所記載本發明的核材料，係在核表面上利用電鍍焊，設有由Sn與Bi所形成(Sn-Bi)系焊料合金之鍍焊層的核材料，其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg等金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；若上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比係在91.4~106.7%範圍內。
申請專利範圍2所記載本發明的核材料，係在核 表面上利用電鍍焊，設有由Sn與58質量%Bi所構成(Sn-58Bi)系焊料合金之電鍍焊層的核材料；其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg等金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；若上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比係在91.4~108.6%範圍內。其中，(Sn-58Bi)係(Sn-58重量%Bi)。
申請專利範圍3所記載本發明的核材料，係在核表面上利用電鍍焊，設有由Sn與40質量%Bi所構成(Sn-40Bi)系焊料合金之電鍍焊層的核材料；其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg等金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；若上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)
表示時，上述濃度比係在90~107.5%範圍內。其中，(Sn-40Bi)係(Sn-40重量%Bi)。
申請專利範圍4所記載本發明的核材料，係在核表面上利用電鍍焊，設有由Sn與3質量%Bi所構成(Sn-3Bi)系焊料合金之電鍍焊層的核材料；其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg等金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；若上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)
表示時，上述濃度比係在90~106.7%範圍內。其中，(Sn-3Bi)係(Sn-3重量%Bi)。
申請專利範圍第5項所記載本發明的核材料，係如申請專利範圍第1至4項中任一項所記載的核材料，其中，上述核材料係從上述核表面起依序設有從Ni及Co中選擇1元素以上的基底鍍敷層與上述電鍍焊層。
申請專利範圍第6項所記載本發明的核材料，係如申請專利範圍第1至5項中任一項所記載的核材料，其中，核係使用Cu球。
申請專利範圍第7項所記載本發明的核材料，係如申請專利範圍第1至5項中任一項所記載的核材料，其中，核係使用Cu管柱。
申請專利範圍第8項所記載本發明的半導體封裝，係使用申請專利範圍第1至7項中任一項所記載核材料的半導體封裝。
申請專利範圍第9項所記載本發明形成凸塊電極的方法，係在核表面上利用電鍍焊，設有由Sn與Bi所構成(Sn-Bi)系焊料合金之電鍍焊層的核材料；其特徵在於包括：在電極上搭載下述核材料的步驟；而，上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg等金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；若上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)
