TWI761637B - 鈀被覆銅接合線及其製造方法 - Google Patents
鈀被覆銅接合線及其製造方法 Download PDFInfo
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- TWI761637B TWI761637B TW107143373A TW107143373A TWI761637B TW I761637 B TWI761637 B TW I761637B TW 107143373 A TW107143373 A TW 107143373A TW 107143373 A TW107143373 A TW 107143373A TW I761637 B TWI761637 B TW I761637B
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- Prior art keywords
- palladium
- concentration
- wire
- less
- coated copper
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 817
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 125
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Abstract
本發明提供一種鈀被覆銅接合線,其在第一接合時不會產生縮孔,接合可靠度高,即使在高溫、高濕的環境下亦可長期維持優良的接合可靠度。 本發明之鈀被覆銅接合線中,相對於銅、鈀與硫族元素的總和,鈀濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共50質量ppm以下;硫濃度為5質量ppm以上、12質量ppm以下,或是硒濃度為5質量ppm以上、20質量ppm以下,或是碲濃度為15質量ppm以上、50質量ppm以下,從形成於線材前端之焊球的前端部表面至5.0nm以上、100.0nm以下的範圍內具有鈀濃化區域,其中相對於銅與鈀的總和,鈀濃度平均為6.5原子%以上、30.0原子%以下。
Description
本發明係關於一種鈀被覆銅接合線及其製造方法,其適用於半導體元件之電極與外部電極的球焊。
一般係藉由打線接合來連接半導體元件的電極與用於半導體的電路配線基板上的外部電極。該打線接合中,藉由稱為球體接合的方式來接合半導體元件的電極與接合線的一端(第一接合),而藉由稱為楔形接合的方式來接合接合線的另一端與外部電極(第二接合)。球體接合中,接合線的前端會形成熔融球體,使接合線透過該熔融球體連接於例如半導體元件上的鋁電極表面。
熔融球體的形成中,首先使接合線的前端成為鉛直方向,在與放電炬之間藉由放電結球(EFO)方式形成電弧放電,藉由該放電電流對於線材前端輸入熱能。接合線的前端會因為該熱能的輸入被加熱而熔融。熔融金屬藉由其表面張力沿著線材向上,而在線材前端形成正球狀的熔融球體,再藉由凝固而形成焊球(FAB)。接著,加熱半導體元件的電極至140~300℃左右的同時、施加超音波的狀態下,將焊球壓接於電極上,藉此將接合線的一端接合至鋁電極上。
打線接合中,雖使用線徑10~30μm左右的金線,但因為金非常昂貴,因此在部分可替代之處使用銅線。然而,銅線具有容易氧化的問題,為了解決氧化的問題,而使用在表面被覆鈀的鈀被覆銅線。
然而,鈀被覆銅線中,例如具有要兼顧球體表面的氧化所影響的鋁電極的接合穩定性與迴路穩定性的課題。對此,有人提出例如使銅芯材含硫的鈀被覆銅線(例如,參照專利文獻1。)。
鈀被覆銅線,雖具有銅本身所具有的線材及焊球氧化的問題以及因被覆而經常有損其特性改良的問題,但因為比金更為低價,因此在個人電腦及其周邊設備、通信用設備等的民生設備等,於較為寬鬆之條件下的使用中快速普及。再者,近幾年鈀被覆銅線的改良持續進步,即使針對在車用裝置等,在嚴苛條件下使用的接合線,亦逐漸轉移至鈀被覆銅線。因此要求鈀被覆銅線可承受極嚴苛且變化激烈的條件,以適用於車用裝置。具體而言,要求其可承受從熱帶地方或沙漠等的高溫、高濕地區到寒冷地區、並且從山區到臨海地區的廣泛自然環境及其變化,更要求其能夠承受因道路事件或交通事件所產生的衝擊及振動。再者,近年來不僅是汽車的引擎室內部,亦開始研究將其應用於飛機所搭載的半導體產品。因此,要求一種鈀被覆銅接合線,其接合可靠度可承受從民生用途之較為和緩的條件到嚴苛條件下的使用,而能夠滿足比以往更高等級的可靠度之要求。
在開發滿足這種高可靠度之要求的鈀被覆銅線的過程中,嘗試藉由在焊球表面形成鈀濃度高的合金層及濃化層,以提升接合壽命(例如參照專利文獻2、3)。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2012-156307號公報 [專利文獻2]國際公開2016/189758號 專利文獻3]日本特開2017-92078號公報
[發明所欲解決之課題]
然而得知,相較於以往用於較寬鬆條件之用途的線材(未提高鈀濃度的線材),藉由提高焊球表面的鈀濃度,雖可提升接合壽命,但在以嚴苛條件下使用為目標時,仍然偶爾會有接合壽命不夠長的情況。本案發明人等在這種接合壽命未延長的鈀被覆銅線中,觀察到焊球的表面產生很大的縮孔,因此推定其為阻礙接合壽命延長的主要原因。亦即,本案發明人等認為若在焊球具有縮孔的狀態下接合至鋁電極上,則在接合界面上會產生間隙,而以該間隙作為起點進行腐蝕,結果導致接合壽命降低。
關於其原因,本案發明人等詳細研究的結果,得到以下的結論:在第二接合後,在被截斷的線材端部上,附著有鍍覆於外部電極表面的金或銀的一部分,以該金或銀成為起點,而在焊球中產生了縮孔。
本發明為了解決上述課題,而提供一種鈀被覆銅接合線,其在球體形成時,不會在球體表面產生會演變為問題的大縮孔,即使在高溫、高濕的環境中,亦可維持球焊的接合可靠度。又,本發明之目的係提供一種即使在高溫、高濕的環境中仍可維持高接合可靠度的鈀被覆銅接合線的製造方法。 [解決課題之手段]
本發明的鈀被覆銅接合線,具有以銅為主成分的芯材與該芯材上之鈀層、且含有硫族元素;相對於該鈀被覆銅接合線的銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共50質量ppm以下;硫(S)濃度為5質量ppm以上、12質量ppm以下,或是硒(Se)濃度為5質量ppm以上、20質量ppm以下、或是碲(Te)濃度為15質量ppm以上、50質量ppm以下;且從形成於線材前端之焊球的前端部表面至5.0nm以上、100.0nm以下的範圍內具有鈀濃化區域,其中相對於銅與鈀的總和,鈀的濃度為平均6.5原子%以上、30.0原子%以下。
本發明的鈀被覆銅接合線,係在上述組成的線材中,於形成焊球時,可在其前端部表面形成上述組成的鈀濃化區域,因此可提升第一接合的接合可靠度,並且可抑制焊球產生縮孔。
本發明的鈀被覆銅接合線中,相對於銅、鈀與硫族元素的總和,源自該鈀層的鈀濃度較佳為1.0質量%以上、2.5質量%以下。
本發明的鈀被覆銅接合線中,特別是若源自鈀層的鈀濃度在上述範圍內,容易形成上述組成的鈀濃化區域,因此容易兼顧提升第一接合的接合可靠度與抑制焊球產生縮孔。
