TW201544214A - Ｏｓｐ處理銅球、焊接接頭、泡沫焊及焊膏 - Google Patents

Ｏｓｐ處理銅球、焊接接頭、泡沫焊及焊膏 Download PDF

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Publication number
TW201544214A
TW201544214A TW103145414A TW103145414A TW201544214A TW 201544214 A TW201544214 A TW 201544214A TW 103145414 A TW103145414 A TW 103145414A TW 103145414 A TW103145414 A TW 103145414A TW 201544214 A TW201544214 A TW 201544214A
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Taiwan
Prior art keywords
osp
copper ball
copper
ball
treated
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TW103145414A
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English (en)
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TWI647030B (zh
Inventor
Hiroyoshi Kawasaki
Tomoaki Nishino
Takahiro Roppongi
Daisuke Soma
Isamu Sato
Yuji Kawamata
Hirohiko Hirao
Jun Tasaka
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Senju Metal Industry Co
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Publication of TW201544214A publication Critical patent/TW201544214A/zh
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Publication of TWI647030B publication Critical patent/TWI647030B/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
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic 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
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • 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
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Abstract

本發明係為抑制發生軟錯誤的同時，確保銅球對電極上構裝時的對位性。 本發明之OSP處理銅球11，其係包括：銅球1；及含有將該銅球1的表面披覆的咪唑化合物的有機披膜2之OSP處理銅球。銅球1，係純度為99.9%以上99.995%以下，鈾的含量為5ppb以下，釷的含量為5ppb以下，鉛或鉍的含量或合併鉛及鉍兩者之含量的合計量為1ppm以上，真球度為0.95以上，α射線劑量為0.0200cph/cm2以下。

Description

OSP處理銅球、焊接接頭、泡沫焊及焊膏
本發明係關於OSP處理銅球、焊接接頭、泡沫焊、及焊膏。
近年，由於小型資訊機器發達，裝載的電子零件迅速小型化。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，係藉由將焊球柱接合於半導體晶片的電極而形成。使用BGA的半導體封裝，係藉由加熱熔融的焊料凸塊與印刷基板的導電性接點接合，而裝載於印刷基板。再者，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之情形。如發生如此之情形，可認為焊料可能會由電極溢出，將電極間連接，而發生短路。
因此，有使用焊膏在電子零件的電極上將銅球電 性接合的焊料凸塊之研究。使用銅球形成的焊料凸塊，係在將電子零件構裝於印刷基板時，即使半導體封裝的重量施加於焊料凸塊，由於可藉由在焊料的熔點不會熔融的銅球支撐半導體封裝。因此，並不會因半導體封裝的自重將焊料凸塊壓潰。相關技術，可舉例如專利文獻1。
在此，銅球，具有容易被氧化的性質，按照保管 環境的溫度或濕度，會在銅球表面形成氧化膜。將形成該氧化膜的銅球構裝在電極上之後進行回焊，則有在銅球與焊膏中的焊料粒子之間發生沾濕性不良之情形。結果，會發生構裝的焊料球由電極上脫落，或焊料球由電極的中心錯位構裝的問題。
第4圖A係表示，構裝於電極230上的銅球210 沒有錯位的狀態，第4圖B係表示構裝於電極230上的銅球錯位的狀態之圖。於電極230上，印刷著焊膏220。如第4圖B所示，將一部分形成氧化膜212的銅球210構裝於電極230上進行回焊處理，則會引起沾濕性不良，而使銅球210由電極230的中心錯位構裝。
如此，銅球由電極的既定位置錯位接合時，包含 銅凸塊的各電極的高度會離散。高度高的電極可與接點接合，但是高度低的電極無法與接點接合。銅球由既定位置錯位接合的電子零件，將作為不良處理。此外，當銅球由電極脫落，則將作為不良處理。因此，要求以很高的水準的對位。