表示時，上述濃度比在91.4~106.7%範圍內的核材料；以及藉由對所搭載的上述核材料施行加熱，而形成凸塊電極的步驟。
鍍焊層中的Bi係依相對於鍍敷厚度，從內周側起朝外周側，以及包含內周側、外周側在內的全區域中，濃度分佈均呈均質的方式施行處理(但，當核有施行Ni電鍍等基底鍍敷層時，基底鍍敷層除外)。
Sn系焊料合金係除(Sn-Bi)系焊料合金之外，尚亦可含有其他添加元素。(Sn-Bi)系焊料合金中可添加的元素，係有如Ag、Cu、Ni、Ge、Ga、In、Zn、Fe、Pb、Sb、Au、Pd、Co等中之一種或二種以上的元素。可考慮例如(Sn-Bi-Cu-Ni)系焊料合金、(Sn-Ag-Cu-Bi)系焊料合金等。
該核材料係在將由Sn與Bi所構成(Sn-Bi)系焊料合金，利用電鍍焊在核表面上形成鍍敷被膜的核材料，而鍍焊層中的Bi在鍍焊層中依既定範圍濃度比分佈的核材料，且Bi濃度比在鍍焊層中依91.4~106.7%既定範圍內分佈的核材料。相關濃度比(%)，容後述。
根據本發明的核材料，因為電鍍焊層中的Bi呈均質，因而相對於鍍焊層膜厚，在包含Bi內周側、外周側在內的全區域中，Bi濃度比在既定範圍內。所以，不會發生內周側較外周側更早熔融，導致內周側與外周側出現體積膨脹差，致使核材料發生爆裂飛散的狀況。
再者，因為電鍍焊層中的Bi呈均質，因而橫跨核 材料全面幾乎均勻熔融，故在鍍焊層內的熔融時序幾乎不會發生時間差。結果，不會發生因熔融時序落差而出現核材料位置偏移情形，故不會有因位置偏移等所衍生的電極間短路等情形。所以，藉由使用該核材料便可提供高品質的半導體封裝。此處，針對膜厚可均勻控制的另一面會造成濃度呈不均質的電鍍焊問題，藉由本發明將Bi濃度比控制成收束於既定範圍內，便可獲得具有均質電鍍焊層的核材料。
10‧‧‧Cu核球
12‧‧‧Cu球
14‧‧‧基底鍍敷層
16‧‧‧鍍焊層
16a‧‧‧內層
16b‧‧‧中間層
16c‧‧‧外層
17a~17c‧‧‧切片(測量區域)
圖1係本發明一實施形態的Cu核球構成例剖視圖。
圖2係本發明另一實施形態的Cu核球構成例剖視圖。
圖3係表示鍍焊層中的Bi分佈狀態之Cu核球構成例放大剖視圖。
圖4係圖3的更加放大剖視圖。
圖5係放大Sn與Bi分佈狀態的要部剖視圖(場發射式電子探束微分析儀(FE-EPMA)照片)。
圖6係實施例1的電鍍處理中，相關鍍液中的Bi濃度、與鍍焊層中所含有Bi濃度的關係，在以Cu核球徑為基準時的特性曲線圖。
圖7係核材料之Bi濃度分佈的測定方法一例說明圖。
圖8係實施例2的電鍍處理中，相關鍍液中的Bi濃度、與鍍焊層中所含有Bi濃度的關係，在以Cu核球徑為基準時的特性曲線圖。
[實施例1]
以下，針對本發明較佳實施形態進行詳細說明。
本發明係提供在核表面上，利用電鍍處理將由Sn與Bi所構成Sn系焊料合金形成鍍敷被膜的核材料，且鍍焊層中的Bi分佈呈均質之核材料，以及使用其的半導體封裝。
本發明鍍焊層的組成係由含有Sn與Bi的(Sn-Bi)系合金構成。相關Bi含有量，若Bi量相對於合金全體在0.1~99.9質量%範圍內，便可將Bi的濃度比控制於91.4~106.7%既定範圍內，便可使鍍焊層中的Bi分佈呈均質。
例如(Sn-58Bi)系焊料合金的情況，目標值的Bi分佈係將58質量%設為目標值，容許範圍係52質量%(濃度比91.4%)~63質量%(濃度比108.6%)。
另外，所謂「容許範圍」係指若在該範圍內，便可毫無問題地施行凸塊形成等焊接的範圍。又，所謂「濃度比(%)」係指測量值(質量%)相對於目標含有量(質量%)的比、或者測量值的平均值(質量%)相對於目標含有量(質量%)的比(%)。即，濃度比(%)可依下式表示：濃度比(%)=測量值(質量%)/目標含有量(質量%)或者濃度比(%)=測量值的平均值(質量%)/目標含有量(質量%)
