TW201446980A - 球焊用貴金屬薄銀合金絲 - Google Patents

球焊用貴金屬薄銀合金絲 Download PDF

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TW201446980A
TW201446980A TW103111911A TW103111911A TW201446980A TW 201446980 A TW201446980 A TW 201446980A TW 103111911 A TW103111911 A TW 103111911A TW 103111911 A TW103111911 A TW 103111911A TW 201446980 A TW201446980 A TW 201446980A
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silver alloy
noble metal
wire
bonding
mass
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TW103111911A
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TWI521070B (zh
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Kazuhiko Yasuhara
Yuki ANTOKU
Wei Chen
Nanako Maeda
Jun Chiba
Junichi Okazaki
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Tanaka Electronics Ind
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Abstract

【課題】本發明旨在通過在貴金屬銀合金絲的整體表面上設置極薄的碳層，利用該碳(C)的還原作用防止大氣對貴金屬銀合金的硫化和氧化，而且，表面鬆散結合的硫化銀(Ag2S)膜等也能藉由第二次鍵合時超聲波的低熱能，從鍵合面上去除。【解決方法】本發明之球焊用貴金屬銀合金絲的特徵在於，在質量百分比純度99.9%以上的鈀(Pd)、鉑(Pt)及金(Au)中的至少一種之總量佔質量百分比0.1~6%，且其他部分由質量百分比純度99.99%以上的銀(Ag)所構成的球焊用貴金屬銀合金絲的表面結構中，該鍵合絲表面是連續鑄造面經金剛石模具縮徑後的拉絲加工面，該拉絲加工面的整體表面上係形成總有機碳量(TOC值)為50~3,000μg/m2的有機碳層。

Description

球焊用貴金屬薄銀合金絲
本發明涉及適用於半導體裝置中使用的IC晶片電極與外部引線等電路板連接的鍵合用貴金屬銀合金絲，特別是指第二次鍵合性優良的球焊用貴金屬銀合金絲。
一直以來，作為連接半導體裝置的IC晶片電極與外部引線的球焊鍵合絲，因連接可靠性優良而大量使用在質量百分比純度99.99%以上的金(Au)中只添加了不到100質量比ppm其他金屬元素的純金絲。這種純金絲在其一端形成熔球後，通過熱壓超聲波鍵合法被連接至IC晶片電極上的鋁焊盤，另一端被連接至印刷電路板、引線框架及器件等外部引線等。然後，連接好的純金絲被模製樹脂(molded resin)密封，形成半導體裝置。此外，鋁焊盤由純鋁(Al)、Al-1%Si(質量百分比)合金、Al-0.5%Cu(質量百分比)合金、Al-1%Si(質量百分比)-0.5%Cu(質量百分比)合金等構成，一般採用真空蒸鍍等乾式塗佈成形。