然而，近年，隨著電子零件的小型化而實現高密 度構裝，但有隨著進行高密度構裝而有引起被稱為軟錯誤的問題。軟錯誤，係指α射線進入半導體積體電路(以下，稱為「IC」。) 的記憶胞中，而將記憶內容改寫的可能性。α射線，一般認為係由焊料合金中的鈾、釷、210釙等的放射性元素α衰變而放射。因此，近年，進行降低放射性元素含量的低α射線的焊料材料的開發。相關文獻，可舉例如專利文獻2。
於專利文獻2，揭示有α射線較低的錫晶柱的發 明，記載有為了降低α射線劑量，並不是單僅進行電解精煉，而係藉由在電解液懸浮吸附劑，將鉛及鉍吸附減低α射線。於專利文獻3，記載有α射線劑量低的銅及銅合金。
[先前技術文獻] [專利文獻]
專利文獻1：國際公開第95/24113號小冊
專利文獻2：專利第4472752號公報
專利文獻3：國際公開第2012/120982號小冊
但是，在於專利文獻1，完全沒有考慮降低銅球的α射線劑量，有無法在高密度構裝抑制發生軟錯誤的問題。
此外，在於專利文獻2，如上所述，藉由將電解液及電極以靜止的狀態進行電解精煉，去除錫晶柱中的鉛及鉍，減低α射線劑量。但是，在於同文獻，完全沒有揭示關於防止銅球在構裝時的錯位等。
再者，在於專利文獻3上，並沒關於於銅球的記述，完全沒有揭示關於銅球中的鉍、鉛的添加量與銅球的真球 度的關係。
因此，本發明係為解決上述課題，邊確保對電極 上構裝時的對位性，邊可抑制發生軟錯誤的水溶性預焊劑處理銅球(以下，稱為OSP(Organic Solderability Preservative：有機保焊劑)處理球)，焊接接頭、泡沫焊，及焊膏。
本發明者們，首先進行使用於OSP處理銅球的銅球之選定。結果，發現若銅球裏的鉛或鉍的含量或合併鉛及鉍兩者的含量沒有達到一定的量時，則銅球的真球度會降低，而所得OSP處理銅球的真球度會降低。
接著，為提高銅球的對位性，著眼於銅球的接合形態。具體而言，有鑑於銅球係以焊膏中的焊料粒子與電極電性接合，著眼於銅球的表面狀態會對焊膏中的焊料粒子的沾濕性造成影響。因此，本發明者們，得到藉由在銅球表面形成含有咪唑化合物的有機披膜，可防止銅球的氧化之見解。
在此，本發明係如下所示。
(1)一種OSP處理銅球，包括：銅球；及含有將該銅球的表面披覆的咪唑化合物的有機披膜之OSP處理銅球，其特徵在於：上述銅球，係純度為99.9%以上99.995%以下，鈾的含量為5ppb以下，釷的含量為5ppb以下，鉛或鉍的含量或合併鉛及鉍兩者之含量的合計量為1ppm以上，真球度為0.95以上，α射線劑量為0.0200cph/cm2以下。
(2)根據上述(1)之OSP處理銅球，其中α射線為0.0200cph/cm2以下。
(3)根據上述(1)之OSP處理銅球，其中α射線為 0.0020cph/cm2以下。
(4)根據上述(1)之OSP處理銅球，其中α射線為 0.0010cph/cm2以下。
(5)根據上述(1)~(4)中任一項之OSP處理銅球，其 中直徑為1~1000μm。
(6)根據上述(1)~(5)中任一項之OSP處理銅球，其 中上述銅球，在以上述有機披膜披覆之前，預先以選自由Ni及Co之1元素以上所組成之層披覆。
(7)根據上述(1)~(6)中任一項之OSP處理銅球，其 中上述OSP處理銅球的真球度為0.95以上。
(8)一種焊料接頭，使用上述(1)~(7)中任一項之 OSP處理銅球。
(9)一種泡沫焊，使用上述(1)~(7)中任一項之OSP 處理銅球。
(10)一種焊膏，使用上述(1)~(7)中任一項之OSP 處理銅球。
1‧‧‧銅球
2‧‧‧OSP披膜
11‧‧‧OSP處理銅球
第1圖係表示關於本發明之OSP處理銅球的構成例之圖。
第2圖係搭載關於本發明之OSP處理銅球的焊料凸塊的光學顯微鏡照片。
第3圖係搭載在於比較例之銅球之焊料凸塊的光學顯微鏡照片。
第4圖A係用於說明將在於先前的銅球構裝於電極上時所產生的錯位。
第4圖B係用於說明將在於先前的銅球構裝於電極上時所產生的錯位。
藉由以下詳細說明本發明。在於本說明書，關於OSP處理銅球披膜的組成的單位(ppm、ppb，及%)，只要沒有特別提及係表示對OSP處理銅球披膜的質量的比例(質量ppm、質量ppb，及質量%)。此外，關於銅球的組成的單位(ppm、ppb，及%)只要沒有特別提及係表示對銅球的質量的比例(質量ppm、質量ppb，及質量%)。
第1圖係表示關於本發明的OSP處理銅球11之構成之一例。如第1圖所示，關於本發明之OSP處理銅球11，包括：銅球1；及有機披膜2，其係含有披覆銅球1表面的咪唑化合物(以下稱為OSP披膜)，具有如下所示特徵。銅球1的純度為99.9%以上99.995%以下，鉛或鉍的含量或者合併鉛及鉍兩者的含量的合計量為1ppm以上，真球度為0.95以上，α射線劑量為0.0200cph/cm2以下。根據關於本發明的OSP處理銅球11，藉由具有上述特徵，可減低焊接接頭的α射線劑量的同時，藉由防止在銅球1表面形成氧化膜，可確保銅球1的對位性。
以下詳細說明OSP處理銅球11的構成要素的OSP披膜2及銅球1。
1. OSP披膜
首先，詳述關於構成本發明之OSP披膜2。OSP披膜2，係作用作為防止銅球1的表面氧化，實現良好的焊接性的保護膜。
．OSP處理銅球α射線劑量：0.0200cph/cm2以下
關於本發明之OSP處理銅球11的α射線為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OSP處理銅球11的α射線劑量，係藉由構成OSP處理銅球11的OSP披膜2的α射線劑量在0.0200cph/cm2以下而達成。因此，關於本發明之OSP處理銅球11，由於係以如此之OSP披膜2披覆，故顯示很低的α射線劑量。α射線劑量，在由抑制更進一步的高密度構裝中的軟錯誤的觀點，以0.0020cph/cm2以下為佳，以0.0010cph/cm2以下更佳。
．OSP披膜的膜厚：5μm以下
關於本發明之第1圖之T所示之OSP披膜2的膜厚在由製造上的觀點為5μm以下。
．OSP披膜的組成