再者，由Sn、Bi所構成的二元電鍍焊層中，即便添加該等以外的添加元素，仍可將Bi的濃度比控制於91.4~106.7%既定範圍內。
添加元素係可考慮使用例如Ag、Cu、Ni、Ge、Ga、In、 Zn、Fe、Pb、Sb、Au、Pd、Co等中之一種或二種以上。
核(core)係使用金屬材料。核的形狀可考慮球體、及其他形狀(柱狀管柱、或片狀等)。本例係針對使用球體，特別係核由Cu所構成球(以下稱「Cu球」)的Cu核球情況進行說明。
Cu球的粒徑(球徑)係依照BGA尺寸等而有所差異，以下例係200μm 程度的球狀，且鍍焊層徑向單側厚度係20~100μm。Cu核球的粒徑係依照所使用電子零件的密度、尺寸再行適當選定，可使用1~1000μm範圍內的Cu球，配合所使用Cu球的粒徑再行適當選定鍍敷厚度。施行鍍敷處理的鍍敷裝置係使用電鍍裝置。
接著，例示使用Cu球的Cu核球例。
圖1所示係本發明的Cu核球10一例的剖視圖。為求說明方便，圖示係採誇張行性描繪。
Cu核球10係由Cu球12、以及本例中隔著Ni基底鍍敷層14形成由Sn系焊料合金所構成的鍍焊層16。Ni基底鍍敷層14係負責防止在Cu球12與鍍焊層16之間，因金屬擴散造成鍍焊層16發生組成變化用的基底鍍敷功用，厚度1~4μm左右。該Ni基底鍍敷層14並非必要要件，亦可如圖2所示，直接在Cu球12的表面上形成鍍焊層。另外，形成基底鍍敷層14時，基底鍍敷層14亦可由從Ni、Co中選擇1元素以上所形成的層構成。
Cu球12所使用的Cu係可為純銅、亦可為銅的合金。
當使用以Cu為主成分之合金組成的Cu球12時， 純度並無特別的限定，就從抑制因純度降低而導致Cu核球的導電率、熱導率劣化，以及視需要抑制α線量的觀點，較佳係99.9質量%以上。
核係除Cu之外，尚亦可由例如：Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg等金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成。
Cu球12就從控制間隙高度的觀點，真球度較佳係0.95以上、更佳係0.990以上。若Cu球12的真球度未滿0.95，則因為Cu球12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Cu核球10搭載於電極上施行迴焊時，若真球度偏低，則會導致Cu核球10發生位置偏移，亦會造成自對準性惡化。
另外，所謂「真球度」係表示偏離正球的程度。真球度係利用例如：最小平方圓法(LSC法)、最小環帶圓法(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，真球度係例如將500個各Cu球的直徑除以長徑時所計算出的算術平均值，值越接近上限的1.00，則表示越接近正球。所謂「長徑長度」係指利用MITUTOYO公司製Ultra Qucik Vision、ULTRA QV350-PRO測定裝置所測定的長度。
含有鍍焊層16的Cu核球10直徑最好全體均為1~1000μm。若在此範圍內，便可安定地製造球狀Cu核球10，又藉由選定粒徑，當電極端子間屬窄間距的情況便可抑制連接 短路情形。
粒徑1~300μm程度的Cu核球10之集合體，亦有稱「Cu核粉末」的情況。該Cu核粉末有被當作焊料膏中的粉末用焊料，並依摻合狀態使用的情況。
鍍焊層16係焊料合金，本例中係由Sn與Bi構成。
此情況，如前述，鍍焊層16中的Bi含有量相對於目標值58質量%的容許範圍，較佳係53質量%(濃度比91.4%)~63質量%(濃度比108.6%)程度。