本發明的鈀被覆銅接合線中,在檢測該鈀濃化區域時,焊球的形成條件,較佳為放電電流值65mA,球體直徑為線徑的1.8倍,且在氮與氫的混合氣體的存在下。
檢測鈀濃化區域時,要在可用於球體接合的所有形成條件中進行分析非常困難,但只要代表性地在上述條件下檢測到鈀濃化區域,則在其他條件下亦可檢測到同等的鈀濃化區域。因此,可提升第一接合的接合可靠度,並且抑制焊球產生縮孔。
另外,本發明中,該鈀濃化區域之鈀濃度的測量條件是,使歐傑電子能譜分析條件作為裝置的設定條件如下即可:一次電子束的加速電壓10kV,從設定值算出的測量區域在15μm2
以上、20μm2
以下,氬離子濺鍍的加速電壓1kV、濺鍍速度2.5nm/分(SiO2
換算)。
另外,鈀被覆銅接合線的線徑較佳為10μm以上、30μm以下。
本發明的鈀被覆銅接合線中,該硫族元素的50.0%以上較佳係被包含於該鈀層內。
本發明的鈀被覆銅接合線中,較佳係在「從該鈀被覆銅接合線的表面」至「相對於鈀與銅之總和,鈀成為50.0原子%的部位」之間,含有該硫族元素的50.0%以上。
本發明的鈀被覆銅接合線中,因為鈀層內含有硫族元素,因此容易形成上述的鈀濃化區域。
本發明的鈀被覆銅接合線中,該鈀層的表面較佳係具有金層。
本發明的鈀被覆銅接合線,即使在鈀層表面具有金層,亦可與不具有金層的情況相同地形成鈀濃化區域,而能夠提升第一接合的接合可靠度,並且抑制焊球產生縮孔。
本發明的鈀被覆銅接合線的製造方法,鈀被覆銅接合線具有以銅為主成分的芯材與在該芯材上的鈀層,並且含有硫族元素;其中相對於銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下;硫族元素濃度共50質量ppm以下,硫(S)濃度為5質量ppm以上、12質量ppm以下,或是硒(Se)濃度為5質量ppm以上、20質量ppm以下,或是碲(Te)濃度為15質量ppm以上、50質量ppm以下;其中準備以銅為主成分的銅線材,並在該銅線材的表面形成包含該硫族元素的鈀層。
本說明書中「~」的符號表示包含其左右之數值的數值範圍。 [發明之效果]
根據本發明的鈀被覆銅接合線,在球體形成時,不會在球體表面產生會演變為問題的大縮孔,在用於球焊的情況中,即使在高溫、高濕的環境下,亦可長期維持優良的接合可靠度。又,根據本發明的鈀被覆銅接合線的製造方法,可提供一種即使在高溫、高濕的環境下亦可維持高接合可靠度的鈀被覆銅接合線。
以下詳細說明本發明的實施態樣。本實施態樣的鈀(Pd)被覆銅接合線,具有以銅為主成分的芯材與該芯材上的鈀層。接著,鈀被覆銅接合線包含硫族元素,且相對於銅、鈀與硫族元素之總和的鈀濃度為1.0~4.0質量%,在包含2種以上的硫族元素的情況下,其濃度共為50質量ppm以下。
本實施態樣的鈀被覆銅接合線中,相對於線材整體的銅、鈀與硫族元素的總和,源自銅芯材的鈀濃度較佳為1.5質量%以下。若含有1.5質量%以下的源自銅芯材的鈀,則不會使電阻值上升,容易得到第一接合的高可靠度。銅芯材含鈀的情況,係以源自鈀層的鈀濃度與源自銅芯材的鈀濃度之總和作為線材整體的鈀濃度。相對於線材整體的銅、鈀與硫族元素的總和,源自鈀層的鈀濃度較佳為1.0~2.5質量%。
本實施態樣的鈀(Pd)被覆銅接合線,鈀的濃度為1.0質量%以上,且以既定量包含硫族元素的各元素,藉此可提高球體接合的可靠度,因此即使在高溫、高濕下亦可長期間維持優良的球體接合性。藉由使鈀的濃度在4.0質量%以下,尤其使源自鈀層的鈀濃度為2.5質量%以下,可抑制焊球(FAB)產生縮孔。如此,鈀的濃度為1.0~4.0質量%、且以既定量包含硫族元素的各元素,可兼具球體接合的高可靠度與抑制在焊球形成時產生縮孔。
從可得到球體接合之高可靠度的觀點來看,源自鈀層的鈀濃度較佳為1.3質量%以上。從抑制縮孔之觀點來看,源自鈀層的鈀濃度較佳為2.3質量%以下。
分別測量線材整體的鈀濃度與銅芯材中的鈀濃度,使用該等濃度可算出源自鈀層的鈀濃度。具體而言,可藉由二次離子質譜分析(SIMS)分析,以下述方式進行分析。首先,將測量對象的線材加壓以使其平坦化。使用SIMS分析裝置(例如,CAMECA製IMS-7f二次離子質譜分析裝置),對其測量銅(Cu)芯材中的鈀濃度。在上述分析裝置內,藉由濺鍍去除上述經平坦化之線材表面的鈀層,使銅露出。為了使銅(Cu)露出,例如在線徑10μm~30μm的線材中,在鈀(Pd)換算下,從表面開始濺鍍至少0.5μm以上,去除鈀層後開始進行SIMS分析,在深度方向上分析至2.0μm。從分析開始的點到分析結束的點(深度2.0μm),測量例如100點以上,算出該100點的平均濃度。分析條件,例如係以一次離子種為Cs+
、一次離子加速電壓15.0keV、1次離子照射區域約30μm×30μm、分析區域約12μm×12μm,以作為SIMS裝置的設定條件。SIMS分析,係藉由質量分析儀檢測使用Cs+
等的一次離子進行濺鍍而放出的二次離子,以進行元素分析,但鈀濃度可使用測量到的鈀(Pd)的二次離子強度,並以鈀(Pd)濃度已知的銅(Cu)線材作為標準樣品,再進行濃度換算而求得。
硫族元素主要係被含有於鈀層內。然而,因為硫族元素極微量,特別在鈀層為極薄的構成中,目前藉由各種分析方法皆無法正確測量硫族元素的存在位置與其濃度。因此,作為與鈀被覆銅接合線整體相對的量,而使硫族元素的量為上述範圍。
本實施態樣的鈀被覆銅接合線,從使用其形成焊球的前端部分(線材頸縮部與相反側之焊球的大約前端部分)的表面,至深度方向5.0nm以上、100.0nm以下的範圍內,可觀測到鈀濃化區域,其中相對於銅與鈀的總和,包含平均6.5~30.0原子%的鈀。
若具有這樣的鈀濃化區域,則可推定在球體表面附近整體或包含前端部分的部分範圍內,形成有層狀且富含鈀的狀態的鈀濃化區域。鈀濃化區域中所含有的鈀,可源自芯材,亦可源自鈀層,亦可為兩者。接著,本案發明人等,根據若形成這樣的鈀濃化區域即可提升第一接合的接合可靠度並且抑制焊球產生縮孔的見解,而完成本發明。具體而言,根據本實施態樣的鈀被覆銅接合線,即使在高溫、高濕的環境下,亦可長期間維持優良的接合可靠度。鈀濃化區域的鈀濃度較佳為7.0~25.0原子%,若在該範圍內,可進一步抑制晶片損傷,並且提升半導體裝置的良率。鈀濃化區域如後所述,可藉由歐傑(FE-AES)分析觀測。
本實施態樣的鈀被覆銅接合線,典型而言,係在鈀層中以上述特定量含有硫族元素,藉此可形成鈀濃化區域。
若使用本實施態樣的鈀被覆銅接合線形成焊球,則在球體熔融時,大部分的鈀不會擴散至球體內部而被吸收,而是留在表面附近。殘留於該表面附近的鈀,在凝固後的球體表面上形成鈀濃化區域。因此,鈀濃化區域,具有上述組成作為殘留於凝固前之焊球表面附近的鈀的痕跡。在與鋁電極接合時,因為在焊球與電極的接合處具有鈀濃化區域,因此可提高球體接合(第一接合)的接合可靠度。
如上所述,本實施態樣的鈀被覆銅接合線,在實施態樣中形成既定組成之鈀濃化區域以作為殘留於焊球表面的鈀的痕跡,藉由這樣的構成,可兼具第一接合的高可靠度與防止焊球形成時的縮孔。