於OSP披膜2上，包含咪唑化合物。在於本實施例使用之咪唑化合物並無限制，可良好使用例如下述化1~8之通式(I)~(VIII)所示之咪唑化合物。此外，亦可將該等咪唑化合物組合二種以上使用。
[化1]
(式中，R1係表示氫原子，或碳數為1~25可具有 取代基之直鏈狀或分枝狀烷基或烯基。R2及R3係表示氫原子、鹵素原子或碳數1~8之直鏈狀或分枝狀烷基。)
(式中，R1係表示氫原子，或碳數為1~25可具有 取代基之直鏈狀或分枝狀烷基或烯基。R2及R3係表示可為相同或相異之氫原子、鹵素原子或碳數1~8之直鏈狀或分枝狀烷基。)
(式中，R1係表示氫原子、鹵素原子或碳數1~17 之直鏈狀或分枝狀的烷基。R2、R3、R4及R5係表示可為相同或相異之氫原子、鹵素原子或碳數1~8的直鏈狀或分枝狀烷基。)
(式中，R1係表示氫原子、鹵素原子或碳數1~17 之直鏈狀或分枝狀的烷基。R2、R3、R4及R5係表示可為相同或相異之氫原子、鹵素原子或碳數1~8的直鏈狀或分枝狀烷基。)
(式中，R1係表示氫原子、鹵素原子或碳數1~17 之直鏈狀或分枝狀的烷基。R2、R3、R4及R5係表示可為相同或相異之氫原子、鹵素原子或碳數1~8的直鏈狀或分枝狀烷基。)
(式中，R1、R2、R3、及R4係表示可為相同或相異 之氫原子、鹵素原子或碳數1~8之直鏈狀或分枝狀烷基。n係表示0~6的整數。)
(式中，R1、R2、R3、及R4係表示可為相同或相異 之氫原子、鹵素原子或碳數1~8之直鏈狀或分枝狀烷基。n係表示0~6的整數。)
(式中，R1及R2可為相同或相異，表示氫原子、鹵素原子或碳數1~8之直鏈狀或分枝狀烷基。n係表示0~6的整數。)
以化1的通式(I)所示之咪唑化合物，可例示，咪唑、2-甲基咪唑、2-乙基咪唑、2-丙基咪唑、2-異丙基咪唑、 2-丁基咪唑、2-第三丁基咪唑、2-戊基咪唑、2-己基咪唑、2-庚基咪唑、2-(1-乙基戊基)咪唑、2-辛基咪唑、2-壬基咪唑、2-癸基咪唑、2-十一烷基咪唑、2-十二烷基咪唑、2-十三烷基咪唑、2-十四烷基咪唑、2-十五烷基咪唑、2-十六烷基咪唑、2-十七烷基咪唑、2-十八烷基咪唑、2-十九基咪唑、2-二十烷基咪唑、2-二十一烷基咪唑、2-二十二烷基咪唑、2-二十三烷基咪唑、2-二十四烷基咪唑、2-二十五烷基咪唑、 2-(1-甲基戊基)咪唑、2-(1-乙基戊基)咪唑、2-(1-庚基癸基)咪唑、2-(5-己烯基)咪唑、2-(9-辛烯基)咪唑、2-(8-十七烯基)咪唑、2-(4-氯丁基)咪唑、2-(9-羥基壬基)咪唑、2-乙基-4-甲基咪唑、2-十一烷基-4-甲基咪唑、2-十七烷基-4-甲基咪唑、4-甲基咪唑、4-異丙基咪唑、4-辛基咪唑、2,4,5-三甲基咪唑、4,5-二甲基-2-辛基咪唑、2-十一烷基-4-甲基-5-溴咪唑、4,5-二氯-2-乙基咪唑等的烷基咪唑化合物。
化2的通式(II)所示之咪唑化合物，可例示，苯並咪唑、2-甲基苯並咪唑、2-乙基苯並咪唑、2-丙基苯並咪唑、2-異丙基苯並咪唑、 2-丁基苯並咪唑、2-第三丁基苯並咪唑、2-戊基苯並咪唑、2-己基苯並咪唑、2-(1-甲基戊基)苯並咪唑、2-庚基苯並咪唑、2-(1-乙基戊基)苯並咪唑、2-辛基苯並咪唑、2-(2,4,4-三甲基戊基)苯並咪唑、2-壬基苯並咪唑、2-癸基苯並咪唑、2-十一烷基苯並咪唑、2-十二烷基苯並咪唑、2-十三烷基苯並咪唑、2-十四烷基苯並咪唑、2-十五烷基苯並咪唑、2-十六烷基苯並咪唑、2-十七烷基苯並咪唑、2-(1-庚基癸基)苯並咪唑、2-十八烷基苯並咪唑、2-十九烷基苯並咪唑、2-二十烷基苯並咪唑、2-二十一烷基苯並咪唑、2-二十二烷基苯並咪唑、 2-二十三烷基苯並咪唑、2-二十四烷基苯並咪唑、2-二十五烷基苯並咪唑、2-(8-辛基十六烷基)苯並咪唑、2-(9-辛烯基)苯並咪唑、2-(8-十七烯基)苯並咪唑、2-(4-氯丁基)苯並咪唑、2-(9-羥基壬基)苯並咪唑、2-己基-5-甲基苯並咪唑、2-庚基-5,6-二甲基苯並咪唑、2-辛基-5-氯苯並咪唑、2-乙基-5-辛基-6-溴苯並咪唑、2-戊基-5,6-二氯苯並咪唑、4-氟苯並咪唑、2-戊基-5-碘苯並咪唑等的烷基苯並咪唑化合物。
化3的通式(III)所示之咪唑化合物，可例示，2,4-二苯基咪唑、2-(2-甲基苯基)-4-苯基咪唑、2-(3-辛基苯基)-4-苯基咪唑、2-(2,4-二甲基苯基)-4-苯基咪唑、2-苯基-4-(4-己基苯基)咪唑、2-苯基-4-(2-甲基-5-丁基苯基)咪唑、2,4-二苯基-5-甲基咪唑、2,4-二苯基-5-己基咪唑、 2-(2,4-二乙基)-4-(3-丙基-5-辛基)-5-異丁基咪唑、2-(2-氯苯基)-4-苯基咪唑、2-(3-氯苯基)-4-苯基咪唑、2-(4-氯苯基)-4-苯基咪唑、2-(2-溴苯基)-4-苯基咪唑、2-(3-溴苯基)-4-苯基咪唑、2-(4-溴苯基)-4-苯基咪唑、2-(2-碘苯基)-4-苯基咪唑、2-(3-碘苯基)-4-苯基咪唑、2-(4-碘苯基)-4-苯基咪唑、2-(2-氟苯基)-4-苯基咪唑、2-(3-氟苯基)-4-苯基咪唑、2-(4-氟苯基)-4-苯基咪唑、2-(2,3-二氯苯基)-4-苯基咪唑、2-(2,4-二氯苯基)-4-苯基咪唑、2-(2,5-二氯苯基)-4-苯基咪唑、2-(2,6-二氯苯基)-4-苯基咪唑、2-(3,4-二氯苯基)-4-苯基咪唑、2-(3,5-二氯苯基)-4-苯基咪唑、2-(2,4-二溴苯基)-4-苯基咪唑、2-(2-甲基-4-氯苯基)-4-苯基咪唑、2-(3-溴-5-辛基苯基)-4-苯基咪唑、2-(2-氯苯基)-4-苯基-5-甲基咪唑、2-(3-氯苯基)-4-苯基-5-甲基咪唑、 