鍍焊層16的厚度係依照Cu球12的粒徑而有所差異，較佳係徑向單側100μm以下。例如粒徑215μm 之Cu球12時，便依厚度成為50~70μm的方式形成鍍焊層16。理由係可確保充分的焊料接合量。
鍍液係使用有機酸、甲磺酸鉍及界面活性劑的混合液。鍍液的濃度係控制成在鍍焊層形成中呈一定狀態。
當由Sn與Bi所構成Sn-Bi系焊料合金組成的鍍焊層係利用電鍍形成時，因為Bi會較Sn更優先被取入於鍍焊層中，因而會有鍍液中的Bi濃度與鍍焊層中的Bi量不一致之問題，無法形成Bi濃度分佈呈均質的焊料合金鍍敷層。所以，依成為圖6所示條件的方式，對陽極電極與陰極電極間施加既定的直流電壓，且一邊使Cu球擺動，一邊依鍍液中的Bi濃度呈均勻方式調整來施行電鍍處理。
相關此種利用鍍敷處理而生成鍍焊層16的過程，參照圖6進行更詳細說明。圖6所示係電鍍處理時，相關鍍液中的Bi濃度(曲線Lb)、與鍍焊層16中的Bi濃度(曲線La)之 關係，在以Cu核球徑為基準時的特性曲線圖。
本例係使用Cu球初始值為粒徑215μm的情況。逐一監視鍍焊層16的厚度，本例係將鍍焊層16的厚度依序逐次增加既定值時的Cu核球10，採集為樣品。所採集樣品經洗淨後再乾燥，然後才測量粒徑。
若測量時序的Cu核球粒徑成為目標值時，依序測定鍍焊層中的Bi含有量，便可獲得圖6的曲線La之結果。從該結果得知，即便鍍焊層16依序增加既定厚度，但此時的Bi含有量幾乎與前一個的含有量同值。曲線La的情況，Bi含有量幾乎為58~60質量%。所以，從圖6的曲線La可以得知Bi的濃度分佈係相對於鍍敷厚度呈均質(均等)，並無濃度斜率。
圖3所示係此時的Cu核球10之剖視圖。由該圖放大的圖4、以及更放大的圖5中明顯得知，鍍焊層16的成長過程係由Sn與Bi一邊均質混雜一邊成長的過程。圖5係使用FE-EPMA拍攝。
鍍焊層16中的Bi濃度係即便鍍焊層16的厚度成長，但仍維持幾乎相同狀態，因而得知鍍焊層16中的Bi幾乎依均質分佈的狀態成長(析出)。在依Bi濃度收束於期待值內的方式，使鍍液中的Bi濃度呈均質狀態下施行電鍍處理。本例中，因為鍍焊層16中的Bi含有量目標值係設為58質量%，因而控制鍍液中的Bi濃度到達目標值。
為使鍍焊層16中的Bi濃度分佈收束於期待值，便一邊施行電壓‧電流控制，一邊施行鍍敷處理。藉由此種電鍍處理，便可將鍍焊層16中的Bi分佈維持於期待值。
實施例中，鍍液中的Bi濃度在鍍敷處理中幾乎呈42~44質量%，理由係如上述，鍍焊層16中的Bi濃度成為53~63質量%是因一邊隨時調整鍍液中的Bi濃度，一邊施行鍍敷處理的緣故所致。
曲線La所示鍍焊層16內的Bi濃度、與曲線Lb所示鍍液中的Bi濃度不一致的原因，係鍍液中的Bi較鍍液中的Sn更優先被取入於鍍焊層內的緣故所致。
為確認鍍焊層16的Bi濃度分佈已成為目標值的相應值，便施行如下述實驗。
(1)依下述條件，製作鍍焊層16之組成成為(Sn-58)Bi的Cu核球10。
‧Cu球12的直徑：250μm
‧Ni基底鍍敷層14的膜厚：2μm
‧鍍焊層16的膜厚：23μm
‧Cu核球10的直徑：300μm
為使實驗結果的測定較為容易，Cu核球10便製作具有厚度較薄鍍焊層的Cu核球。
鍍敷方法係利用電鍍工法，依成為圖6所示條件的方式進行製作。
(2)試料係準備10個由相同組成(Sn-58Bi)系焊料合金形成鍍焊層的Cu核球10。將該等使用為試料A。
(3)各試料A1~A10分別利用樹脂密封。
(4)經密封的各試料A1~A10，分別利用樹脂施行研磨，並觀察各試料A1~A10的截面。觀察器材係使用日本電子製的 FE-EPMAJXA-8530F。