第一接合時的焊球,例如係以下述條件形成。鈀被覆接合線的線徑為10~30μm,較佳為15~25μm,更佳為18~20μm的情況中,電弧放電條件設定如下:放電電流值為30~90mA,焊球徑成為線徑的1.5~2.3倍。接合裝置,例如可使用K&S公司製的接合裝置(IConn ProCu PLUS)等的市售品。使用該接合裝置的情況,裝置的設定較佳係放電時間為50~1000μs,EFO-Gap為25~45mil(約635~1143μm),尾端長度6~12mil(約152~305μm)。使用該接合裝置以外的其他接合裝置的情況,只要因應目標球體直徑,來調整裝置的設定條件而得到與上述相同的球體直徑即可。又,為了使線材前端部為氮與氫之混合氣體環境或氮氣環境,而以氣體流量例如0.2~0.8L/分鐘,較佳為0.3~0.6L/分鐘,更佳為0.5L/分鐘噴吹上述氣體。焊球形成時的氣體,較佳為氮95.0體積%與氫5.0體積%的混合氣體,而作為焊球徑的目標值,可使其在上述的範圍內。
因此,在觀測既定線材是否形成鈀濃化區域時,在上述範圍之中,亦可使放電電流值為65mA、球體直徑成為線徑的1.8±0.3倍、並於氮與氫的混合氣體的存在下所形成的焊球作為代表,藉此測量上述濃化區域。球體直徑為目標值或實測值,但較佳為實測值。
以FE-AES分析來測量鈀濃化區域的情況,其代表性的測量條件,係在線徑10~30μm,較佳為15~25μm,更佳為18~20μm的線材中,以FE-AES電子能譜裝置從焊球前端部的表面分析至深度方向上100.0nm。此時的測量條件,例如FE-AES電子能譜裝置的設定,係一次電子束的加速電壓10kV,電流50nA以下(較佳為50nA),氬離子濺鍍的加速電壓1kV,濺鍍速度2.5nm/分(SiO2
換算)。從設定值算出的測量區域之面積為15μm2
以上、20μm2
以下,使其為例如略圓形或略正方形。具體而言,測量區域可使用直徑5μm的略圓形,或是4μm×4μm的略正方形。另外,設定值的分析區域,較佳係在上述面積中周長較小的區域,例如正方形或圓形較佳。更具體而言,調整到至少由分析區域之外周線所形成之平面圖形的重心,到外周線的最大距離在3μm以下,可得到更正確的分析。為了提升分析精度,在深度方向上均等間隔的9個以上的點進行歐傑分析,並算出其平均值。又,測量區域,可不考量樣品的傾斜,而假設光束垂直照射既定平面的區域,藉此進行評價。
鈀濃化區域,可作為在從該表面至5.0~100.0nm之深度的FE-AES數據圖表中測量到相對於銅與鈀的總和,鈀平均為6.5~30.0原子%的區域。此時,根據測量處,鈀為6.5~30.0原子%的區域有時不會連續,而這樣的情況中,可將包含鈀為6.5~30.0原子%的區域之全部範圍指定為鈀濃化區域。另外,FE-AES數據圖表中,因為會含有附著物等所造成的雜訊,因此係從表面測量至比5nm更深的範圍。
若使用本實施態樣的鈀被覆銅接合線,焊球的鈀濃化區域的鈀濃度,從表面起在深度方向上大致為定值,但通常係形成鈀濃度逐漸減少的態樣。因此,鈀濃化區域較佳在5nm以上、300nm以下的範圍,更佳為400nm以下的範圍。亦即,較佳係從表面到該較佳厚度的範圍內,可觀察到鈀平均濃度為上述特定濃度的鈀濃化區域。鈀濃化區域較厚者,容易得到接合可靠度提升的效果。另一方面,因為鈀相對於線材整體的濃度為上述特定的濃度,因此在線徑為10~30μm時,可視為將鈀濃化區域的厚度抑制在約1.5μm以下,較佳為1.0μm以下。因為鈀濃化區域抑制在上述的厚度,因此不易對半導體晶片造成損傷。
又,若使用上述實施態樣的鈀被覆銅接合線在含鋁的電極上進行球體接合,則在接合面附近可形成鈀濃度相對於鋁、鈀及銅之總和為2.0質量%以上的鈀濃化接合區域。亦即,包含下述區域的範圍即為鈀濃化接合區域:相對於鈀、銅及鋁的總質量,在鋁超過0質量%且在100質量%以下之範圍的各深度中,鈀的質量比例為2.0質量%以上,較佳為5.0質量%以上。接合面係焊球與電極接觸而接合的面。接合面,例如,在FE-SEM/EDX射線分析中,可定義為鋁與銅在圖表中的交點。
藉由具有這種組成的鈀濃化接合區域,可抑制球體接合部的腐蝕,防止破斷及剝離,而可提升接合可靠度。電極,例如係在矽(Si)母材表面被覆Al、AlSiCu(例如,Al-Cu(0.2~0.9質量%)-Si(0.5~1.5質量%))、AlCu(例如,Al-Cu(0.2~0.9質量%))等的電極材料而形成。又,球體接合時的電極溫度為例如140~200℃。
以使用純鋁電極作為接合對象的情況為例,說明該鈀濃化接合區域的分析方法。使用鈀被覆銅接合線,以上述觀測時的焊球形成條件形成焊球,在鋁電極上進行球焊。以使與線材長邊方向之中心線平行的面露出的方式,將球體接合部切斷。從線材側的既定處,在與接合面略為垂直的方向(深度方向)上,對於切剖面進行線型分析。作為線型分析,較佳為例如場發射型掃描式電子顯微鏡/能量色散型X射線光譜分析(FE-SEM/EDX)。
例如在以FE-SEM/EDX射線分析觀察鈀濃化接合區域的情況中,相對於鈀、銅及鋁的總質量,在鋁超過0.5質量%、95.0質量%以下之範圍的各個測量點中,求得相對於鈀、銅及鋁之總和的鈀的質量比例。可將該質量比例為2.0質量%以上,較佳為5.0質量%以上的既定範圍作為鈀濃化接合區域以進行評價。於此,在鋁濃度超過0.5質量%、95.0質量%以下的範圍內進行測量的理由是,會因為分析中的雜訊等的影響,使不存在鋁之處的分析值不會為0質量%,而僅有鋁之處的分析值亦不會為100質量%。
鈀濃化接合區域中的鈀濃度為例如30.0質量%以下,較佳為20.0質量%以下。
鈀接合濃化區域,例如亦有相對於鈀、銅及鋁的總和,鈀為2.0質量%以上的區域不連續的情況。這樣的情況下,在線徑為10~30μm的線材中,例如在FE-SEM/EDX分析的濃度數據圖表中,在將鋁、鈀及銅的總和作為100質量%的情況下,鈀濃度為2.0質量%以上的範圍只要在0.2μm以上,即可評價為存在有鈀接合濃化區域。該鈀濃度為2.0質量%以上的範圍,較佳係存在於從銅與鋁的交點往線材側1.0μm的範圍之間。另外,線分析區域較佳係分析在FE-SEM/EDX對照分析中檢測到鈀強度峰值的區域。
實施態樣的鈀被覆銅接合線,因為可形成這樣的鈀濃化接合區域,因此可抑制球體接合部的腐蝕,並且防止破斷或剝離,而可提升接合可靠度。
從得到高可靠度之接合的觀點來看,上述接合面附近的鈀濃化接合區域的寬度較佳為0.2μm~2.0μm,更佳為0.5μm~1.8μm。
綜合以上所述,實施態樣的鈀被覆銅接合線,係具有以銅為主成分的芯材與該芯材上的鈀層、且含有硫族元素的鈀被覆銅接合線,其中相對於該鈀被覆銅接合線的銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共50質量ppm以下,硫(S)濃度為5質量ppm以上、12質量ppm以下,或是硒(Se)濃度為5質量ppm以上、20質量ppm以下,或是碲(Te)濃度為15質量ppm以上、50質量ppm以下,在將該鈀被覆銅接合線於鋁電極上進行球體接合的線材接合結構中,該鋁電極上的該球體接合面附近形成鈀濃化接合區域,其相對於鋁、鈀與銅之總和的鈀濃度為2.0質量%以上。
又,實施態樣的線材接合結構,係將具有以銅為主成分的芯材與該芯材上的鈀層、且含有硫族元素的鈀被覆銅接合線,在半導體晶片的含鋁電極上進行球體接合的線材接合結構,該鈀被覆銅接合線的線材部分中,相對於銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共50質量ppm以下,硫(S)濃度為5質量ppm以上、12質量ppm以下,或是硒(Se)濃度為5質量ppm以上、20質量ppm以下,或是碲(Te)濃度為15質量ppm以上、50質量ppm以下,該電極上的該球體接合面附近具有鈀濃化接合區域,其中相對於鋁、銅與鈀的總和的鈀濃度為2.0質量%以上。