銀合金來代替這種純金絲在很早以前就一直被考慮使用。例如，特開2012-99577號公報(後述的“專利文獻1”)中披露了“特徵為以銀(Ag)為主要成分；至少含有一種以上從10000~90000質量比ppm的金(Au)、10000~50000質量比ppm的鈀(Pd)、10000~30000質量比ppm的銅(Cu)、10000~20000質量比ppm的鎳(Ni)中選出的成分；且氯(Cl)含量不到1質量比ppm的鍵合絲”的發明。該發明“旨在廉價提供鍵合絲表面不施加金屬塗層、波長380 ~560nm處的光反射率高、提高了化學穩定性的鍵合絲，從而提高發光裝置的光特性(該公報0008段落)”。
與純銀鍵合絲相比，該銀合金絲因鈀(Pd)等的耐氯性、耐硫性的相互作用，在氯(Cl)、硫(S)等大氣及特殊環境下的污染均比純銀絲大致有了改善。但是，與純金絲相比，合金成分的貴金屬含量為6%以下的所謂貴金屬銀合金絲依然存在鍵合絲表面易髒、硫化程度易加深的缺點。因此，也存在如下缺點：即使是在使用鍵合絲的一般潔淨室內，如果將貴金屬銀合金絲放置30天左右，鍵合絲表面就會因從室外氣體引入的空氣中存在的硫(S)而形成硫化銀(Ag2S)，該硫化銀(Ag2S)會妨礙良好的第二次鍵合，降低採用超聲波時與外部引線的鍵合强度。
另一方面，為了提高與鍵合工具間的滑動已知的還有“以Au、Al、Cu中的任意一種為主要元素，拉絲加工成10~50μm左右的極細絲，在線軸上捲繞規定長度，並以這種狀態安裝在鍵合機上使用(特開平6-151497號公報(後述的“專利文獻2”)0002段落)”的鍵合絲，和熔鑄後對鑄塊進行酸洗等“特徵為表面的總有機碳量為50~1500μg/m2的半導體器件鍵合絲(該公報請求項1)”。關於該方法，記載如下：“經一般製程，即溶解、鑄造、拉絲、退火、捲繞製程所製造的鍵合絲表面已可發現超過1500μg/m2的總有機碳量，因此，製造表面總有機碳量為50~1500μg/m2的鍵合絲的方法之一就是採用…酸洗…等方法對其進行沖洗，使表面總有機碳量在50~1500μg/m2範圍內(請求項2)。該方法的特徵在於，於一般製程的退火製程前或後適當提供沖洗製程，容易實施。(該公報0010段落)”，而且，“潤滑劑成分有石蠟烴、環烷烴、芳烴等礦物油類；聚烯烴、烷基苯、脂肪酸、高級醇、脂肪酸皂、聚乙二醇、聚苯醚、脂肪酸二酯、多元醇酯、聚氧乙烯烷基醚、磺酸鹽、胺、胺鹽、矽酮、磷酸酯、碳氟化合物、氟聚醚、氟乙二醇等合成 油類；牛油、猪油、棕櫚油、豆油、菜油、蓖麻油、松油等天然油脂類，可以使用任何一種。此外，也可以使用上述多種成分的混合(該公報0012段落)”。
但是，該有機碳是作為潤滑劑成分使用，並非以隔離大氣中的硫(S)成分為目的。儘管本發明之貴金屬銀合金絲不是質量百分比純度99.9%以上的純銀絲，但仍具有容易吸收大氣中的硫(S)成分的性質。因此，如果碳層薄，則具有銀(Ag)成分容易與大氣中存在的硫(S)成分結合，在鍵合絲表面形成硫化銀的性質。於是存在如下缺點，即一旦在鍵合絲表面形成牢固的硫化銀(Ag2S)後，該硫化銀(Ag2S)繼續向鍵合絲內部深入，形成不均一的硫化銀(Ag2S)膜，使得第二次鍵合不穩定，而使第二次鍵合的鍵合面不穩定。而且，在對貴金屬銀合金絲進行第二次鍵合時，一般都會將電路板、引線框架、器件等加熱到高溫(100℃~250℃左右)狀態，因此，由於其周圍環境的熱氣，存在於鍵合面的由鍵合絲衍生的硫(S)就更容易與大氣中存在的硫(S)成分結合。因此，還存在第二次鍵合後鍵合面的硫化程度進一步加深，鍵合面變得更容易剝離的缺點。