試料A1的剖視圖係如圖7所示。鍍焊層16中，為求方便，從Cu球12的表面側起分為內層16a、中間層16b及外層16c。內層16a係設為距Cu球12表面9μm，中間層16b係設為距9~17μm，而外層16c係設為距17~23μm，從內層16a、中間層16b及外層16c，如圖7所示，本例係分別切取厚度5μm、寬40μm的區域17a、17b、17c，利用定性分析施行Bi的濃度測量。此項操作係各內層16a、中間層16b及外層16c均針對10視野實施。
結果整理如(表-1)所示。根據該(表-1)，得知內層、中間層、外層均在最小值53.29質量%(濃度比91.9%)、最大值60.97質量%(濃度比105.1%)的範圍內。依如上述，將Bi的容許範圍設為53質量%(濃度比91.4%)~63質量%(濃度比108.6%)，但由該實驗結果的實測值得知，可容許至53.29質量%(濃度比91.9%)~60.97質量%(濃度比105.1%)範圍。
然後，計算試料A1~A10的算術平均，結果：
內層區域17a=57.46(質量%)(濃度比99.1%)
中間層區域17b=56.32(質量%)(濃度比97.1%)
外層區域17c=56.62(質量%)(濃度比97.6%)
再者，得知內層、中間層及外層各區域17a~17c的算術平均，因為鍍焊層中的Bi係在上述53質量%~63質量%容許範圍內，因而幾乎成為目標值的Bi濃度比。
此種測量操作亦針對試料A外另行製成的試料B~D同樣實施，結果如(表-2)所示。
由(表-2)的結果得知，雖多少有出現變動，但鍍焊層16中的Bi濃度均收束於目標值的53~63質量%。
然後，抽選出與該等試料A~D同批次製造的Cu核球各10個(例)，分別利用普通的迴焊處理接合於基板上。
接合結果亦合併記於(表-2)。
針對接合結果，將所有樣品均完全沒有設定到接合不良者評為「良」，將接合時只要有1個樣品發生位置偏移者、以及在接合時只要有1個樣品的Cu核球10發生爆裂飛散者評為「不良」。
任一者均沒有發生內周側較外周側更早熔融，造成在內周側與外周側發生體積膨脹差，導致Cu核球10出現爆裂飛散的狀況，又因為鍍焊層16全體幾乎均勻熔融，故不會發生因熔融時序偏差而造成的核材料位置偏移情形，故不會有因位置偏移等所衍生電極間短路等等的可能性。所以，獲得完全沒有發生接合不良的良好結果，故判定屬「良」。
[實施例2]
第2實施例係由除Sn、Bi之外，尚含有Cu與Ni的(Sn-Cu-Bi-Ni)所構成四元Sn系焊料合金，形成鍍焊層16的例子。目標值的組成比係如下。
Bi：40質量%、Cu：0.5質量%、Ni：0.03質量%、Sn：其餘。此時Bi分佈的目標值係40質量%，而容許範圍係36質量%(濃度值90%)~43質量%(濃度比107.5%)。
具體而言，在下述條件下，根據上述表述，製成鍍焊層組成成為(Sn-40Bi-0.5Cu-0.03Ni)的Cu核球。
‧Cu球直徑：180μm
‧Ni基底鍍敷層膜厚：2μm
‧鍍焊層膜厚：33μm
‧Cu核球直徑：250μm
Cu核球之製作方法係依照與實施例1同樣的電鍍條件，依鍍液中的Bi濃度呈均質方式實施。
相關實驗方法，除將內層16a設為距Cu球表面11μm、將中間層16b設為距11~22μm、並將外層16c設為距22~33μm之外，其餘均與實施例1相同條件。
測定結果如(表-2)的E~H所示。
由(表-2)試料E~H的結果得知，此時的Bi目標值係40質量%，但此時鍍焊層16中的Bi平均值係最小37.81質量%(濃度比94.5%)~最大41.33質量%(濃度比103.3%)(均係對同一組成焊料合金測量10次的平均值)，雖多少有變動，但幾乎在目標值對應值，即容許範圍的36質量%(濃度值比90.0%)~43質量%(濃度值比107.5%))內。然後，所有樣品的接合判定均係與實施例1同樣獲得完全沒有發生接合不良的良好結果，故判定屬「良」。