接著說明本實施態樣的鈀被覆銅接合線的構成。 本實施態樣的鈀被覆銅接合線中的芯材,係以銅為主成分所構成的銅或銅合金。此處的主成分,係指其在含量或特性上為主要成分,若是含量則至少為50.0質量%。作為主成分的特性,係其構成所要求的特性,例如銅芯材的情況,則為線材的破斷力及伸率等的機械性質。主成分,例如係指主要影響這種特性的成分。
銅芯材中,除了銅(Cu)以外,亦可包含不可避免的雜質及添加元素等的微量元素。添加元素,一般係以提升鈀被覆銅接合線的抗氧化性、強韌性等特性為目的而微量添加的元素。這樣的微量元素為例如P、Au、Pd、Pt、Ni、Ag、Rh、In、Ga、Fe等。銅芯材中的微量元素的比例較佳為1.5質量%以下,更佳為1.0質量%以下,再佳為0.01質量%以下,再更佳為0.001質量%以下,特佳為0.0001質量%以下。銅芯材中的微量元素濃度若超過1.5質量%,則會有線材的伸線加工性變差、比電阻上升、或是在第一接合時產生晶片損傷等的疑慮。
銅中的微量元素及線材所含有之元素的含有比例,一般係由感應偶合電漿(ICP)發光光譜分析等的化學分析測量,但不限於此。例如在銅芯材中含有與被覆層相同種類之金屬元素的情況,該金屬元素的含有比例,可與上述銅芯材中的鈀相同地藉由SIMS分析測量。
從線材的表面於深度方向上所進行的歐傑(FE-AES)分析數據圖表中,可將鈀的比例相對於銅與鈀的總和為50.0原子%之處,至鈀層表面的區域作為鈀層來分析。鈀的比例為50.0原子%之處為銅芯材與鈀層的邊界。若鈀層太薄而難以藉由FE-AES分析明確測量鈀層厚度及特定位置的鈀存在比例,則在這樣的情況中,除了FE-AES分析,亦可進一步適當併用掃描式穿透型電子顯微鏡/能量色散型X射線光譜分析(TEM/EDX)進行分析,或是球面像差補償掃描穿透式電子顯微鏡/能量色散型X射線光譜分析(STEM/EDX)進行分析、原子序對比影像(HAADF像)等。
鈀層的厚度雖與鈀被覆銅接合線的線徑相關,但在線徑10μm~30μm的情況中較佳為0.020μm以上、0.150μm以下,更佳為0.030μm以上、0.130μm以下。這是因為鈀層的厚度在上述範圍內越均勻,則在將接合線進行接合時,越能提升耐傾倒性及迴路高度的穩定性等迴路特性的品質。可使用上述FE-AES分析作為鈀層厚度的測量手法,與上述相同地為了提升測量精度,亦可適當併用以TEM/EDX所進行的分析、以STEM/EDX所進行的分析、HAADF像等。
本實施態樣的鈀被覆銅接合線包含硫族元素(硫、硒及碲的1種以上),在包含2種以上硫族元素的情況,硫族元素占線材整體的濃度共50質量ppm以下。較佳為硫族元素占線材整體的濃度共5質量ppm以上,藉此容易得到球體接合的可靠度。從球體接合的可靠度之觀點來看,硫族元素占線材整體濃度的濃度,較佳為總計6質量ppm以上。又,硫族元素濃度若超過50質量ppm,則鈀層變脆,而在伸線加工中鈀層發生裂縫,該裂縫成為起點而導致線材斷線,使得伸線加工性變差。為了提升伸線加工性,硫族元素濃度較佳為45質量ppm以下,更佳為41質量ppm以下。
本實施態樣的鈀被覆銅接合線,在上述硫族元素之中,硫(S)濃度為線材整體的5質量ppm以上,較佳為6質量ppm以上。藉由使硫(S)濃度為5質量ppm以上,可提高球體接合的可靠度。另一方面,硫(S)濃度在線材整體的12質量ppm以下,若超過此值則鈀層變脆而在鈀層中產生裂縫,並以該裂縫為起點而導致線材斷線,使得伸線加工性變差。硫(S)濃度較佳為線材整體的10質量ppm以下
又,硒(Se)濃度為線材整體的5質量ppm以上、較佳為6質量ppm以上,更佳為8質量ppm以上。藉由使硒(Se)濃度為5質量ppm以上,可提高球體接合的可靠度。另一方面,硒(Se)濃度為線材整體的20質量ppm以下,若超過此值則鈀層變脆,而在鈀層中產生裂縫,該裂縫成為起點而導致線材斷線,使得伸線加工性變差。硒(Se)濃度較佳為線材整體的15質量ppm以下。
又,碲(Te)濃度為線材整體的15質量ppm以上,更佳為16質量ppm以上。藉由使碲(Te)濃度為15質量ppm以上,可提高球體接合的可靠度。另一方面,碲(Te)濃度較佳為線材整體的50質量ppm以下,若超過此值則鈀層變脆,而在鈀層中產生裂縫,該裂縫成為起點導致線材斷線,使得伸線加工性變差。碲(Te)濃度較佳為線材整體的45質量ppm以下,更佳為41質量ppm以下。
本實施態樣的鈀被覆銅接合線中,在硫族元素濃度共50質量ppm以下的範圍內,硫、硒、碲任一者若滿足上述濃度範圍,則可僅包含1種硫族元素,亦可包含2種以上。
本實施態樣的鈀被覆銅接合線中,在鈀層上亦可具有由鈀以外的金屬所構成的第二層。第二層的金屬可為純金屬,亦可為2種以上的金屬混合的合金。鈀被覆銅接合線在鈀層上具有第二層的情況,鈀層與第二層的交界的測量,可以第二層的主成分金屬濃度相對於最大濃度為50.0%的部分而測定。第二層表面上具有第三層、第四層的情況中,可依照上述方法進行分析。
本實施態樣的鈀被覆銅接合線,作為鈀層以外的層,較佳係最外層具有金層。本實施態樣的鈀被覆銅線,藉由具有金層,可提升第二接合的接合性,並且可降低伸線加工時的模具損耗。金層係以金為主成分而形成的層。金層只要形成於鈀層的整個表面上,則其一部分亦可間斷,金層中含有鈀亦無妨。金層中含有鈀的情況,鈀濃度可在厚度方向上均勻,亦可具有朝向表面減少的濃度梯度。又,以2種以上之金屬混合的合金構成金層的情況,只要不損及本發明的效果,則在金層中除了鈀與金以外亦可含銀、銅等。此情況的金層中,鈀以外之金屬元素的量,例如小於50.0質量%。
本實施態樣的鈀被覆銅接合線具有金層的情況,源自該金層的金濃度較佳係占線材整體0.01質量%以上,更佳為0.05質量%以上。若源自金層的金濃度為0.01質量%以上,則第二接合性良好,容易降低伸線加工時的模具損耗。源自金層的金濃度較佳係占線材整體0.20質量%以下,更佳為0.15質量%以下。源自金層的金濃度若為0.20質量%以下,則不易對於線材性能有不良的影響,且不易損及焊球的正球性。另外,銅芯材含金的情況中,線材整體的金濃度係上述源自金層之金濃度與銅芯材中的金濃度的總和。因此,測量源自金層的金濃度的情況中,可分別測量線材整體的金濃度與銅芯材中的金濃度,再使用該等濃度算出源自金層的金濃度。源自金層的金濃度,具體而言與上述源自鈀層的鈀濃度相同地可藉由SIMS分析測量。
金層的厚度雖亦與鈀被覆銅接合線的線徑有關,但較佳為8nm以下,更佳為5nm以下。金層的厚度若在8nm以下,則即使在具有金層的情況中,亦不會損及焊球的正球性,而容易維持第一接合的高可靠度。金層厚度的下限並未特別限定,但後述濃度換算的平均膜厚若為1nm以上即充分。作為金層厚度的測量手法,與鈀層相同地可使用FE-AES分析。
另外,若金占線材整體的濃度為上述較佳的範圍,則金層的厚度明顯變薄。像這樣金層厚度明顯變薄的情況,目前難以一般的測量手法正確測量金層的厚度。因此,金層的厚度明顯變薄的情況中,可藉由使用金占線材整體之濃度與線徑所算出的濃度,來換算出平均膜厚以評價金層的厚度。該濃度換算平均膜厚,係從金濃度與金的比重算出每單元長度的金的質量,並假設線材剖面為正圓,金均勻存在於最表面而求得其膜厚的方法,以及使用鍍覆線徑中的金被覆之厚度(亦可為設計值)與最終線徑以進行比例計算的方法。
