TW202037756A - 鍍金方法及鍍層皮膜 - Google Patents
鍍金方法及鍍層皮膜 Download PDFInfo
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Abstract
本發明的課題在於提供防止因實裝等的熱履歷而造成導線接合特性降低之鍍金方法及鍍層皮膜。此外,提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法及鍍層皮膜。
解決手段之鍍金方法,係於銅或銅合金皮膜上使用銀觸媒進行鍍層而供導線接合連接之用的鍍金方法,特徵為具有:為了形成鈀皮膜而形成銀皮膜作為銀觸媒之銀觸媒形成步驟,於前述銀觸媒上形成鈀皮膜之鈀皮膜形成步驟,以及在前述鈀皮膜上形成金鍍層皮膜之金鍍層皮膜形成步驟;前述銀皮膜的膜厚為0.05μm~0.5μm。
Description
本發明係關於在銅或銅合金皮膜上使用銀觸媒進行鍍層之供導線接合連接之用的鍍金方法及鍍層皮膜。
從前,供導線接合連接之用的鍍金,係於銅或銅合金皮膜上根據置換反應賦予鈀觸媒,完成鍍鈀之後才進行的。此外,在銅或銅合金皮膜上鍍金,然後鍍鈀,再進行鍍金。
例如在專利文獻1,為了得到導線接合特性良好地導線接合用端子,於導線接合用端子的銅表面,形成鈀純度為99.5重量%(重量百分比)以上的置換鈀鍍層皮膜或者鈀純度為99.5重量%以上的無電解鈀鍍層皮膜、置換金鍍層皮膜、無電解金鍍層皮膜。
此外,在專利文獻2,為了解消無電解鈀的安定性低所導致的異常析出的問題,對被設置電路圖案的基板施以鍍金、鍍鈀、再進行鍍金。
此外,在專利文獻3,揭示了在銅系金屬之上賦予0.05~3mg/dm2
之金作為觸媒核金屬之後,於該銅系金屬之上,使用供進行無電解還原鍍鈀之用的觸媒賦予液,而且構成成分為含有水溶性金化合物、及具有氮原子為2個以上的5元環構造的雜環化合物、以及具有亞胺二乙酸構造的螯合劑之觸媒賦予液,在銅系金屬之上賦予以進行無電解還原鍍鈀為特徵之銅系金屬上的鈀鍍層皮膜。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開2005-197442號公報
[專利文獻2] 日本特開2013-108180號公報
[專利文獻3] 日本特許第5567478號公報
[發明所欲解決之課題]
然而,在專利文獻1~3所記載的方法,由於實裝等熱履歷而有導線接合特性降低的傾向。此外,特別在薄化金鍍層皮膜的膜厚的場合,因前述熱履歷而使導線接合特性降低。
在此,本發明提供防止因實裝等的熱履歷而造成導線接合特性降低之鍍金方法及鍍層皮膜。此外,提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法及鍍層皮膜。
[供解決課題之手段]
相關於本發明之一態樣之鍍金方法,係於銅或銅合金皮膜上使用銀觸媒進行鍍層而供導線接合連接之用的鍍金方法,特徵為具有:為了形成鈀皮膜而形成銀皮膜作為銀觸媒之銀觸媒形成步驟,於前述銀觸媒上形成鈀皮膜之鈀皮膜形成步驟,以及在前述鈀皮膜上形成金鍍層皮膜之金鍍層皮膜形成步驟;前述銀皮膜的膜厚為0.05μm~0.5μm。
如此一來,可以提供防止因實裝等的熱履歷而造成導線接合特性降低之鍍金方法。
此外,在本發明之一態樣,前述鈀皮膜的粒徑為0.09μm以上亦可。
如此一來,鈀的粒徑變大到0.09μm以上,可以提供防止因熱履歷而使鈀粒子擴散/固溶到金皮膜,可以防止導線接合特性的降低。
此外,在本發明之一態樣,前述金鍍層皮膜的膜厚為0.2μm以下亦可。
如此一來,可以提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法。