2-(4-氯苯基)-4-苯基-5-甲基咪唑、2-(2-溴苯基)-4-苯基-5-甲基咪唑、2-(3-溴苯基)-4-苯基-5-甲基咪唑、2-(4-溴苯基)-4-苯基-5-甲基咪唑、2-(2-碘苯基)-4-苯基-5-甲基咪唑、2-(3-碘苯基)-4-苯基-5-甲基咪唑、2-(4-碘苯基)-4-苯基-5-甲基咪唑、2-(2-氟苯基)-4-苯基-5-甲基咪唑、2-(3-氟苯基)-4-苯基-5-甲基咪唑、2-(4-氟苯基)-4-苯基-5-甲基咪唑、2-(2,3-二氯苯基)-4-苯基-5-甲基咪唑、2-(2,4-二氯苯基)-4-苯基-5-甲基咪唑、2-(2,5-二氯苯基)-4-苯基-5-甲基咪唑、2-(2,6-二氯苯基)-4-苯基-5-甲基咪唑、2-(3,4-二氯苯基)-4-苯基-5-甲基咪唑、2-(3,5-二氯苯基)-4-苯基-5-甲基咪唑、2-(2,4-二氯苯基)-4-苯基-5-乙基咪唑、2-(2,3-二氯苯基)-4-苯基-5-癸基咪唑、2-(3,4-二氯苯基)-4-苯基-5-十七烷基咪唑、2-(2,4-二氯苯基)-4-苯基-5-異丙基咪唑、2-(2-庚基-4-氯苯基)-4-苯基-5-異丁基咪唑、2-苯基-4-(2-氯苯基)咪唑、2-苯基-4-(3-氯苯基)咪唑、2-苯基-4-(4-氯苯基)咪唑、 2-苯基-4-(2-溴苯基)咪唑、2-苯基-4-(3-溴苯基)咪唑、2-苯基-4-(4-溴苯基)咪唑、2-苯基-4-(2-碘苯基)咪唑、2-苯基-4-(3-碘苯基)咪唑、2-苯基-4-(4-碘苯基)咪唑、2-苯基-4-(2-氟苯基)咪唑、2-苯基-4-(3-氟苯基)咪唑、2-苯基-4-(4-氟苯基)咪唑、2-苯基-4-(2,3-二氯苯基)咪唑、2-苯基-4-(2,4-二氯苯基)咪唑、2-苯基-4-(2,5-二氯苯基)咪唑、2-苯基-4-(2,6-二氯苯基)咪唑、2-苯基-4-(3,4-二氯苯基)咪唑、2-苯基-4-(3,5-二氯苯基)咪唑、2-苯基-4-(2,3-二溴苯基)咪唑、2-苯基-4-(2-丙基-3-氯苯基)咪唑、2-苯基-4-(3-溴-4-庚基苯基)咪唑、2-苯基-4-(2-氯苯基)-5-甲基咪唑、2-苯基-4-(3-氯苯基)-5-甲基咪唑、2-苯基-4-(4-氯苯基)-5-甲基咪唑、2-苯基-4-(2-溴苯基)-5-甲基咪唑、2-苯基-4-(3-溴苯基)-5-甲基咪唑、2-苯基-4-(4-溴苯基)-5-甲基咪唑、 2-苯基-4-(2-碘苯基)-5-甲基咪唑、2-苯基-4-(3-碘苯基)-5-甲基咪唑、2-苯基-4-(4-碘苯基)-5-甲基咪唑、2-苯基-4-(2-氟苯基)-5-甲基咪唑、2-苯基-4-(3-氟苯基)-5-甲基咪唑、2-苯基-4-(4-氟苯基)-5-甲基咪唑、2-苯基-4-(2,3-二氯苯基)-5-甲基咪唑、2-苯基-4-(2,4-二氯苯基)-5-甲基咪唑、2-苯基-4-(2,5-二氯苯基)-5-甲基咪唑、2-苯基-4-(2,6-二氯苯基)-5-甲基咪唑、2-苯基-4-(3,4-二氯苯基)-5-甲基咪唑、2-苯基-4-(3,5-二氯苯基)-5-甲基咪唑、2-苯基-4-(2,3-二氯苯基)-5-丙基咪唑、2-苯基-4-(2,4-二氯苯基)-5-丙基咪唑、2-苯基-4-(2,4-二溴苯基)-5-(1-甲基丁基)咪唑、2-苯基-4-(2-己基-4-碘苯基)-5-丙基咪唑、2,4-雙(4-氯苯基)咪唑、2-(2,4-二氯苯基)-4-(3,4-二氯苯基)-5-甲基咪唑、2-(2-溴-4-辛基苯基)-4-(2-甲基-4-碘苯基)-5-辛基咪唑、2,4-二苯基-5-氟咪唑、2,4-二苯基-5-氯咪唑、2,4-二苯基-5-溴咪唑、2,4-二苯基-5-碘咪唑、2-(4-甲基苯基)-4-苯基-5-氯咪唑、 2-(4-氯苯基)-4-苯基-5-溴咪唑、2-苯基-4-(2-氯苯基)-5-碘咪唑。
化4的通式(IV)所示之咪唑化合物，可例示，2-苯基-4-(1-萘基)咪唑、2-苯基-4-(2-萘基)咪唑、2-(4-甲基苯基)-4-(4-氯6-丁基-1-萘基)咪唑、2-(2-辛基-4-乙基苯基)-4-(5-氯-7-丁基-1-萘基)咪唑、2-(2,4-二氯苯基)-4-(2-異丁基-6-溴-2-萘基)咪唑、2-苯基-4-(1-萘基)-5-甲基咪唑、2-(4-碘苯基)-4-(5,6-二甲基-1-萘基)-5-癸基咪唑、2-苯基-4-(2-萘基)-5-甲基咪唑、2-(2,3-二氟苯基)-4-(7-辛基2-萘基)-5-十七烷基咪唑、2-苯基-4-(1-萘基)-5-氟咪唑、2-苯基-4-(1-萘基)-5-氯咪唑、2-苯基-4-(1-萘基)-5-溴咪唑、2-苯基-4-(1-萘基)-5-碘咪唑、2-苯基-4-(2-萘基)-5-氟咪唑、2-苯基-4-(2-萘基)-5-氯咪唑、2-苯基-4-(2-萘基)-5-溴咪唑、2-苯基-4-(2-萘基)-5-碘咪唑、2-(4-甲基苯基)-4-(5-氯1-萘基)-5-氯咪唑。
化5之通式(V)所示之咪唑化合物，可例示，2-(1-萘基)-4-苯基咪唑、2-(2-萘基)-4-苯基咪唑、 2-(2-甲基-5-氯-1-萘基)-4-(4-己基苯基)咪唑、2-(2-丁基-5-碘-2-萘基)-4-(2-戊基-5-氟苯基)咪唑、2-(1-萘基)-4-苯基-5-甲基咪唑、2-(3,6-二氯-2-萘基)-4-(2-丙基-5-氟苯基-5-癸基咪唑、2-(6-丙基-7-碘-1-萘基)-4-(3-己基-6-溴苯基)-5-十七烷基咪唑、2-(1-萘基)-4-苯基-5-氟咪唑、2-(1-萘基)-4-苯基-5-氯咪唑、2-(1-萘基)-4-苯基-5-溴咪唑、2-(1-萘基)-4-苯基-5-碘咪唑、2-(2-萘基)-4-苯基-5-氟咪唑、2-(2-萘基)-4-苯基-5-氯咪唑、2-(2-萘基)-4-苯基-5-溴咪唑、2-(2-萘基)-4-苯基-5-碘咪唑、2-(4-氯-2-萘基)-4-(2-己基苯基)-5-氯咪唑等。