此處,藉由上述實施態樣的構成而可兼具球體接合的可靠度與抑制縮孔產生的理由為例,推測如下。球體接合中,從放電炬在線材前端形成電弧放電,藉由電弧電流的熱使球體前端熔融而形成焊球。此時,在此之前球體接合部的鈀濃度並未變高的鈀被覆銅線,在藉由電弧導入熱能而熔融的線材之金屬及添加元素形成焊球的過程中,線材外側的鈀被吸收而擴散至熔融球體內部。若將這種以往的線材在含鋁的電極上進行球體接合,則接合面附近並未成為富含鈀的狀態,而在含鋁的電極與球體接合部的接合界面,銅與鋁的金屬間化合物,例如Cu9
Al4
等容易被腐蝕。
半導體產品中,通常係以樹脂等將打線接合整體密封。源自該密封樹脂的氯、溴等的鹵素元素及源自環境中的水分及硫等侵入球體接合界面,腐蝕球體接合界面的銅與鋁的金屬間化合物,而成為了問題。接著,半導體元件的環境越高溫高濕,則具有腐蝕擴大的傾向。若球體接合界面的腐蝕進一步發展,則會有球體接合界面發生剝離或破斷,導致電阻上升而產生通電不良的問題。
相對於此,本實施態樣的特定組成及構成的線材,在焊球的形成過程中,抑制鈀往熔融球體內擴散而被吸收,因而可認為未被吸收的鈀在球體表面附近濃縮分布,覆蓋球體表面。若在該未被吸收的鈀覆蓋焊球表面的狀態下,在含鋁電極上進行球體接合,則成為在接合界面富含耐腐蝕性強的鈀的狀態。因此推測,可抑制銅與鋁的金屬間化合物的形成,並且可抑制從外部侵入的鹵素(特別是氯)、硫、水等所造成的腐蝕。結果,球體接合的可靠度提升,特別是可明顯提升在高溫高濕條件下的可靠度。從這樣的觀點來看,在使球體接合的可靠度提升的範圍內,決定線材中的鈀濃度的下限。
另一方面,如上所述,即使焊球表面為富含鈀的構成,在目標為於嚴苛條件下使用的情況下,有時仍無法提升接合可靠度。其理由被認為是打線接合的第二接合對象物,其表面大多鍍金或鍍銀,而源自該鍍覆的金或銀,在打線接合的第二接合後切斷線材時,會附著於線材的端部(被截斷之線材的端部),而成為縮孔的原因。
「縮孔」係在凝固後的焊球表面觀察到的皺褶狀的溝。在凝固後的焊球表面具有縮孔的情況,會在半導體晶片上之電極中的球體接合面上,與上述溝所對應的地方產生空隙。因此認為,球體接合面的接合強度會根據空隙的尺寸並以該空隙為起點隨著時間變弱,而容易發生腐蝕,導致接合可靠度降低。
於此,本案發明人等詳細研究的結果是,上述縮孔之中,分成會演變為問題的大縮孔與不會演變為問題的小縮孔。亦即,凝固後的焊球表面具有既定尺寸以上之縮孔的情況,電極與球體接合部界面的空隙容易變大,明顯因此導致接合可靠度降低。相對於此,若為小於上述尺寸的縮孔,因為空隙小而對於接合可靠度的影響不會演變為問題。作為這種不會演變為問題的縮孔尺寸,在縮孔的SEM觀察影像中,只要縮孔的最大長度為線材直徑的3分之2以下的長度即可。例如線材直徑為18μm的情況,則可明確地將縮孔的最大長度超過12μm的縮孔判定為會演變為問題的大縮孔。該尺寸以下的縮孔,則可推定為幾乎不影響接合可靠度。
接著發現,產生會演變為問題之大縮孔的原因,與覆蓋焊球表面的鈀濃化區域(實際為鈀與銅混合的區域)之鈀濃度相依。亦即,焊球表面的鈀濃化區域的鈀濃度若超過既定濃度,在鈀濃化區域凝固時,球體內部尚為軟化狀態,故因為在焊球表面附近的金附著處與金未附著之區域的組成差異等的主要原因,導致凝固速度差擴大,金的附著部成為最終凝固部分。接著推論,在熔融球體成為固體時,收縮集中的金附著部分收縮至球體內側,而成為會演變為問題的大縮孔。這在銀附著於端部的情況中亦相同。
相反地,鈀濃化區域的鈀濃度若夠低,則可認為鈀濃化區域與球體內部銅凝固的時間差變小。結果,即使金附著亦不會收縮至球體內側,因此不會產生會演變為問題的大縮孔。從這樣的觀點來決定焊球表面的鈀濃度的上限。焊球產生大縮孔的狀態下,若在含鋁的電極上進行球體接合,則在電極與球體接合部的界面產生空隙。結果,球體接合界面的接合強度變弱,而具有容易腐蝕的問題。
鈀被覆銅接合線中的硫族元素,對於形成上述焊球表面附近的鈀分布區域有所貢獻。硫族元素因為與銅的反應性,而被認為主要在線材之金屬熔融初期的段階,集中於銅與鈀接觸的區域。該集中於銅與鈀之接觸區域的硫族元素與銅的反應產物阻擋了鈀溶入熔融銅之中。從這樣的觀點來決定硫族元素量。
為了得到上述效果,鈀被覆銅接合線整體所含有之硫族元素的50.0%以上,較佳係被含有於從鈀被覆銅接合線的表面到相對於鈀與銅的總和,鈀為50.0原子%的部位之間。藉此認為可輕易在焊球表面附近形成鈀分布區域,而可更提升球體接合的接合可靠度。
接著說明本實施態樣的鈀被覆銅接合線的製造方法。本實施態樣的鈀被覆銅接合線,係使鈀被覆於成為芯材的以銅為主成分的銅線材表面,再進行伸線加工及因應需求的熱處理而得之。鈀被覆後亦可被覆金,又,被覆鈀或金後,亦可實施階段性伸線及熱處理。
使用銅作為芯材的情況,使既定純度的銅熔解,又或者使用銅合金的情況,則使既定純度的銅與添加元素一起熔解,藉此可得到銅芯材的材料或銅合金芯材的材料。可使用電弧加熱爐、高頻加熱爐、電阻加熱爐、連續鑄造爐等的加熱爐進行熔解。為了防止源自大氣中的氧或氫混入的目的,銅熔解時加熱爐中的環境較佳保持為真空或氬、氮等的惰性氣體環境。已溶解之芯材的材料,從加熱爐以成為既定線徑的方式將其鑄造凝固,又或者在鑄造模具中對熔融芯材的材料進行鑄造,製作鑄錠,反覆對該鑄錠實施輥壓延,並伸線至既定線徑,而得到銅線材。
作為在銅線材的表面被覆鈀或金的方法,具有鍍覆法(濕式法)與蒸鍍法(乾式法)。鍍覆法可為電鍍法與無電鍍覆法的任一方法。衝擊電鍍或閃鍍等的電鍍,其鍍覆速度快,若用於鈀鍍覆,則鈀層對於芯材的密合性良好,因而較佳。作為以鍍覆法使鈀層內含有硫族元素的手法,具有在上述電鍍中使用含有硫、硒或碲之鍍覆添加劑的鍍覆液作為鈀鍍覆液,而調整鍍覆添加劑的種類及量的手法。藉此,可調整線材中的硫族元素的濃度。
作為蒸鍍法,可利用濺鍍法、離子鍍法、真空蒸鍍等的物理吸附以及電漿CVD等的化學吸附。根據該等的方法,在形成鈀被覆及金被覆之後不需要進行洗淨,而不會有洗淨時表面汙染等的疑慮。作為以蒸鍍法使鈀層內含硫族元素的手法,具有使用含硫族元素的鈀靶材,藉由磁控濺鍍等形成鈀層的手法。
如此,將經實施鈀被覆與金被覆的銅線材伸線至最終線徑,並進行熱處理。該伸線加工與熱處理亦可階段性進行。又,上述雖說明將施予鈀被覆與金被覆的銅線材伸線至最終線徑的方法,但亦可將已被覆鈀的銅線材伸線至既定線徑後施予金被覆,之後再伸線至最終線徑。
伸線加工的加工率,可因應欲製造之鈀被覆銅接合線所要求的破斷力及伸率等的機械特性決定。加工率,一般而言係作為將鈀被覆與因應需求實施金被覆的銅線材加工至最終線徑時的加工率(從最終鍍覆之後的線徑至最終線徑時的加工率),其較佳為90.0%以上。該加工率,可作為線材剖面積的減少率而算出。較佳係使用複數的鑽石拉絲模階段性地進行伸線加工。此情況中,每一個鑽石拉絲模的面積減少率(加工率)較佳為5.0~15.0%。
最終熱處理,係在最終線徑時執行去除應變的熱處理,以將殘留於線材內部之金屬組織的應變去除。去除應變熱處理條件,可考量所需之線材特性來決定溫度及時間。