此外,在本發明之一態樣,前述鈀皮膜的膜厚為0.04μm~0.6μm亦可。
如此一來,鈀粒徑可成長到充分大,所以可防止因熱履歷而使鈀粒子擴散/固溶到金皮膜,可以防止導線接合特性的降低。
此外,相關於本發明之其他態樣的鍍層皮膜,係於銅或銅合金皮膜上使用銀觸媒進行鍍層的供導線接合連接之用的鍍層皮膜,特徵為具有:前述銅或銅合金皮膜、被形成於前述銅或銅合金皮膜上的作為銀觸媒之銀皮膜、被形成於前述銀觸媒上之鈀皮膜,以及被形成於前述鈀皮膜上的金皮膜;前述銀皮膜的膜厚為0.05μm~0.5μm。
如此一來,可以提供防止因實裝等的熱履歷而造成導線接合特性降低之鍍層皮膜。
此外,在本發明之其他態樣,前述鈀皮膜的粒徑為0.09μm以上亦可。
如此一來,鈀的粒徑變大到0.09μm以上,可以提供防止因熱履歷而使鈀粒子擴散/固溶到金皮膜,可以防止導線接合特性的降低。
此外,在本發明之其他態樣,熱處理後的拉線(wire-pull)平均強度為10.0g以上亦可。
如此一來,可以提供即使熱處理後也充分保持導線接合強度之鍍層皮膜。
[發明之效果]
如以上所說明的,根據本發明可以提供防止因實裝等的熱履歷而造成導線接合特性降低之鍍金方法及鍍層皮膜。此外,可以提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法及鍍層皮膜。
以下,參照圖式詳細說明本發明之適宜的實施型態。又,以下說明之本實施型態,並非不當地限定記載於申請專利範圍之本發明的內容者,在本實施型態所說明的構成全部,都不限於作為本發明的解決手段所必須者。
[鍍金方法]
相關於本發明之一實施型態的鍍金方法,係在銅或銅合金皮膜上使用銀觸媒進行鍍層之供導線接合連接之用的方法。如先前已說明的,由於實裝等的熱履歷而有導線接合特性降低的傾向。此外,特別在薄化金鍍層皮膜的膜厚的場合,因前述熱履歷而使導線接合特性降低。這是因為由於熱履歷而使鈀等金屬粒子由金鍍層皮膜的粒界侵入,擴散到金鍍層皮膜中,使金濃度降低,所以導線接合特性降低。
在此,根據相關於本發明之一實施型態之鍍金方法,可以解決前述問題。詳述如下。
相關於本發明之一實施型態之鍍金方法,如圖1所示,特徵為具有:為了形成鈀皮膜而形成銀皮膜作為銀觸媒之銀觸媒形成步驟S10,於前述銀觸媒上形成鈀皮膜之鈀皮膜形成步驟S20,以及在前述鈀皮膜上形成金鍍層皮膜之金鍍層皮膜形成步驟S30;前述銀皮膜的膜厚為0.05μm~0.5μm。
相關於本發明之一實施型態之鍍金方法,具有前述3道步驟。又,銀觸媒形成步驟S10,鈀皮膜形成步驟S20,金鍍層皮膜形成步驟S30之後的水洗,或是供形成銀觸媒、鈀皮膜及金鍍層皮膜之用的前處理,也包含於前述步驟。
銀觸媒形成步驟S10,形成供形成鈀皮膜之用的作為銀觸媒之銀皮膜。相關於本發明之一實施型態的鍍金方法所包含的銀觸媒形成步驟S10,作為供使後述的鈀金屬粒子(粒徑)成長之用的觸媒來使用。
亦可考慮以其他金屬替代銀觸媒作為觸媒使用,例如鈀觸媒(使形成鈀觸媒,形成鈀鍍層皮膜的場合)的場合,鈀膜為晶種狀析出,所以1個1個的結晶粒徑都很小。因此,鈀粒子容易進入金鍍層皮膜的粒界,擴散/固溶。另一方面,銀皮膜為層狀析出,所以1個1個的結晶粒徑很大。接著藉由大幅成長的銀粒子,可以使次一步驟之鈀皮膜的結晶也大幅成長。因此大幅成長的鈀粒子,變得無法容易進入被形成於鈀皮膜上的金鍍層皮膜之粒界,可以防止鈀粒子往金鍍層皮膜之擴散/固溶。也就是說,可以防止金鍍層皮膜中的鈀濃度的上升,維持金鍍層皮膜中的金濃度,所以可防止導線接合特性的降低。