化6之通式(VI)所示之咪唑化合物，可例示，2-苯基苯並咪唑、2-(4-甲基苯基)苯並咪唑、2-(2,4-二氯苯基)苯並咪唑、2-(2-己基苯基)-5-氯苯並咪唑、2-(苯基甲基)苯並咪唑、2-(4-乙基苯基甲基)苯並咪唑、2-(4-氯苯基甲基)苯並咪唑、2-(2,4-二氯苯基甲基)苯並咪唑、 2-(3,4-二氯苯基甲基)苯並咪唑、2-(4-溴苯基甲基)-5-乙基苯並咪唑、2-(3-碘苯基甲基)-4-氯苯並咪唑、2-(2-苯基乙基)苯並咪唑、2-[2-(3-異丙基苯基)乙基]苯並咪唑、2-[2-(4-氯苯基)乙基]苯並咪唑、2-[2-(4-氯苯基)乙基]-4,5-二甲基苯並咪唑、2-(3-苯基丙基)苯並咪唑、2-[3-(4-第三丁基苯基)丙基]苯並咪唑、2-[3-(2-氯苯基)丙基]苯並咪唑、2-[3-(4-溴苯基)丙基]-5-丁基苯並咪唑、2-(4-苯基丁基)苯並咪唑、2-[4-(4-氯苯基)丁基]苯並咪唑、2-[4-(2,4-二氯苯基)丁基]-4,7-二氯苯並咪唑、2-(5-苯基戊基)苯並咪唑、2-[5-(2-辛基苯基)戊基]苯並咪唑、2-[5-(3,4-二氯苯基)戊基]-5-庚基苯並咪唑、2-(6-苯基己基)苯並咪唑、2-[6-(3-己基苯基)己基]苯並咪唑、2-[6-(2-乙基-3-氟苯基)-己基]-4-丁基-5-辛基苯並咪唑等。
化7之通式(VII)所示之咪唑化合物，可例示，2-(1-萘基)苯並咪唑、2-(1-萘基)-4-甲基苯並咪唑、2-(2-萘基)苯並咪唑、 2-(1-氯2-萘基)-5,6-二氯苯並咪唑、2-(1-萘基甲基)苯並咪唑、2-(4,6-二甲基-1-萘基甲基)-5-乙基苯並咪唑、2-(7-溴-1-萘基甲基)-5-溴苯並咪唑、2-(2-萘基甲基)苯並咪唑、2-(4-異丙基-2-萘基甲基)-5-第三丁基苯並咪唑、2-[2-(1-萘基)乙基]苯並咪唑、2-[2-(5-戊基-1-萘基)乙基]-5-氯苯並咪唑、2-[2-(2-萘基)乙基]苯並咪唑、2-[2-(6-庚基-2-萘基)乙基]-4-甲基-5-己基苯並咪唑、2-[3-(1-萘基)丙基]苯並咪唑、2-[3-(4-碘-1-萘基)丙基]-5,6-二溴苯並咪唑、2-[3-(2-萘基)丙基]苯並咪唑、2-[3-(8-異丙基-2-萘基)丙基]-5-(2-甲基戊基)苯並咪唑、2-[4-(1-萘基)丁基]苯並咪唑、2-[4-(5-氟-1-萘基)丁基]-4-(2丙基丁基)苯並咪唑、2-[4-(2-萘基)丁基]苯並咪唑、2-[4-(7-辛基-2-萘基)丁基]-4,6-二乙基苯並咪唑、2-[5-(1-萘基)戊基]苯並咪唑、2-[5-(6-戊基-7-氟1-萘基)戊基]-4,7-二丙酯苯並咪唑、2-[5-(2-萘基)戊基]苯並咪唑、2-[5-(6,7-二甲基2-萘基)戊基]-5,6-二氯苯並咪唑、2-[6-(6,7-二乙基-1-萘基)己基]-5-辛基苯並咪唑、2-[6-(2-萘基)己基]苯並咪唑、 2-[6-(7-乙基-8-溴-2-萘基)己基]-4-己基-6-氟苯並咪唑等。
化8之通式(VIII)所示之咪唑化合物，可例示，2-環己基苯並咪唑、2-環己基-5,6-二甲基苯並咪唑、2-環己基-5-氯苯並咪唑、2-環己基-4-丙基苯並咪唑、2-(環己基甲基)苯並咪唑、2-(環己基甲基)-5-乙基苯並咪唑、2-(環己基甲基)-5-溴苯並咪唑、2-(2-環己基乙基)苯並咪唑、2-(2-環己基乙基)-5-氯-6-甲基苯並咪唑、2-(3-環己基丙基)苯並咪唑、2-(3-環己基丙基)-5-丁基苯並咪唑、2-(3-環己基丙基)-4,7-二甲基苯並咪唑、2-(4-環己基丁基)苯並咪唑、2-(4-環己基丁基)-5-碘苯並咪唑、2-(4-環己基丁基)-4-氯-5-乙基苯並咪唑、2-(4-環己基丁基)-5-辛基苯並咪唑、2-(5-環己基戊基)苯並咪唑、2-(5-環己基戊基)-5-己基苯並咪唑、2-(5-環己基戊基)-5,6-二溴苯並咪唑、2-(6-環己基己基)苯並咪唑、2-(6-環己基己基)-5-庚基咪唑、2-(6-環己基己基)-4-氯-5-(2-丙基丁基)苯並咪唑等。
2.銅球
接著，詳述關於構成本發明之銅球1。
構成本發明之銅球1，係將OSP處理銅球11使用於焊料凸塊時，由於以焊接的溫度並不會熔融，故可抑制焊接接頭高度的離散。因此，銅球1的真球度高且直徑離散少較佳。此外，如上所述，銅球1的α射線劑量亦與OSP披膜2同樣地低為佳。以下記載銅球1之較佳的態樣。
鈾：5ppb以下，釷：5ppb以下
鈾及釷係放射性同位素，為抑制軟錯誤需要抑制該等的含量。鈾及釷的含量，在為使銅球1的α射線劑量為0.0200cph/cm2以下，需分別為5ppb以下。此外，在現在或未來的高密度構裝抑制軟錯誤的觀點，鈾及釷的含量，分別以2ppb以下以下為佳。
．銅球的純度：99.9%以上99.995%以下
構成本發明之銅球1，以純度為99.9%以上99.995%以下為佳。銅球1的純度在此範圍，則可於熔融銅中確保充分量用於提高銅球1之真球度之結晶核。提高真球度的理由，詳述如下。
製造銅球1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1。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1。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1，真球度低。雜質元素，可考慮錫、銻、鉍、鋅、砷、銀、銦、鎘、鎳、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1的導電及熱傳導率的惡化的觀點，以99.9%以上為佳。。
在此，即使在銅球1，不將純度提高到必要以上， 亦可減低α射線劑量。由於銅的熔點較錫高，製造時的加熱溫度，銅較高。於本發明，製造銅球1時，由於會如後所述進行先前的銅材並不會進行的加熱處理，故以210釙、210鉛、210鉍為代表的放射性元素將會揮發。特別是該等放射性元素之中，210Po容易揮發。
．α射線劑量：0.0200cph/cm2以下
構成本發明之銅球1的α射線劑量，以0.0200cph/cm2以下為佳。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1的步驟，施以再度加熱處理。因此，使些微殘存於銅材料的210釙揮發，而與銅材料相比，銅球1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。
．鉛或鉍的含量或合併鉛及鉍之兩者之含量合計 為1ppm以上