此外,可在製造線材的任意段階,因應目的來實施熱處理。作為這樣的熱處理,擴散熱處理在鈀被覆或金被覆後,使相鄰的金屬彼此擴散而提升接合強度。藉由進行擴散熱處理,可提升不同種金屬之間的接合強度。關於擴散熱處理條件,可考量所需之線材特性來決定溫度及時間。
熱處理的方法中,使線材通過加熱至既定溫度的加熱用容器環境之中來進行熱處理的移動式熱處理,因為容易調節熱處理條件而較佳。移動式熱處理的情況,熱處理時間可藉由線材的通過速度與線材在加熱用容器內的通過距離來算出。使用管狀電爐等作為加熱用容器。
根據以上說明的本實施態樣之鈀被覆銅接合線,可抑制球體形成時的縮孔,並且在高溫高濕下球體接合的可靠度亦為優良。因此,由於可形成長期可靠度高的接合結構,而適用於車用裝置等的高溫、高濕的環境。 (半導體裝置及其製造方法)
接著,說明使用上述實施態樣之鈀被覆銅接合線的半導體裝置。如第七圖所示,本實施態樣的半導體裝置1具有:半導體晶片2;含鋁的鋁電極3,其設於半導體晶片2上;外部電極4,其設於半導體晶片2的外部,且具有金被覆;及接合線5,其連接鋁電極3與外部電極4的表面。另外,第七圖中雖以在外部電極上具有金被覆的情況舉例來說明,但與金被覆同時具有銀被覆或是以銀被覆取代金被覆的情況亦相同。
半導體裝置1中,接合線5係由上述實施態樣的鈀被覆銅接合線所構成。又,鋁電極3與接合線5的接合面,具有鈀濃化接合區域,其中相對於鋁電極3之表面的構成元素、銅與鈀的總和,鈀濃度為2.0質量%以上。
半導體晶片2具備由矽(Si)半導體或化合物半導體等所構成的積體電路(IC)而成。鋁電極,例如在矽(Si)母材的表面被覆Al、AlSiCu、AlCu等的電極材料所形成。外部電極4,係用以從外部對半導體晶片2供給電力的電極。源自外部電極4的電力,則是透過接合線5供給至半導體晶片2。
本實施態樣的半導體裝置1的製造中,以接合線5連接鋁電極3與外部電極4,係例如以下述方式進行。使用接合裝置以及使接合線通入其內部而用於連接的焊針工具等,例如藉由電弧放電對於焊針所載持的線材前端輸入熱能,而將線材前端加熱熔融。藉此,在線材前端形成焊球。之後,例如在140~200℃的範圍內將半導體晶片2加熱的狀態下,將該焊球進行壓接於鋁電極3上,而形成第一接合。之後,將與接合線5之第一接合相反的一端藉由超音波壓接直接與外部電極4接合。
本實施態樣的半導體裝置的製造方法中,焊球的形成條件與上述的條件相同。具體而言,例如使用接合裝置,在接合線5的線徑為10~30μm,較佳為15~25μm,更佳為18~20μm的情況中,以使放電電流值為30~90mA、使焊球徑成為線徑之1.5~2.3倍的方式設定電弧放電條件。接合裝置,例如可使用K&S公司製的接合裝置(全自動Cu線接合機;IConn ProCu PLUS)等的市售品。使用該接合裝置的情況,裝置的設定較佳係使放電時間為50~1000μs,EFO-Gap為25~45mil(約635~1143μm),尾端長度為6~12mil(約152~305μm)。使用該接合裝置以外的其他接合裝置的情況,可與上述條件相同,例如焊球徑成為與上述相同之大小的條件即可。又,為了使線材前端部為氮與氫的混合氣體環境或氮氣環境,以氣體流量0.2~0.8L/分鐘,較佳為0.3~0.6L/分鐘噴吹上述氣體。焊球形成時的氣體,較佳為氮95.0體積%與氫5.0體積%的混合氣體,焊球徑的目標值只要在上述範圍內即可。
綜合以上所述,實施態樣的半導體裝置及半導體裝置的製造方法如下。實施態樣的半導體裝置,係具有半導體晶片、設於半導體晶片上的含鋁的鋁電極、設於半導體晶片外部且具有金被覆或銀被覆的外部電極、連接該鋁電極與該外部電極表面之接合線的半導體裝置,其中該接合線係由本發明的鈀被覆銅接合線所構成。
又,實施態樣的半導體裝置,係具有半導體晶片、設於半導體晶片上的含鋁的鋁電極、設於半導體晶片外部且具有金被覆或銀被覆的外部電極、連接該鋁電極與該外部電極表面的接合線的半導體裝置,其中該接合線係由鈀被覆銅線構成,且具有下述線材接合結構:在該鋁電極與該接合線的接合面附近具有鈀濃化接合區域,其中相對於鋁、銅與鈀之總和,鈀濃度為2.0質量%以上。
實施態樣的半導體裝置的製造方法,係具有半導體晶片、設於半導體晶片上的含鋁的鋁電極、設於半導體晶片外部且具有金被覆或銀被覆的外部電極、連接該鋁電極與該外部電極表面的接合線的半導體裝置的製造方法,其中該接合線係具有以銅為主成分的芯材與該芯材上的鈀層、且含有硫族元素的鈀被覆銅接合線所構成,其中相對於該鈀被覆銅接合線的銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共5.0質量%以上、50質量ppm以下。接著,該鈀被覆銅接合線前端,即從球體前端部表面至5.0nm以上、100.0nm以下的範圍內,形成具有鈀濃化區域的焊球,該鈀濃化區域中,相對於銅與鈀的總和,鈀的濃度為平均6.5原子%以上、30.0原子%以下;透過該焊球將該鈀被覆銅接合線接合至該鋁電極,使從該鈀被覆銅接合線的該焊球大致相隔該接合線之長度之處在該外部電極表面上進行第二接合。
實施態樣的半導體裝置例如為車輛用途。
根據以上所說明的本實施態樣的半導體裝置,可在打線接合中,抑制於球體接合時球體的縮孔,即使在高溫高濕下,球體接合可靠度亦優良。因此,可形成長期可靠度高的接合結構,而適合在車用裝置等的高溫、高濕環境下使用。又,根據本實施態樣之半導體裝置的製造方法,可形成長期可靠度高的接合結構,因此可得到適合在車用裝置等的在高溫、高濕環境使用的半導體裝置。 [實施例]
接著說明實施例。本發明不限於以下的實施例。例1~19及例32~34為實施例,例20~31為比較例。
(例1~18)芯材係使用純度99.99質量%以上的銅(Cu),將其進行連續鑄造,一邊進行前熱處理、一邊進行壓延,之後進行一次伸線,得到銅線材(直徑0.5mm)。
鈀被覆層係以下述方式形成。在市售的鈀電鍍浴中添加含硫、硒、碲的添加劑,控制鍍覆浴中的硫、硒、碲的濃度,而使相對於線材整體(銅、鈀及硫族元素的總和)之濃度成為下表記載的濃度,分別製作鍍覆浴。在將銅線材浸漬於該鍍覆浴中的狀態下,以電流密度0.75A/dm2
對銅線材通入電流,以形成含硫、硒或碲的鈀被覆。形成含硫、硒及碲之中2種以上的鈀被覆的情況中,係使用添加上述2種以上之添加劑的鍍覆浴。
之後,不進行烘烤處理,以濕式藉由鑽石拉絲模連續進行二次伸線,進行480℃×1秒的調質熱處理,得到最終線徑18μm或25μm的鈀被覆銅接合線。
另外,以從被覆後的線材到最終線徑為止的伸線前後之線材剖面積所算出各例的平均加工率,其中最終線徑18μm與25μm的平均加工率皆為99.0%以上,伸線加工中的線速為100~1000m/分鐘。
鈀被覆銅接合線中的鈀濃度係以下述方式測量。以王水溶解製造線材1000m左右,以高頻感應偶合電漿發光分光分析法(島津製作所股份有限公司的ICPS-8100)求得該溶液中的鈀(Pd)濃度。
鈀被覆銅接合線中的硫族元素的濃度係以下述方式測量。以王水溶解製造線材100m左右,以感應偶合電漿質量分析計(Agilent Technologies股份有限公司製Agilent8800)求得其溶液中的硫(S)、硒(Se)或碲(Te)濃度。所得之鈀被覆銅接合線的組成顯示於表1、2。