而且，如果鍵合前硫化銀(Ag2S)膜進一步向鍵合絲內部深入，則第一次鍵合前就會發生晶片開裂、鍵合不良等不良影響。
【早期技術文獻】
【專利文獻】
【專利文獻1】特開2012-99577號公報
【專利文獻2】特開平6-151497號公報
本發明是為了解決上述第二次鍵合的課題所開發，旨在提供一個鍵合絲，而該鍵合絲可使貴金屬銀合金絲達到即使其 為貴金屬銀合金仍可防止大氣中的硫所引起的硫化之效果。
本發明人等著眼於熔鑄後的貴金屬銀合金表面的活性(與大氣中的硫(S)的化學反應性)比純銀合金小此點，旨在實現下列目的：首先通過採用貴金屬銀合金減弱大氣中的硫(S)與鍵合絲表面的銀(Ag)成分的化學反應性；繼而通過對該表面實施縮徑、減小表面積、降低表面活性；然後通過在貴金屬銀合金絲的整體表面上設置極薄的碳層，利用該碳(C)的還原作用防止大氣對貴金屬銀合金的硫化和氧化；而且，即使不是如第一次鍵合時的熔化熱般的强大熱能，而是第二次鍵合時超聲波的低熱能，也能從鍵合面上去除與銀合金絲表面鬆散結合的硫化銀(Ag2S)膜等。
用以解決本發明之課題的球焊用貴金屬銀合金絲的表面結構，其特徵在於：，在質量百分比純度99.9%以上的鈀(Pd)佔質量百分比0.1~6%，且其餘部分由質量百分比純度99.99%以上的銀(Ag)構成的球焊用貴金屬銀合金絲的表面結構中，鈀(Pd)占質量百分比3.0~4.8%，且其餘部分由銀(Ag)構成的鍵合絲表面是連續鑄造面經金剛石模具縮徑後的拉絲加工面，該拉絲加工面的整體表面形成總有機碳量(TOC值)為50~3,000μg/m2且由沸點比上述貴金屬銀合金的熔點低的水溶性非硫系有機高分子衍生的有機碳層。
在本發明之貴金屬銀合金絲的表面結構中，以連續鑄造面狀態保存該鍵合絲表面，是為了使鍵合絲表面不形成新的活性面。此外，通過金剛石模具對該連續鑄造面進行拉絲加工，是因為金剛石模具對貴金屬銀合金的滑動性好，能在保存連續鑄造面的狀態下進行縮徑。利用金剛石模具的縮徑至少需要最終的拉絲模具是金剛石模具。一般的縮徑是在水中或採用噴淋的濕式連續拉絲方式進行的。藉由使本發明之貴金屬銀合金絲表面變成連續鑄造面經縮徑後的惰性拉絲加工面，並在該表面上設置有機碳層，可以防止大氣中的硫 (S)與鍵合絲表面的銀(Ag)成分的結合。
在本發明之貴金屬銀合金絲的表面結構中，上述貴金屬銀合金為質量百分比純度99.9%以上的鈀(Pd)佔質量百分比0.1~6%且其餘部分為質量百分比純度99.99%以上的銀(Ag)，是因為考慮到與鋁焊盤的鍵合性及可靠性壽命。即，如果事先不將貴金屬銀合金絲本身的硬度降低一定程度，則熔球與純鋁(Al)焊盤及Al合金焊盤等連接時，會更容易發生晶片損傷。此外，這也是為了讓第一次鍵合的鍵合面上銀(Ag)與鋁(Al)的鍵合面沒有硫(S)成分殘留。鈀(Pd)具有在第一次鍵合時，在無空氣焊球(FAB)的氮環境中不與鋁焊盤形成金屬間化合物(intermetallic compound)且以正球體形狀連接熔球的效果。令合金元素的含量為質量百分比6%以下，是因為超過質量百分比6%後，在無空氣焊球(FAB)中形成的熔球會過硬，更容易發生晶片損傷。此外，合金元素的含量為質量百分比0.1%以上，是因為合金元素的含量過少，就不能獲得抗硫化性，即使表層形成了有機碳膜，也不能抑制連續鑄造面上硫化程度的加深。貴金屬銀合金絲的連續鑄造面上形成硫化銀(Ag2S)膜後，就會形成熔球，即使有機碳層高溫裂解，熔球也會變硬，更容易發生晶片損傷。