因此,銀皮膜為0.05μm~0.5μm。銀皮膜未滿0.05μm的場合,在次一步驟之鈀皮膜形成步驟形成鈀皮膜變得困難。另一方面,銀皮膜超過0.5μm的話,銀粒徑變小,鈀粒徑也變小所以不佳。因此,導線接合特性降低。
前述鈀皮膜的平均粒徑(以下簡稱粒徑)以0.09μm以上為佳,進而較佳為0.20μm以上。如此一來,鈀的粒徑變大到0.09μm以上,可以提供防止因熱履歷而使鈀粒子擴散/固溶到金皮膜,可以防止導線接合特性的降低。
又,皮膜的粒徑,係以掃描型電子顯微鏡(SEM)觀察皮膜的剖面,把任意選擇的粒子10個取其平均。以下所示的皮膜測定方法也相同。
前述金鍍層皮膜的膜厚以0.30μm以下為佳,進而較佳為0.20μm以下。如此一來,可以提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法。這是因為防止前述鈀擴散/固溶到金鍍層皮膜的緣故。
前述鈀皮膜的膜厚以0.04μm~0.6μm為佳,進而較佳為0.05μm~0.5μm。如此一來,鈀粒徑可成長到充分大,所以可防止因熱履歷而使鈀粒子擴散/固溶到金皮膜,可以防止導線接合特性的降低。
此外,銀觸媒形成步驟S10、鈀皮膜形成步驟S20及金鍍層皮膜形成步驟S30使用的分別的鍍層液,可以是電解鍍層、或無電解鍍層,可以選擇置換型、還原型、置換還原型之中任一種。
熱處理的溫度,以溫度60~300℃為佳,更佳為90~300℃,進而更佳為100~150℃。
此外,因應必要,可以追加清潔、蝕刻、酸洗步驟。清潔、蝕刻、酸洗步驟所使用的藥液可選擇習知的藥液。
相關於本發明之一實施型態的鍍金方法,對於被形成於印刷電路板、BGA基板、封裝基板等地銅或銅合金上特別有效。
由以上所述,根據相關於本發明之一實施型態之鍍金方法,可以提供防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法。此外,可以提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法。進而,根據相關於本發明之一實施型態之鍍金方法,因為不使用鈀觸媒,所以僅在銅或銅合金上被形成銀觸媒,防止鍍金的短路等瑕疵,電路的精密圖案性也優異。
此外,與從前的鍍金方法相比,不使用金觸媒,或可以使金鍍層皮膜更薄,所以成本方面是有利的。此外,亦有適用在無青銅鍍銀的可能性。
[鍍層皮膜]
其次說明相關於本發明的其他實施型態之鍍層皮膜。相關於發明的其他實施型態的鍍層皮膜100,係在銅或銅合金皮膜40上使用銀觸媒進行鍍層之供導線接合連接之用的鍍層皮膜。
相關於本發明之其他態實施型態的鍍層皮膜100,如圖2所示,特徵為具有:銅或銅合金皮膜40、被形成於前述銅或銅合金皮膜40上的作為銀觸媒之銀皮膜10、被形成於前述銀觸媒上之鈀皮膜20,以及被形成於前述鈀皮膜20上的金皮膜30;前述銀皮膜10的膜厚為0.05μm~0.5μm。
如前所述,銀皮膜為層狀析出,所以1個1個的結晶尺寸很大。接著藉由大幅成長的銀粒子11,可以使銀觸媒上的鈀皮膜20的結晶也大幅成長。因此大幅成長的鈀粒子21,變得無法容易進入被形成於鈀皮膜20上的金皮膜30之粒界,可以防止鈀粒子21往金皮膜30之擴散/固溶。也就是說,可以防止金皮膜30中的鈀濃度的上升,維持金皮膜中的金濃度,所以可防止導線接合特性的降低。
前述鈀皮膜20的粒徑,以0.09μm以上為佳,進而較佳為0.20μm以上 。如此一來,鈀的粒徑變大到0.09μm以上,可以提供防止因熱履歷而使鈀粒子21擴散/固溶到金皮膜,可以防止導線接合特性的降低。
熱處理後的拉線(wire-pull)平均強度為10.0g以上為較佳。如此一來,可以提供即使熱處理後也充分保持導線接合強度之鍍層皮膜。此處所謂的熱處理,係指175℃處理16小時之條件。此外,拉線平均強度之引線接合強度,使用Dage#4000之裝置,在電線拉力測試之測定方法。