構成本發明之銅球1，雜質元素含有錫、銻、鉍、鋅、砷、 銀、鎘、鎳、鉛、金、磷、硫、鈾、釷等，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以上為佳。於本發明，即使是銅球1在形成焊接接頭時露出時，在減少α射線劑量上，無須將鉛或鉍之任一的含量、或鉛及鉍的合計含量降低至極限。其理由如下。
210鉛及210鉍係藉由β衰變變成210釙。為減少α 射線劑量，可認為雜質元素之鉛或鉍的含量極低較佳。
但是，包含於鉛及鉍中的210鉛及210鉍的含有比 很低。故只要將鉛或鉍的含量減低至某種程度，則可認為大致去除210鉛及210鉍。關於本發明的銅球1，係將銅的熔解溫度設定較先前稍微高，或對銅材及/或造粒後的銅球1進行加熱處理而製造。該溫度，即使是較鉛及鉍的沸點低，還是會發生氣化而使雜質元素量降低。此外，為提高銅球1的真球度，雜質元素的含量高較佳。因此，本發明的銅球1，係鉛或鉍的含量或合併鉛及鉍兩者之含量以合計為1ppm以上。包含鉛及鉍的任何一方時，鉛及鉍的合計含量為1ppm以上。
如此，由於鉛及/或鉍在製造銅球1之後，亦殘存 某種程度的量，故含量測定誤差較少。再者，如上所述，在於鉍及鉛由於在銅球1的製造步驟的熔融時成為結晶核，故在銅中含有一定量鉍及鉛，則可製造真球度高的銅球1。因此，鉛或鉍，係用於推定雜質元素含量的重要元素。由如此的觀點，鉛或鉍的含量或合併鉛及鉍兩者之含量合計以1ppm以上為佳。鉛或鉍的含量或合併鉛及鉍兩者之含量合計以10ppm以上更佳。上限值並無特別限定，由抑制銅球1的導電度惡化的觀 點，鉛或鉍的含量或合併鉛及鉍兩者之含量共計以未滿1000ppm，以100ppm以下更佳。鉛的含量以10ppm~50ppm更佳，鉍的含量10ppm~50ppm更佳。
．銅球的真球度：0.95以上
構成本發明之銅球1，由抑制腳高高度的觀點，真球度為0.95以上。銅球1的真球度未滿0.95，則由於銅球1將成為不定形狀，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。再者將OSP處理銅球11搭載於電極進行回焊時，引起OSP處理銅球11的錯位，而使自我對準性惡化。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個銅球或各銅核球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
構成本發明的銅球1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1，端子間為窄間距時可抑制連接短路。
在此，例如關於本發明的OSP處理銅球11的直徑為1~300μm程度時，「OSP處理銅球」的集合體，亦可稱為 「OSP處理銅粉」。在此，「OSP處理銅粉」，係各個OSP處理銅球11包括上述特性之多數OSP處理銅球11的集合體。例如，調和作為焊膏中的粉末等，與單一的OSP處理銅球11，在於使用形態有所區別。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「OSP處理銅粉」與單一的OSP處理銅球11有所區別。
關於本發明的OSP處理銅球11，亦可在形成OSP披膜2之前，預先將銅球1的表面以Ni、Co等的其他金屬的鍍敷層披覆。金屬的鍍敷層亦可由複數層構成。此外，使用於鍍敷層的金屬並不僅限於Ni、Co等的單一金屬，亦可使用由Ni、Co等之中組合2元素以上的合金。再者，亦可在形成在OSP披膜2上的鍍敷層上形成含有咪唑化合物的OSP披膜。
此外，關於本發明的OSP處理銅球11的真球度以0.95以上為佳。OSP處理銅球11的真球度低時，將OSP處理銅球11裝載到電極進行回焊時，會引起OSP處理銅球11的錯位，而自我對準性亦會惡化。真球度，以0.990以上更佳。
再者，藉由將關於本發明的OSP處理銅球11分散於焊料中，可使用於作為泡沫焊。此外，藉由將關於本發明的OSP處理銅球11與焊料混鍊，可使用於作為焊膏。此外，關於本發明的OSP處理銅球11，可使用於形成相互接合電子零件端子(電極)的焊接接頭。
說明關於本發明之OSP處理銅球11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(以下稱為「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1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1。冷卻後，成形的銅球1，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1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1，可分別以800~1000℃的溫度再度進行加熱處理30~60分鐘。
於本發明之OSP處理銅球11之製造方法，於造粒 銅球1之前，亦可將作為銅球1的原料的銅材，以800~1000℃加熱處理。
銅球1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1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1或異形的銅球1時，亦可將該等銅球1作為原料再利用，可進一步降低α射線劑量。
接著，如上所述地製作的銅球1，浸漬於水溶性預 焊劑(將咪唑化合物溶解在水中的表面處理劑)。藉此，使銅球1的最表面的銅層與咪唑化合物結合，可於銅球1的表面形成OSP披膜2(咪唑銅錯合物)。之後，將形成OSP披膜2的銅球1，水洗處理之後，在大氣中或N2氣氛中乾燥，而製作關於本發明的OSP處理銅球11。再者，銅球1之浸漬後，亦可按照必要將OSP處理銅球11的表面以(去離水)水清洗。