銀(Ag)成分的純度為質量百分比99.99%以上，是為了使金屬雜質不到100質量比ppm，避免金屬雜質在貴金屬銀合金絲的連續鑄造面上發生內部氧化。為了形成優質的貴金屬銀合金絲，銀(Ag)成分的純度應為質量百分比99.999%以上。同樣，為了形成優質的貴金屬銀合金絲，鈀(Pd)、鉑(Pt)及金(Au)等各合金元素的純度應為質量百分比99.99%以上。
在本發明之貴金屬銀合金絲的合金元素中，最佳為鈀(Pd)。這是因為易於分解第二次鍵合時貴金屬銀合金絲表面形成的硫化物。此外，鈀(Pd)不僅可阻礙於第一次鍵合時，銀(Ag)與鋁(Al)在鍵合面上形成金屬間化合物，亦 可有效防止銀(Ag)與鋁(Al)的金屬間化合物在高溫高濕條件下所造成的鍵合面劣化。此外，本發明之貴金屬銀合金應為：質量百分比純度99.99%以上的鈀(Pd)佔質量百分比0.1~5%、鈦(Ti)佔5~60質量比ppm、且其他部分由質量百分比純度99.99%以上的銀(Ag)所構成。鈦(Ti)是為了抑製熔球形成時鈀(Pd)帶來的催化活性。另一方面，鈦(Ti)存在使貴金屬銀合金熔球變硬的傾向，因此，應為5~60質量比ppm。
在本發明之球焊用貴金屬銀合金絲的表面結構中，該拉絲加工面的整體表面上形成總有機碳量(TOC值)為50~3,000μg/m2的有機碳層，是為了降低鍵合絲活性，避免貴金屬銀合金絲與大氣中的硫(S)等結合。本發明之有機碳層指的是成分元素中不含硫(S)的非硫系有機高分子化合物衍生物。由於貴金屬銀合金絲的熔點比純金絲低，因此，有機碳層應為沸點比貴金屬銀合金熔點低的水溶性非硫系有機高分子衍生物，如非離子表面活性劑、陰離子表面活性劑、陽離子表面活性劑、兩性表面活性劑。表面活性劑中，最佳為非離子表面活性劑。例如，和光純藥工業株式會社產的商品名NCW-1001等。此外，也可以是沸點比貴金屬銀合金熔點低的水溶性醇衍生物。可以是總分子量小的乙醇、甲醇或異丙醇衍生物。
本發明之拉絲加工面的整體表面上形成有機碳層，是因為如果存在未形成有機碳層的部位，即使只有一部分，大氣中的硫(S)也會經此與貴金屬銀合金絲的表面結合，形成硫化銀(Ag2S)膜。此外，有機碳層的厚度為總有機碳量(TOC值)50~3,000μg/m2，是因為球焊用鍵合絲的線徑一般為15~25μm，可以根據總有機碳量(TOC值)通過計算簡單地算出有機碳層的有效厚度。50~3,000μg/m2的範圍可以通過純水高溫燙洗及超聲波沖洗、或者有機高分子化合物超稀溶液浸漬來控制，按照控制的容易度，應採用超稀溶液 浸漬。此外，上限為3,000μg/m2，是為了減少鍵合工具上的碳粉粘附/堆積量。因為，雖然本發明之貴金屬銀合金絲的熔點比純金鍵合絲低，但即便如此，碳粉也會粘附、堆積在鍵合工具上。如果考慮鍵合工具更換頻率等操作性，則應為2,400μg/m2，1,800μg/m2則更佳。
水溶性非硫系有機高分子化合物中，如果是非離子表面活性劑、或者乙醇、甲醇或異丙醇等的水溶性醇衍生物，即使表面的總有機碳量超過1,800μg/m2，只要在3,000μg/m2範圍內，在一般鍵合次數為50萬次的連續鍵合作業中不會因碳粉積累而引起毛細管堵塞及夾持器污染等。