由以上所述,根據相關於本發明之其他實施型態之鍍層皮膜,可以提供防止因實裝等之熱履歷而使導線接合特性降低之鍍層皮膜。此外,可以提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍層皮膜。進而,根據相關於本發明之其他實施型態之鍍層皮膜,因為不使用鈀觸媒,所以僅在銅或銅合金上被形成銀觸媒,防止鍍金的短路等瑕疵,電路的精密圖案性也優異。
[實施例]
其次藉由實施例詳細說明相關於本發明之一實施型態之鍍金方法及鍍層皮膜。又,本發明並不以這些實施例為限定。
[實施例1]
在實施例1,作為被鍍物,使用被施作5cm×5cm銅皮膜的上村工業製造的BGA基板。於該基板的銅皮膜上,銀觸媒形成步驟S10,形成了供形成鈀皮膜之用的作為銀觸媒之銀皮膜。
其次,鈀皮膜形成步驟S20,於前述銀觸媒上形成鈀皮膜。又,鈀皮膜藉由無電解鍍來形成。
接著,金鍍層皮膜形成步驟S30,於前述鈀皮膜上形成金鍍層皮膜。又,鈀皮膜藉由無電解鍍來形成。
此時,銀皮膜的膜厚為0.05μm,鈀皮膜的膜厚為0.1μm,金鍍層皮膜的膜厚為0.1μm。此外,鈀的平均粒徑為0.25μm。又,各皮膜的測定,使用螢光X線裝置SFT-9550(SII)來測定。鈀的平均粒徑,係以附屬EBSD檢測器Digiview5(EDAX)的電場放出型掃描型電子顯微鏡(FE-SEM)測定皮膜的剖面,取任意選擇的粒子10個之平均。
如以上所述,形成作為銀觸媒之銀皮膜,鈀皮膜,以及金鍍層皮膜。
前述3道步驟S10、S20、S30之後,在熱處理的前後,實施前述金鍍層皮膜的導線接合及拉線試驗,以得到的拉線平均強度進行評估。導線接合裝置使用HB16(TPT)。接合條件為毛細管B1014-51-18-12(PECO),導線使用1mil Au線(SPM),載台溫度為150℃,超音波250mW(1st)、250(2nd),接合時間200ms(1st)、50ms(2nd),拉伸力25gf(1st)、50gf(2nd),步幅0.7mm。此外,導線接合強度的測定方式為拉線測試,裝置為Dage#4000,測試速度為170μm/秒。
如此進行,測定了在金鍍層皮膜後熱處理前之拉線平均強度。結果為10.8g。
接著,進行175℃、16小時之熱處理,再度以前述方法測定導線接合強度,以拉線平均強度進行了評估。結果為10.7g。
[實施例2]
在實施例2,銀觸媒的膜厚為0.10μm。此外,鈀的平均粒徑為0.28μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.3g,熱處理後的拉線平均強度為10.4g。
[實施例3]
在實施例3,銀觸媒的膜厚為0.20μm。此外,鈀的平均粒徑為0.30μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.2g,熱處理後的拉線平均強度為10.3g。
[實施例4]
在實施例4,銀觸媒的膜厚為0.30μm。此外,鈀的平均粒徑為0.24μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.5g,熱處理後的拉線平均強度為10.2g。
[實施例5]
在實施例5,銀觸媒的膜厚為0.50μm。此外,鈀的平均粒徑為0.09μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.4g,熱處理後的拉線平均強度為10.2g。
[比較例1]