當在將咪唑化合物溶解於水(水溶液化)時，一般， 使用有機酸或無機酸作為酸，但是亦可並用少量的有機溶劑。 此時使用之代表性的有機酸，可舉甲酸、乙酸、丙酸、丁酸、乙醛酸、丙酮酸、乙醯乙酸、乙醯丙酸、庚酸、辛酸、癸酸、月桂酸、乙醇酸、甘油酸、乳酸、丙烯酸、甲氧基醋酸、乙氧基醋酸、丙氧基醋酸、丁氧基醋酸、2-(2-甲氧基乙氧基)醋酸、2-[2-(2-乙氧基乙氧基)乙氧基]醋酸、2-{2-[2-(2-乙氧基乙氧基)乙氧基]乙氧基}醋酸、3-甲氧基丙酸、3-乙氧基丙酸、3-丙氧基丙酸、3-丁氧基丙酸、安息香酸、對硝基安息香酸、對甲苯磺酸、柳酸、苦味酸、草酸、琥珀酸、馬來酸、富馬酸、酒石酸、己二酸等，作為無機酸，鹽酸、磷酸、硫酸、硝酸等。該等酸，係於表面處理劑中以0.1~50重量%的比例含有，以1~30重量%的比例為佳。
此外，作為有機溶劑，可使用甲醇、乙醇、丙醇 等的低級醇或丙酮、N,N-二甲基甲醯胺、乙二醇等可與水自由 混合者。
於表面處理劑，可為加快在銅球1表面形成有機 披膜的速度，而添加銅化合物，此外，亦可為更加提升形成之化成披膜的耐熱性，而添加鋅化合物。
銅化合物的代表性者，醋酸銅、氯化亞銅、氯化 銅、溴化亞銅、溴化銅、碘化銅、氫氧化銅、磷酸銅、硫酸銅、硝酸銅，此外，鋅化合物的代表性者，可舉氧化鋅、蟻酸鋅、醋酸鋅、草酸鋅、乳酸鋅、檸檬酸鋅、硫酸鋅、硝酸鋅、磷酸鋅等，均可於表面處理劑中以0.01~10重量%的比例含有，以0.02~5重量%的比例為佳。
使用該等銅化合物與鋅化合物時，於有機酸或無 機酸之外，亦可添加氨或單乙醇胺、二乙醇胺、三乙醇胺等的胺類等的具有緩沖作用的物質，使溶液的pH穩定為佳。
此外，於水溶性預焊劑，可為更加提升OSP披膜 2的形成速度及耐熱性，於表面處理劑中，將鹵素化合物，以0.001~1重量%的比例添加，以0.01~0.1重量%含有為佳。鹵素化合物，可舉例如，氟化鈉、氟化鉀、氟化銨、氯化鈉、氯化鉀、氯化胺、溴化鈉、溴化鉀、溴化銨、碘化鈉、碘化鉀、碘化銨等。
使用水溶性預焊劑OSP處理銅球1表面時的條 件，使水溶性預焊劑的液溫為10~70℃，處理時間以1秒~10分鐘為佳。處理方法，可舉浸漬、噴霧，塗佈等的方法。
實施例1
以下說明本發明之實施例，惟本發明不應限定於 該等。於本實施例製作真球度高的銅球，於該銅球表面形成OSP披膜，測定α射線劑量。
．銅球的製作
調查真球度高的銅球的製作條件。分別準備純度為99.9%的銅球、純度為99.995%以下的銅線、及純度為99.995%以上的銅板。分別投入坩堝中之後，將坩堝的溫度升溫至1200℃，進行加熱處理45分鐘，由設於坩堝底部的孔滴下熔融銅，將生成的液滴冷卻將銅球造粒。藉此，製作平均粒徑為250μm的銅球。將製作之銅球的元素分析結果及真球度示於第1表。元素分析，在關於鈾及釷係使用感應耦電漿質譜分析(ICP-MS分析)，關於其他的元素係使用感應耦電漿放光光譜分析(ICP-AES分析)進行。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公司製的ULTRA QUICK VISION，ULTRA QV350-PRO。
α射線劑量的測定方法表示如下。
．α射線劑量
於α射線劑量的測定，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JEDEC STANDARD-Alpha Radiation Measurement in Electronic Materials JESD221的方針。
於第1表表示製作之銅球的元素分析結果、α射線 劑量。
如第1表所示，使用純度99.9%的銅錠及99.995% 以下的銅線的銅球真球度均顯示真球度為0.990以上。另一方面，如第1表所示，使用純度為99.995%以上的銅板所製造的銅球真球度為低於0.95。
．實施例1-1
其次，於使用純度99.9%的銅錠製造的銅球表面形成OSP披膜，而製作OSP處理銅球。以下，詳細說明關於OSP處理銅球的製作方法。首先，於100cc的玻璃瓶放入70cc的Glicoat-SMD F2(四國化成工業株式會社製)作為水溶性預焊劑，加溫為40℃。接著，於玻璃瓶加入1g直徑250μm的銅球，迅速蓋上蓋子之後，將玻璃瓶攪拌10分鐘。之後，將抽氣過濾分離的銅球以去離子水清洗，之後，將銅球以100℃溫風乾燥1分鐘。藉此得到於直徑250μm的銅球表面均勻地披覆OSP 披膜的OSP處理銅球。
OSP處理銅球的α射線劑量，以與上述銅球同樣 的方法測定。此外，關於OSP處理銅球的真球度，亦以與銅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1-2、1-3
於實施例1-2，使用第1表所示純度為99.995%以下的銅線的銅球，以與實施例1-1同樣的方法，進行表面處理，製作於銅球表面形成OSP披膜的OSP處理銅球，與實施例1-1進行同樣的評估。關於製作的OSP處理銅球，與實施例1-1同樣地，測定α射線劑量、真球度。將測定結果示於第2表。
於實施例1-3，使用第1表所示純度為99.995%以 上的銅板的銅球，以與實施例1-1同樣的方法，進行表面處理，製作於銅球表面形成OSP披膜的OSP處理銅球，與實施例1-1進行同樣的評估。關於製作的OSP處理銅球，與實施例1-1同樣地，測定α射線劑量、真球度。將測定結果示於第2表。
根據第2表，於實施例1-1，α射線劑量顯示未滿 0.0010cph/cm2。實施例1-1之OSP處理銅球，藉由使用低α射線劑量的銅球的同時，藉由將低α射線劑量的OSP披膜形成於銅球表面，證明總體的α射線劑量並不會上升。
此外，以實施例1-1製作的OSP處理銅球的α射線劑量， 即使在製作後經過1年，並沒有觀察到α射線劑量的上升。
同樣地，於實施例1-2、1-3，α射線劑量亦顯示未 滿0.0010cph/cm2。實施例1-2、1-3之OSP處理銅球，藉由使用低α射線劑量的銅球的同時，藉由將低α射線劑量的OSP披膜形成於銅球表面，證明總體的α射線劑量並不會上升。此外，以實施例1-2、1-3製作的OSP處理銅球的α射線劑量，即使在製作後經過1年，並沒有觀察到α射線劑量的上升。