圖8所示係與圖6同樣，相關電鍍處理時在鍍液中的Bi濃度(曲線Lc)、與鍍焊層16中的Bi濃度(曲線Ld)之關係，在以Cu核球徑為基準時的特性曲線圖。
本例係與實施例1同樣，使用Cu球初始值為粒徑215μm的情況。逐一監視鍍焊層16的厚度，本例係將鍍焊層16的厚度依序逐次增加既定值時的Cu核球10，採集為樣品。所採集 樣品經洗淨後再乾燥，然後才測量粒徑。
若測量時序的Cu核球粒徑成為目標值時，依序測定鍍焊層中的Bi含有量，便可獲得圖8的曲線Lc之結果。從該結果得知，即便鍍焊層16依序剛好增加既定厚度時，但此時的Bi含有量幾乎與前一個的含有量同值。曲線Lc的情況，Bi含有量幾乎為40~42質量%。如曲線Lc所示Bi的濃度分佈相對於鍍敷厚度呈均質(均等)，得知沒有濃度斜率。鍍焊層16內的Bi濃度(曲線Lc)與鍍液中的Bi濃度(曲線Ld)非呈一致的原因，係與圖6同樣，鍍液中的Bi會較鍍液中的Sn更優先被取入於鍍焊層內之緣故所致。
[實施例3]
實施例3係針對由含有Ag、且含少量Bi的(Sn-3Ag-0,8Cu-3Bi)所構成的四元Sn系焊料合金，形成鍍焊層16之情況施行同樣的測量。此時的Bi分佈目標值係3質量%，容許範圍係2.7質量%(濃度值比90.0%)~3.2質量%(濃度比106.7%)。
Cu核球之製作方法係與實施例1及實施例2同樣。
相關所使用Cu球及Cu核球的直徑、Ni基底鍍敷層與鍍焊層的膜厚等規格、以及實驗條件，係除鍍焊層組成之外，其餘均與實施例1相同條件。
結果如(表-2)試料I~L所示。此情況，因為目標值Bi係3質量%，因而如試料I~L所示，具有2.81~3.08質量%(均係針對同試料施行計10次測量的平均值)，雖多少有變動[平均值最小2.81質量%(濃度比93.7%)~最大3.08質量%(濃度比102.7%) 程度]，但仍在容許範圍內。所以，得知收束於2.7質量%(濃度比90.0%)~3.2質量%(濃度比106.7%)。接合判定均係與實施例1同樣獲得完全沒有發生接合不良的良好結果，故判定屬「良」。
上述[實施例1]~[實施例3]的結果整理如表-3。Bi濃度比係91.4%~106.7質量%。
另外，比較例係以往周知在鍍焊層中的Bi分佈具有濃度斜率時的實驗結果，如上述(表-2)中所示。相關所使用的Cu球、Cu核球的球徑、Ni基底鍍敷層與鍍焊層的膜厚等、以及實驗條件，係除下述電鍍方法之外，其餘均與實施例1相同條件。
[比較例1]
比較例1，在鍍液係含有甲磺酸錫、有機酸及界面活性劑的鍍液中施行電鍍。然後，在鍍敷膜厚達目標值一半的階段，更進一步僅追加甲磺酸鉍。藉此，在鍍液中的甲磺酸錫濃度減少狀態下，一邊增加甲磺酸鉍濃度一邊施行電鍍處理。
結果，鍍焊層中的Bi濃度具有內側較低，且朝外側逐漸 提高的濃度斜率(內層0質量%、中層52.12質量%、外層100質量%)，鍍焊層全體形成Bi含有量成為目標值58質量%的鍍焊層。
[比較例2]
比較例2，在含有甲磺酸錫、甲磺酸鉍、有機酸及界面活性劑的鍍液中施行電鍍。從開始進行鍍敷起，便對陽極電極與陰極電極之間施加既定直流電壓，且一邊使Cu球擺動，一邊施行電鍍處理。
結果，鍍焊層中的Bi濃度具有內側較高，且朝外側逐漸提降低的濃度斜率(內層70.7質量%、中層24.8質量%、外層3.8質量%)，鍍焊層全體形成Bi含有量成為目標值58質量%的鍍焊層。
結果，比較例1在接合時有發生位置偏移，比較例2則發生Cu核球爆裂飛散情形，均判定屬「不良」。
依此當改變鍍焊層16內的Bi濃度時，會發生位置偏移、Cu核球10吹飛等現象。
本發明在核表面被覆著鍍焊層的材料中，所含Bi呈均質。例如BGA之類的半導體封裝，焊料凸塊可使用本發明的核材料。核最好為球體，且最好係Cu等金屬球。
另外，本發明的技術範疇並不僅侷限於上述實施形態，舉凡在不脫逸本發明主旨之範圍內，亦包含對上述實施形態追加的各種變更。形狀亦係除球體外，尚涵蓋其他形狀(柱狀管柱、片狀等)。