在比較例1,替代銀觸媒形成步驟S10,而實施賦予鈀觸媒之鈀觸媒賦予步驟。鈀的平均粒徑為0.04μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.4g,熱處理後的拉線平均強度為7.4g。
[比較例2]
在比較例2,實施了銀觸媒形成步驟S10,但銀觸媒的膜厚為0.01μm。此外,因銀觸媒的膜厚太薄,未被形成鈀皮膜。此外,熱處理前的拉線平均強度為10.0g,熱處理後的拉線平均強度為7.1g。
[比較例3]
在比較例3,實施了銀觸媒形成步驟S10,但銀觸媒的膜厚為0.04μm。此外,因銀觸媒的膜厚太薄,鈀皮膜有一部分未析出,無法進行鈀皮膜的測定。此外,熱處理前的拉線平均強度為10.0g,熱處理後的拉線平均強度為7.0g。
[比較例4]
在比較例4,實施了銀觸媒形成步驟S10,但銀觸媒的膜厚為0.55μm。此外,鈀的平均粒徑為0.08μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.6g,熱處理後的拉線平均強度為9.1g。
[比較例5]
在比較例5,銀觸媒的膜厚為1.00μm。此外,鈀的平均粒徑為0.07μm。其他與實施例1相同。此外,熱處理前的拉線平均強度為10.5g,熱處理後的拉線平均強度為8.7g。
以上之條件及結果顯示於表1。
在所有的實施例,在熱處理前後拉線平均強度沒有差異,所以可以防止熱履歷導致導線接合特性的降低。此外,鈀皮膜的粒徑為0.09μm以上時,可以防止因熱履歷而使導線接合特性降低。這應該是鈀粒子無法容易侵入金鍍層皮膜的粒界,防止了擴散/固溶的緣故。
另一方面,在未實施銀觸媒形成步驟S10的比較例1,在熱處理前後拉線平均強度之差異很大,發生了因熱履歷導致導線接合特性的降低。
此外,作為銀觸媒形成步驟S10之銀觸媒的銀皮膜為0.01μm的比較例2或比較例3,銀皮膜太薄,所以無法形成鈀皮膜,鈀皮膜未析出或者部分未析出,發生了因熱履歷導致導線接合特性的降低。
此外,作為銀觸媒形成步驟S10之銀觸媒的銀皮膜為0.55μm以及1.00μm的比較例4及比較例5,發生了因熱履歷導致導線接合特性的降低。進而,越變得厚膜化,鈀的平均粒徑變小,熱履歷導致導線接合特性的降低很大。這應該是厚膜化使銀及鈀的結晶粒徑變小的緣故。
由以上所述,藉由適用相關於本實施型態之鍍金方法及鍍層皮膜,可以提供防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法及鍍層皮膜。此外,可以提供即使薄化金鍍層皮膜的膜厚,也防止因實裝等之熱履歷而使導線接合特性降低之鍍金方法及鍍層皮膜。
又,如前所述針對本發明之各實施型態及各實施例詳細地說明,但也可能包含實體上不逸脫於本發明的新事項以及效果之種種變形,這對熟悉該項技藝者而言應可容易理解。亦即,這樣的變形例全都包含於本發明之範圍。
例如,於說明書或者圖式中,至少出現一次的用語,與更為廣義或是同義的不同用語一起記載的用語,無論在說明書或圖式的哪個地方,都可以置換為該不同的用語。此外,鍍金方法及鍍層皮膜的構成、動作,也不限定於本發明之各實施型態及各實施例所說明的,可以進行種種變形實施。
S10:銀觸媒形成步驟
S20:鈀皮膜形成步驟
S30:金鍍層皮膜形成步驟
10:銀皮膜
11:銀粒子
20:鈀皮膜
21:鈀粒子
30:金皮膜
40:銅或銅合金皮膜
100:鍍層皮膜
[圖1]係顯示關於本發明之一實施形態的鍍金方法的概況之步驟圖。
[圖2]係顯示關於本發明之其他實施型態之鍍層皮膜的剖面之概略圖。
Claims (7)