實施例2
接著，為調查將於銅球表面披覆OSP披膜的OSP處理銅球構裝在電極時的錯位，進行保管條件不同的各種OSP處理銅球的對位性之研究。於以下所示實施例及比較例，均係使用第1表所示99.995%以下的銅線材所製造的銅球進行各種研究。
以如下條件進行以不同的保管條件中保管的OSP處理銅球的錯位的測定。首先，於基板上放置100μm厚的金屬掩模，經由金屬掩模將焊膏(千住金屬工業株式會社製：M705-GRN360-K2-V)印刷在電極。於基板，使用於銅電極進行水溶性預焊劑的OSP處理的銅-OSP基板。其次，將OSP處理銅球搭載到印刷焊膏的電極，藉由回焊製作銅球接合於電極的焊料凸塊。電極的直徑為240μm。回焊條件，係於N2氣氛，波峰溫度為245℃，預備加熱以140~160℃ 20秒，本加熱以220℃以上進行40秒。之後，對製作的焊料凸塊，進行錯位的測定，及對位性的評估。結果示於第3表。各測定及各評估的詳細情況，係如下所示。
．對位性的評估
於本實施例，將以不同的保管條件保管的複數OSP處理銅球，分別構裝於電極做回焊時，測定OSP處理銅球對電極錯位到何種程度。OSP處理銅球對電極的錯位，係藉由圓心間距離測定而進行。所謂圓心間距離測定，係將OSP處理銅球的圓周繪製3點的同時，繪製3點電極的圓周，測定OSP處理銅球的3點繪製中心點與電極的3點繪製中心點之間的距離(圓心間距離)者。再者，繪製數並不限定於3點。於圓心間距離的測定，使用KEYENCE製VH-S30。
於本實施例，將藉由測定所得之複數個圓心間距 離的平均值作為最終的圓心間距離。具體而言，首先使用以完全相同的條件製作的10個OSP處理銅球，製作10個焊料凸塊。其次，使用將1個焊料凸塊的圓心間距離測定5次，算出其平均值之X的方法，對各10個焊料凸塊計算出X，將算出之10個X的平均值之Y作為圓心間距離。將以上的作業對每個各實施例進行，算出各圓心間距離。於比較例，使用10個銅球製作10個焊料凸塊，以與上述OSP處理球同樣的方法算出圓心間距離。
．關於實施例2-1~2-3、比較例2-1
於實施例2-1，係將如上所述地製作的OSP處理銅球放入培養皿中，以放入除氧劑之氧穿透度低的袋子密封，於室溫(20℃、濕度50%)保管。於實施例2-2，係將如上所述方法製作的OSP處理銅球放入培養皿之後，將整個培養皿放入恆溫槽，以200℃加熱10分鐘，故意使OSP處理銅球容易氧化。於實施例 2-3，係將如上所述方法製作的OSP處理銅球放入培養皿之後，以整個培養皿放入溫度40℃、濕度90%的恆溫槽的狀態保管2週。
於比較例2-1，係將沒有進行OSP處理的銅球放入 培養皿之後，將整個培養皿放入恆溫槽，以200℃加熱10分鐘，故意使銅球容易氧化。
將實施例2-1~2-3、比較例2-1的結果示於第3表。 再者，在於第3表，在於OSP處理銅球及銅球之圓心間距離在15μm以下時，表示對位性佳，以「○」表示，在於OSP處理銅球及銅球之圓心間距離超過15μm時，表示對位性差，以「×」表示。
如第3表所示，使用OSP處理銅球的實施例2-1， 圓心間距離均為15μm以下，對位性為「○」。於第2圖表示將實施例2-1之OSP處理銅球11構裝在電極13上時之焊料凸塊的狀態以光學顯微鏡拍攝之照片。再者，於電極13上，塗佈焊膏12。由第2圖亦明顯可知，OSP處理銅球11搭載於半導體晶片10的電極13的中央，可知OSP處理銅球11在電極13上並沒有錯位。同樣地，實施例2-2、2-3之圓心間距離均為15μm以下，對位性均為「○」。再者，將實施例2-2、2-3的OSP處理銅球構裝在電極上時的焊料凸塊的狀態，大致與實 施例2-1相同而沒有發生錯位，故權宜上省略。
另一方面，使用沒有進行OSP披膜處理的銅球的 比較例2-1，如第3表所示，圓心間距離超過15μm，對位性為「×」。於第3圖表示將比較例2-1之OSP處理銅球21構裝在電極23上時以光學顯微鏡拍攝之照片。再者，於電極23上，塗佈焊膏22。由第3圖亦明顯可知沒有進行OSP處理時，OSP處理銅球21由電極23的中央錯位。
由以上，證明藉由對銅球進行OSP處理，可抑制 氧化膜的形成，結果可防止OSP處理銅球在回焊時的錯位。
再者，本發明之技術範圍，並非限定於上述實施 形態，在不脫逸本發明的趣旨的範圍，包含對上述實施形態加以各種變更者。
1‧‧‧銅球
2‧‧‧OSP披膜
11‧‧‧OSP處理銅球

Claims (10)

  1. 一種OSP處理銅球，包括：銅球；及含有將該銅球的表面披覆的咪唑化合物的有機披膜之OSP處理銅球，其特徵在於：上述銅球，係純度為99.9%以上99.995%以下，鈾的含量為5ppb以下，釷的含量為5ppb以下，鉛或鉍的含量或合併鉛及鉍兩者之含量的合計量為1ppm以上，真球度為0.95以上，α射線劑量為0.0200cph/cm2以下。
  2. 根據申請專利範圍第1項之OSP處理銅球，其中α射線為0.0200cph/cm2以下。
  3. 根據申請專利範圍第1項之OSP處理銅球，其中α射線為0.0020cph/cm2以下。
  4. 根據申請專利範圍第1項之OSP處理銅球，其中α射線為0.0010cph/cm2以下。
  5. 根據申請專利範圍第1至4項中任一項之OSP處理銅球，其中直徑為1~1000μm。
  6. 根據申請專利範圍第1至5項中任一項之OSP處理銅球，其中上述銅球，在以上述有機披膜披覆之前，預先以選自由Ni及Co之1元素以上所組成之層披覆。
  7. 根據申請專利範圍第1至6項中任一項之OSP處理銅球，其中上述OSP處理銅球的真球度為0.95以上。
  8. 一種焊料接頭，使用申請專利範圍第1至7項中任一項之 OSP處理銅球。
  9. 一種泡沫焊，使用申請專利範圍第1至7項中任一項之OSP處理銅球。
  10. 一種焊膏，使用申請專利範圍第1至7項中任一項之OSP處理銅球。
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