如果採用本發明之球焊用貴金屬銀合金絲，則由於縮徑後的惰性連續鑄造面上已形成有機碳層，因此，貴金屬銀合金絲不會立即與大氣中的硫(S)結合而形成牢固的硫化銀。因此，即使將本發明之球焊用貴金屬銀合金絲長期放置於室溫下，鍵合絲表面也不會產生大氣中存在的硫(S)成分所造成的牢固硫化銀(Ag2S)膜。即，本發明之球焊用貴金屬銀合金絲除了成分組成帶來的優良鍵合特性之外，利用超聲波的第二次鍵合性也很卓越，因此，可以保證開始使用前的鍵合絲產品壽命。此外，如果採用本發明之貴金屬銀合金絲，即使反復鍵合，毛細管也不會發生污染。
將具有表1所示之成分組成的貴金屬銀合金(貴金屬成分的純度為：銀(Ag)質量百分比99.999%以上，其他合金成分分別為質量百分比99.99%以上)熔化均勻後進行連續鑄造，得到直徑5mm的粗絲。不對該粗絲進行酸洗處理，而是採用濕式通過金剛石模具連續拉絲，為獲得規定的機械 特性而進行調質熱處理(quenching and tempering treatments)，得到保留了連續鑄造面的直徑為20μm的鍵合絲。然後，連續浸漬於表2所示之各種濃度的非硫系有機化合物水溶液中，得到本發明之球焊用貴金屬銀合金絲(實施品1~實施品15)。
此處，實施品9顯示將鍵合絲浸漬於乙醇濃度為1%的水溶液中後，乾燥時的有機碳量為2,800μg/m2。
實施品15是在製造Ag-3%Pd合金鍵合絲後，浸漬於乙醇稀溶液中，再以純水高溫沖洗之物。
此外，表2所示之非離子表面活性劑為BLUEBELL株式會社銷售的服裝用液體洗滌劑(商品名：Natural)。陰離子表面活性劑為日油株式會社產的商品名：PERSOFT(注册商標)。陽離子表面活性劑為日油株式會社產的 商品名：NISSANCATION(注册商標)。兩性表面活性劑為日油株式會社產的商品名：NISSANANON(注册商標)BD。
按照潔淨室環境(溫度25℃、濕度50%)將該貴金屬銀合金絲在實驗室放置30天後，進行硫化銀(Ag2S)膜厚測量、第二次鍵合鍵合性試驗及毛細管堵塞試驗，得到表3的結果。
【比較例】
將具有表1所示之成分組成的貴金屬銀合金熔化均勻後進行連續鑄造，得到直徑5mm的粗絲。對於用稀硝酸對該粗絲進行表面酸洗和未進行酸洗之物進行與實施例一樣的操作，得到比較例之球焊用貴金屬銀合金絲(比較品16~比較品18)。
此處，比較品16是在對Ag-2.5%Pd合金進行連續鑄造，得到直徑5mm的粗絲後，用稀硝酸進行表面酸洗，連續拉絲，製造鍵合絲，然後浸漬於乙醇超稀溶液中，不放置30天，而是在當天開始試驗之物。
比較品17是在對Ag-4%Pt合金進行連續鑄造，得到直徑5mm的粗絲後，用稀硝酸進行表面酸洗，連續拉絲，製造鍵合絲，然後形成非離子表面活性劑衍生的有機碳膜，放置30天后，進行膜厚測量及試驗之物。
比較品18是在製造超出金(Au)含量下限的Ag-0.07%Au合金鍵合絲後，形成了超出有機碳量上限之兩性表面活性劑衍生的有機碳膜之物。
對於該貴金屬銀合金絲(比較品17~18)，進行了以室溫在實驗室放置30天後的硫化銀(Ag2S)膜厚測量、第二次鍵合鍵合性試驗及毛細管堵塞試驗，得到表3的結果。 但是，如上所述，比較品16沒有放置，而是在當天開始了膜厚測量及試驗。
[總有機碳量(TOC)的測量]
總有機碳量的測量為，分別稱量1000m貴金屬銀合金絲，加入200g的0.1N-NaOH水溶液，用水浴煮沸30分鐘，進行萃取，冷却後加入2.5ml的8N-HCl，輕輕振蕩，在高純度空氣下起泡15分鐘。將其放入株式會社島津製作所產TOC-5000型有機碳分析儀中，測量有機碳濃度，根據該值計算總有機碳重量，除以20μm直徑的貴金屬銀合金絲的表面積，作為表面的非離子表面活性劑的總有機碳量。
[硫化銀(Ag2S)膜厚的測量]