- 一種鍍金方法,係於銅或銅合金皮膜上使用銀觸媒進行鍍層而供導線接合連接之用的鍍金方法,其特徵為具有: 為了形成鈀皮膜而形成銀皮膜作為銀觸媒之銀觸媒形成步驟, 於前述銀觸媒上形成鈀皮膜之鈀皮膜形成步驟,以及 在前述鈀皮膜上形成金鍍層皮膜之金鍍層皮膜形成步驟; 前述銀皮膜的膜厚為0.05μm~0.5μm。
- 如請求項1之鍍金方法,其中 前述鈀皮膜的粒徑為0.09μm以上。
- 如請求項1或2之鍍金方法,其中 前述金鍍層皮膜的膜厚為0.2μm以下。
- 如請求項1或2之鍍金方法,其中 前述鈀皮膜的膜厚為0.04μm~0.6μm。
- 一種鍍層皮膜,係於銅或銅合金皮膜上使用銀觸媒進行鍍層的供導線接合連接之用的鍍層皮膜,其特徵為具有: 前述銅或銅合金皮膜、 被形成於前述銅或銅合金皮膜上的作為銀觸媒之銀皮膜、 被形成於前述銀觸媒上之鈀皮膜,以及 被形成於前述鈀皮膜上的金皮膜; 前述銀皮膜的膜厚為0.05μm~0.5μm。
- 如請求項5之鍍層皮膜,其中 前述鈀皮膜的粒徑為0.09μm以上。
- 如請求項5或6之鍍層皮膜,其中 熱處理後的拉線平均強度為10.0g以上。
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JP3594724B2 (ja) * | 1995-09-29 | 2004-12-02 | 大日本印刷株式会社 | リードフレームの部分貴金属めっき方法 |
JP2002057444A (ja) * | 2000-08-08 | 2002-02-22 | Kyocera Corp | 配線基板 |
JP2002111188A (ja) * | 2000-10-04 | 2002-04-12 | Kyocera Corp | 配線基板 |
JP2002124538A (ja) * | 2000-10-12 | 2002-04-26 | Eastern Co Ltd | 回路基板 |
JP2002167676A (ja) * | 2000-11-24 | 2002-06-11 | Millenium Gate Technology Co Ltd | 無電解金メッキ方法 |
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EP1245697A3 (de) * | 2002-07-17 | 2003-02-19 | ATOTECH Deutschland GmbH | Verfahren zum aussenstromlosen Abscheiden von Silber |
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WO2008038681A1 (fr) * | 2006-09-26 | 2008-04-03 | Hitachi Metals, Ltd. | Composant de substrat céramique et composant électronique utilisant celui-ci |
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KR100885673B1 (ko) * | 2008-01-25 | 2009-03-02 | 와이엠티 주식회사 | 솔더링 및 와이어 본딩을 위한 은-팔라듐 도금층이 형성된고밀도 인쇄회로기판 및 그 도금방법 |
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CN111809170A (zh) | 2020-10-23 |
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