(線材表面裂縫的觀察) 針對鈀鍍覆後的銅線材進行捻轉試驗,以光學實體顯微鏡(OLYMPUS公司製,產品名稱:SZX16)觀察捻轉試驗後的線材表面的外觀,評價鈀的龜裂是否到達芯材的銅。將龜裂未到達銅者評價為線材表面無破裂(○),龜裂到達銅者評價為線材表面有破裂(×)。捻轉試驗,係使用前川試驗機製作所製作的裝置名稱TO-202,將約20cm的樣品線材兩端固定,使其順時針選轉180度、逆時針選轉180度,進行7組之後觀察外觀。結果顯示於表1、2。另外,針對龜裂到達銅的線材,並不實施後續的縮孔及HAST評價等,因此表中顯示為未實施(-)。
(焊球的分析)使用K&S公司製的裝置(全自動Cu線接合機;IConn ProCu PLUS)型超音波裝置,使電弧放電電流值(放電結球(EFO)電流值)為65mA,在50~1000μs的範圍內調節放電時間,而使例1中所得之線徑18μm的鈀被覆銅接合線形成球體直徑約33μm(線徑的約1.8倍)的焊球。焊球形成環境係以氮氣95.0體積%與氫氣5.0體積%的混合氣體,以氣體流量5.0L/分鐘噴吹線材前端。以掃描式歐傑電子能譜儀(日本電子公司製的JAMP-9500F(裝置名))對於形成焊球的前端側(線材頸部與相反側)的約略中心進行深度方向分析。歐傑電子能譜儀的設定條件為一次電子束的加速電壓10kV、電流50nA、電子束徑5μm、氬離子濺鍍的加速電壓1kV、濺鍍速度2.5nm/分鐘(SiO2
換算)。從焊球前端部表面至深度方向上5.0~100.0nm為止,以等間隔分析9個點以上,求得相對於銅與鈀之總和之鈀的平均濃度。分析處具體而言係從表面至約略0~30.0nm為止,每1.0nm一處、共31處,從31.0至60.0nm為止,每6nm一處、共5處,從61.0至480.0nm為止,每12.0nm一處、共35處。
例2~32中,使用與上述相同的全自動Cu線接合機,分別調節放電結球(EFO)電流為30~90mA的範圍內及放電時間在50~1000μs的範圍內為既定的值,其他則以與例1相同的條件,使上述所得之鈀被覆銅接合線形成焊球,而使球體直徑成為線徑之1.5~2.3倍的範圍的既定大小。針對例10及例31,使用相對於芯材整體包含1.3質量ppm之鈀的銅芯材。針對所得之各例的焊球,與例1相同地求得從球體前端部表面至深度方向上5.0~100.0nm的鈀的平均濃度。其結果與線材的組成、焊球形成條件一併顯示於表1、2。又,第三圖中顯示例5之焊球中,從前端部至深度方向上的歐傑分析數據圖表。另外,例2~31中,雖求得從球體前端部表面至深度方向上5.0~100.0nm的鈀的平均濃度,但即使在5.0~400.0nm的範圍內,鈀的平均濃度亦成為與下表的值大約相同的濃度。
(縮孔評價)又,針對以與上述相同條件作成的30個焊球,以SEM觀察球體表面有無大縮孔。在SEM觀察影像中,縮孔的最大長度超過12μm者評價為成為問題的縮孔,在12μm以下者則評價為不會演變為問題的縮孔。另外,第一圖顯示具有不會演變為問題之小縮孔的焊球,第二圖顯示具有演變為問題之大縮孔的焊球,在影像中以虛線將縮孔圈出。演變為問題的大縮孔,如第二圖所示,係形成於焊球表面的如同大皺褶的溝。無縮孔及產生不會演變為問題之程度的小縮孔者評價為無縮孔(○),只要具有1個成為問題的縮孔即評價為具有縮孔(×)。
(HAST及HTS用的試片製作)針對各例中所得之鈀被覆銅接合線,以與上述相同的全自動接合裝置,在BGA(ball grid array)基板上的厚度400μm的Si晶片上的厚度2μm的Al-1.0質量%Si-0.5質量%Cu合金電極上,分別以與上述焊球的製作條件相同的條件製作焊球,以壓接徑50μm、迴路長2mm製作1,000條的打線接合。此時,晶片上的Al-1.0質量%Si-0.5質量%Cu合金電極,僅與相鄰的接合部電性連接,相鄰的2條線材彼此電性地形成1個電路,而形成共500個電路。之後,使用市售的轉注成型機(第一精工製股份有限公司,GPGP-PRO-LAB80)對該BGA基板上的Si晶片進行樹脂密封,得到試片。 <HAST(Highly Accelerated Temperature and Humidity Stress Test)(高溫高濕環境暴露試驗)>
針對該試片使用HAST裝置(平山製作所股份有限公司,PCR8D),以130℃×85.0%RH(相對濕度)保持400小時及600小時。在各別的時間中,於保持前後測量上述500個電路的電阻值,只要有一個電路在保持後的電阻值超過保持前電阻值的1.1倍,即評價為不良(×),500個電路中電阻值皆小於1.1倍的情況則評價為優良(◎)。另外,密封樹脂係使用市售的無鹵素樹脂。保持400小時後,所有的樣本中,電阻值皆小於1.1倍。 <HTS(High Temperature Storage Test)(高溫放置試驗)>
又,針對試片使用HTS裝置(ADVANTEC公司製,DRS420DA),於220℃下保持2000小時。保持前後,與上述相同地測量500個電路的電阻值,只要有一個電路其保持後的電阻值超過保持前電阻值的1.1倍,即評價為不良(×),500個電路中電阻值皆小於1.1倍的情況則評價為優良(◎)。另外,密封樹脂係使用市售的非無鹵素樹脂。將HAST試驗及HTS試驗的評價結果顯示於表1、2。表2中的「不良數」,係保持後的電阻值超過保持前電阻值1.1倍之電路的數量。
從表1、2可得知,相較於不具有鈀濃化區域的比較例之鈀被覆銅接合線,包含占線材整體的濃度為1.0~4.0質量%的鈀和分別既定濃度範圍的硫、硒、碲,且在凝固後的焊球表面上具有平均含有6.5~30.0原子%以下之鈀的鈀濃化區域的鈀被覆銅接合線,一方面可抑制縮孔的產生,一方面可提升在HAST及HTS中的可靠度。
例如,上述車用裝置中,特別是接合焊球與電極的球體接合部(第一接合)的接合壽命會成為最大的問題。要求車用裝置適合下述條件:接合鋁電極與球體並進行樹脂密封的半導體裝置,必須將其暴露於HAST下200小時以上後的電阻值,抑制在暴露前的1.1倍以下。在球體接合後所實施的密封樹脂中所含的氯等的鹵素元素及水分,對於接合壽命、即電阻值的上升有不良影響。該等的氯及水分會腐蝕在球體接合部所產生的金屬間化合物,而導致接合部的電阻值上升。電阻值上升會使通電不良及阻礙電子信號的傳導,若作為車用則具有導致汽車事故的疑慮,而成為嚴重的問題。上述實施例的鈀被覆銅接合線,進行HAST試驗的結果,即使暴露600小時後亦為良好,因此接合可靠度高,可得知用於車用裝置的情況,亦不會發生上述嚴重的問題。
(例33~35)接著確認在鈀層上具有金層的鈀被覆銅接合線的特性。在例1、4、7的鈀被覆銅接合線的製造過程中被覆鈀後,更使用市售的金鍍覆浴實施金鍍覆,除此之外。與例1、4、7相同地製作具有金層的鈀被覆銅接合線(例33~35)。另外,關於表3的各元素的濃度,係在線材整體中不含金層的金濃度的情況下所算出。
針對該等具有金層的鈀被覆銅接合線與不具有金層的例1、4、7的鈀被覆銅接合線進行模具磨耗試驗,結果顯示於表3的「模具損耗」欄位。模具損耗試驗,係從將各樣本的線材鍍金完成後的線徑開始,使其通過複數的模具以進行連續伸線,而伸線至最終線徑18μm、50,000m。關於伸線前後的模具損耗,將最終過程的18μm的模具內徑相較於加工前的尺寸增加小於0.1μm者評價為非常良好(◎),將尺寸增加小於0.1μm以上、0.2μm者評價為良好(○)。