例如在上面與底面直徑：1~1000μm、高度：1~3000μm的 Cu製管柱之表面上，設計單側1~4μm的Ni基底鍍敷層、Fe基底鍍敷層、Co基底鍍敷層等，依照與實施例相同條件施行(Sn-Bi)系鍍焊層被覆的Cu核管柱，在鍍焊層中的Bi成為91.4~106.7%的既定範圍濃度比，將與本案實施例的Cu核球同樣，並不會發生接合不良。
[產業上之可利用性]
本發明的核材料係可利用為BGA等半導體封裝的接合材。

Claims (9)

  1. 一種核材料，係在核表面上利用電鍍焊，設有由Sn與Bi所形成(Sn-Bi)系焊料合金之鍍焊層的核材料，其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；將上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比係在91.4~106.7%範圍內。
  2. 一種核材料，係在核表面上利用電鍍焊，設有由Sn與58質量%Bi所構成(Sn-58Bi)系焊料合金之電鍍焊層的核材料；其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；將上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比係在91.4~108.6%範圍內。
  3. 一種核材料，係在核表面上利用電鍍焊，設有由Sn與40質量%Bi所構成(Sn-40Bi)系焊料合金之電鍍焊層的核材料；其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；將上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比係在90~107.5%範圍內。
  4. 一種核材料，係在核表面上利用電鍍焊，設有由Sn與3質量%Bi所構成(Sn-3Bi)系焊料合金之電鍍焊層的核材料；其特徵在於：上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；將上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比係在90~106.7%範圍內。
  5. 如申請專利範圍第1至4項中任一項之核材料，其中，上述核材料係從上述核表面起依序設有從Ni及Co中選擇1元素以上的基底鍍敷層與上述電鍍焊層。
  6. 如申請專利範圍第1至4項中任一項之核材料，其中，核係使用Cu球或Cu管柱。
  7. 如申請專利範圍第5項之核材料，其中，核係使用Cu球或Cu管柱。
  8. 一種半導體封裝，係將申請專利範圍第1至7項中任一項所記載核材料，使用為焊料凸塊。
  9. 一種形成凸塊電極的方法，其特徵在於包括：在電極上搭載核材料的步驟；以及藉由對所搭載的上述核材料施行加熱，而形成凸塊電極的步驟；其中，上述核材料係在核表面上利用電鍍焊，設有由Sn與Bi所構成(Sn-Bi)系焊料合金之電鍍焊層的核材料；上述核係由Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金屬單體、或者該等二種以上的合金、金屬氧化物、或金屬混合氧化物構成；將上述鍍焊層中所含的Bi濃度比，依下式：濃度比(%)=Bi測量值(質量%)/目標Bi含有量(質量%)或者濃度比(%)=Bi測量值的平均值(質量%)/目標Bi含有量(質量%)表示時，上述濃度比在91.4~106.7%範圍內的核材料。
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