形成於鍵合絲表面的硫化銀(Ag2S)的測量使用膜厚測量儀(ECI公司產、型號QC200)進行。實施品1~實施品15、以及比較品16的硫化銀(Ag2S)膜厚均為10nm以下。而比較品17~18均為20nm以上。
[經過30天後的第二次鍵合鍵合性試驗]
第二次鍵合之鍵合性試驗是使用株式會社新川產鍵合機，使環長為2mm、環高為200μm，用規定的拉鈎對距第二鍵合點20%的位置進行拉伸試驗時的鍵合强度。實施品1~實施品15、以及比較品16的結果優良，但與比較品16對比的比較品17的結果不理想。這是因為硫化銀(Ag2S)形成所致。
[毛細管堵塞試驗]
毛細管堵塞試驗使用新毛細管開始鍵合，計算鍵合次數，直到毛細管堵塞、不能鍵合為止。結果如表3所示。
從經過30天後的第二次鍵合鍵合性試驗可以明確知道，本發明之球焊用貴金屬銀合金絲實施品1~實施品15、以及比較品16的斷裂强度均為4.0克力(gf)以上，優良；而比較例之球焊用貴金屬銀合金絲(比較品17~18)則不理想。
從毛細管堵塞試驗可以明確知道，本發明之球焊用貴金屬銀合金絲(實施品1~8及10~15、比較品16及17)均在鍵合次數超過100萬次後也沒有發生毛細管堵塞，優良；而比較例之球焊用貴金屬銀合金絲(特別是比較品18)在25萬次時就發生了毛細管堵塞。
從上述實施例及比較例可以明確知道，本發明之相關實施品不僅沒有發生毛細管堵塞，而且以室溫在實驗室中放置30天後的鍵合特性優良。具體可知，就比較品而言，儘管鍵合絲剛製造後，第二次鍵合特性優良(比較品16)，但經過30天後，硫化銀(Ag2S)膜深入，第二拉伸强度變得極低(比較品17~18)；而本發明的相關實施品1~15在放置30天後也未產生或基本上未產生硫化銀(Ag2S)膜，第二拉伸强度高。此外還得知，TOC值越高則毛細管堵塞發生越快(比較品18)使得操作性變差。
【產業利用性】
本發明之球焊用貴金屬銀合金絲除了應用於通用IC、離散式IC(discrete IC)、記憶體IC外，還具有既要求高溫高濕用途又要求低成本的LED用IC封裝、汽車半導體用IC封裝、難以使用銅(Cu)鍵合絲的防禦、航天、航空產業用IC封裝、或醫療用途及光電耦合器等半導體用途。

Claims (5)

  1. 一種球焊用貴金屬銀合金絲，其特徵在於：在質量百分比純度99.9%以上的鈀(Pd)佔質量百分比0.1~6%，且其餘部分由質量百分比純度99.99%以上的銀(Ag)構成的球焊用貴金屬銀合金絲的表面結構中，鈀(Pd)佔質量百分比3.0~4.8%，且其餘部分由銀(Ag)構成的鍵合絲表面是連續鑄造面經金剛石模具縮徑後的拉絲加工面，該拉絲加工面的整體表面上係形成總有機碳量(TOC值)為50~3,000μg/m2且由沸點比上述貴金屬銀合金的熔點低的水溶性非硫系有機高分子衍生的有機碳層。
  2. 如請求項第1項所述之球焊用貴金屬銀合金絲，其中，該鈀(Pd)的純度為質量百分比99.99%以上。
  3. 如請求項第1項所述之球焊用貴金屬銀合金絲，其中，該貴金屬銀合金係質量百分比純度99.99%以上的鈀(Pd)佔質量百分比3.0~4.8%、鈦(Ti)佔5~60質量比ppm、且其他部分由質量百分比純度99.99%以上的銀(Ag)所構成。
  4. 如請求項第1項所述之球焊用貴金屬銀合金絲，其中，該有機碳層為沸點比該貴金屬銀合金熔點低之水溶性醇的衍生物。
  5. 請求項第1項所述之球焊用貴金屬銀合金絲，其中，該有機碳層為乙醇、甲醇或異丙醇的衍生物。
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