又,具有金層的鈀被覆銅接合線與不具有金層的鈀被覆銅線,為了比較第二接合的接合強度,而測量拉伸強度。第二接合的拉伸強度接合性試驗,係使用與上述相同的K&S公司製的接合裝置,使迴路長度為2mm、迴路高度為200μm以進行打線接合,評價以既定的拉伸鈎對於從第二接合點開始打線接合長度20.0%的第一接合側位置進行拉伸試驗時的破斷強度。結果顯示於表3的「2nd拉伸強度」的欄位,破斷強度4.0gf以上評價為優良(◎),3.5gf以上、小於4.0gf評價佳(○)。又,表3中金層的厚度,係從金濃度與金的比重算出每單位長度的金的質量,而針對單位長度的線材,係假設線材剖面為正圓,金均勻存在於最表面而求得的值。
又,針對各例,與例1相同地進行縮孔、HAST、HTS的評價。如表3所示,具有金層的鈀被覆銅接合線中,縮孔、HAST、HTS的評價與不具有金層的鈀被覆銅接合線相同,皆為良好。這被認為是因為相較於在第二接合時附著的金,源自金層之金的量非常微量,而且金覆蓋線材整體而無局部凝集,因此未產生縮孔。
例1中,使鈀濃度為1.7質量%,使硫濃度為8質量ppm,除此之外,與例1相同地作成鈀被覆銅接合線,使用此接合線,以與例1相同的焊球形成條件在鋁電極上形成球焊。以使與線材長邊方向之中心線平行的面露出的方式切斷所得之球體接合處。從線材側的既定處在與接合面略為垂直的方向上,以掃描式電子顯微鏡/能量色散型X射線光譜分析(SEM-EDX),對切面進行線分析。分析條件,係以加速電壓6keV、測量區域φ0.18μm、測量間隔0.02μm作為SEM-EDX的設定條件。在第四圖所示的兩個接合處進行該測量。所得之SEM-EDX數據圖表顯示於第五圖及第六圖。另外,第五圖係第四圖的測量處1的分析結果,第六圖係測量處2的分析結果。從第五圖、第六圖可知,在相對於鋁、銅及鈀之總和的鋁為0質量%以上、100質量%以下的接合面附近所檢測出的鈀的比例5.0質量%以上的區域,其寬度(深度)以2點的平均計約為1.24μm。又針對例1~19、例32~34,在相同地進行確認鈀濃化接合區域之試驗時,皆在相對於鋁、銅及鈀的總和之鋁為0質量%以上、100質量%以下的接合面附近,以0.50μm以上的寬度檢測到鈀的比例在5.0質量%以上的區域。
接著,針對既定的實施例的鈀被覆銅接合線,進行晶片損傷的評價,以及使設定溫度上升5℃而在135℃下、600小時的嚴苛規格下進行HAST試驗評價。晶片損傷性能評價係以下述方法進行:藉由各例中所得之鈀被覆銅接合線,以與上述相同的條件進行球體接合,並以光學顯微鏡觀察球體接合部正下方的基板。觀察球體接合部100處。例19因為具有1處使用上不會成為問題的小龜裂,因此特別表記為佳(○)。其他例中,因為完全未產生龜裂,因此表記為優良(◎)。嚴苛規格的HAST試驗中,與一般的HAST試驗相同,將試驗後的電阻值小於試驗前1.1倍的例子評價為◎,具有1.1倍以上、1.2倍以下者的例評價為○。另外,例1中500個電路中有5個電路在試驗後的電阻值為試驗前的1.1倍以上、1.2倍以下,其他皆小於1.1倍。又,作為綜合評價,將晶片損傷的評價與嚴苛規格的HAST試驗的結果皆為◎的例子評價為◎,任一者為○、另一者為◎的例則評價為○。結果顯示於表4。
從表4可得知,焊球的前端部表面(鈀濃化區域)的鈀濃度為7.0原子%以上的例1~9中,即便係在使HAST試驗溫度為135℃的比一般更為嚴苛的條件下,亦可承受試驗。焊球的前端部表面的鈀濃度為6.7原子%的例1,電阻值在試驗後成為1.1倍以上、1.2倍以下,可得知其略差於鈀濃化區域之鈀濃度為7.0原子%以上的例子。又,焊球前端部表面的鈀濃度為25.0原子%以下的例子,未產生晶片損傷,超過該比例的例19中,產生微量的不會成為問題的晶片損傷。從該等結果可得知,焊球表面的鈀濃度較佳為7.0原子%以上、25.0原子%以下。焊球表面的鈀濃度為7.0原子%以上、25.0原子%以下的鈀被覆銅接合線適用於車用裝置,並且亦可提升良率。
無
第一圖係在實施例中觀察到的凝固後的焊球影像,其具有不會演變為問題的小縮孔。 第二圖係在比較例中觀察到的凝固後的焊球影像,其具有大縮孔。 第三圖係實施例之凝固後的焊球前端部表面的歐傑(FE-AES)分析數據圖表。 第四圖係顯示實施例之接合結構的分析處的影像。 第五圖係實施例之接合結構的掃描式電子顯微鏡/能量色散型X射線光譜分析(SEM-EDX)數據圖表。 第六圖係實施例之接合結構的其他位置的SEM-EDX數據圖表。 第七圖係顯示實施態樣之半導體裝置的示意圖。
Claims (12)
- 一種鈀被覆銅接合線,其具有以銅為主成分的芯材與該芯材上的鈀層、且含有硫族元素(硫、硒或碲);相對於該鈀被覆銅接合線的銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共50質量ppm以下;硫(S)濃度為5質量ppm以上、12質量ppm以下,或是硒(Se)濃度為5質量ppm以上、20質量ppm以下,或是碲(Te)濃度為15質量ppm以上、50質量ppm以下;從形成於線材前端之焊球的前端部表面至5.0nm以上、100.0nm以下的範圍內具有鈀濃化區域,其中相對於銅與鈀的總和,鈀濃度平均在6.5原子%以上、30.0原子%以下。
- 如請求項1之鈀被覆銅接合線,其中相對於銅、鈀與硫族元素的總和,該鈀被覆銅接合線中,該源自鈀層的鈀濃度為1.0質量%以上、2.5質量%以下。
- 如請求項1或2之鈀被覆銅接合線,其中該鈀被覆銅接合線的線徑在10μm以上、30μm以下。
- 如請求項1或2之鈀被覆銅接合線,其中檢測該鈀濃化區域時,焊球的形成條件為放電電流值65mA、球體直徑為線徑的1.8倍,且在氮與氫的混合氣體的存在下。
- 如請求項1或2之鈀被覆銅接合線,其中該鈀濃化區域的鈀濃度,係以下述歐傑電子能譜分析條件作為裝置的設定條件進行測量時的濃度:一次電子束的加速電壓10kV,從設定值算出的測量區域在15μm2以上、20μm2以下,氬離子濺鍍的加速電壓1kV,濺鍍速度2.5nm/分鐘(SiO2換算)。
- 如請求項1或2之鈀被覆銅接合線,其中該硫族元素的50.0%以上係被包含於該鈀層內。
- 如請求項1或2之鈀被覆銅接合線,其中該硫族元素的50.0%以上係被包含於,從該鈀被覆銅接合線的表面,至相對於鈀與銅的總和,鈀為50.0原子%的部位之間。
- 如請求項1或2之鈀被覆銅接合線,其中該鈀層的表面具有金層。
- 如請求項1或2之鈀被覆銅接合線,其中在該鈀被覆銅接合線整體中,硫(S)所占的濃度為6質量ppm以上、10質量ppm以下。
- 如請求項1或2之鈀被覆銅接合線,其中在該鈀被覆銅接合線整體中,硒(Se)所占的濃度為6質量ppm以上、15質量ppm以下。
- 如請求項1或2之鈀被覆銅接合線,其中在該鈀被覆銅接合線整體中,碲(Te)所占的濃度為16質量ppm以上、45質量ppm以下。
- 一種鈀被覆銅接合線的製造方法,該鈀被覆銅接合線具有以銅為主成分的芯材與該芯材上的鈀層、且含有硫族元素;其中相對於銅、鈀與硫族元素的總和,鈀的濃度為1.0質量%以上、4.0質量%以下,硫族元素濃度共50質量ppm以下;硫(S)濃度為5質量ppm以上、12質量ppm以下,或是硒(Se)濃度為5質量ppm以上、20質量ppm以下,或是碲(Te)濃度為15質量ppm以上、50質量ppm以下;其中準備以銅為主成分的銅線材,在該銅線材的表面形成包含該硫族元素的鈀層。
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