TW201347114A - 半導體裝置及其製造方法 - Google Patents

半導體裝置及其製造方法 Download PDF

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Publication number
TW201347114A
TW201347114A TW102109344A TW102109344A TW201347114A TW 201347114 A TW201347114 A TW 201347114A TW 102109344 A TW102109344 A TW 102109344A TW 102109344 A TW102109344 A TW 102109344A TW 201347114 A TW201347114 A TW 201347114A
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Taiwan
Prior art keywords
copper wire
electrode pad
semiconductor device
copper
semiconductor element
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TW102109344A
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English (en)
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TWI574362B (zh
Inventor
Shingo Itoh
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Sumitomo Bakelite Co
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Publication of TW201347114A publication Critical patent/TW201347114A/zh
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Publication of TWI574362B publication Critical patent/TWI574362B/zh

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Abstract

一種半導體裝置，其係具有搭載於基板之半導體元件、以鋁為主成分且設置於半導體元件的電極墊、設置於基板之將連接端子與電極墊予以連接且以銅為主成分之銅線、及密封半導體元件及銅線之密封樹脂。此種半導體裝置，於大氣中、以200℃加熱16小時之際，在銅線與電極墊之接合部，形成有從鈀及鉑中之任一者所選取的金屬之阻障層。

Description

半導體裝置及其製造方法
本發明係關於半導體裝置及其製造方法。
近年來，已提議以銅線代替金線來作為連接線(bonding wire)。
於專利文獻1中記載著：在以銅之連接線連接引導半導體元件的電極與引線的半導體裝置中，於線與電極之接合界面形成有銅-鋁系金屬間化合物之半導體裝置。依照專利文獻1之記載，由於藉由使之於銅球珠與鋁電極之界面形成CuAl2層、而使得銅球珠與電極成為密合的狀態，因而從耐蝕性等之觀點來看，可視為可靠性提高了。
《先前技術文獻》 《專利文獻》
(專利文獻1)日本特開昭62-265729號公報
然而，由於藉由對銅線與鋁墊之接合部更進一步地進 行熱處理，因而Cu從銅線擴散到CuAl2層，而形成Cu組成比高於CuAl2之合金層。按照本發明人的認知見解，Cu組成比高於CuAl2之合金層就會變得明顯容易因鹵素而受到腐蝕、容易斷線。
本發明為鑑於上述事情而完成者，藉由抑制銅從銅線向銅線與電極墊之接合部擴散，來抑制Cu組成比高於CuAl2的合金層之成長，藉以提高在高溫高濕環境下之連接可靠性。
依照本發明可提供一種半導體裝置，其係具有：搭載於基板的半導體元件、以鋁為主成分且設置於前述半導體元件之電極墊、設置於前述基板的將連接端子與前述電極墊予以連接且以銅為主成分之銅線、以及密封前述半導體元件及前述銅線之密封樹脂；在大氣中、以200℃加熱16小時之際，於前述銅線與前述電極墊之接合部，形成含有從鈀及鉑中之任一者所選取的金屬之阻障層。
又，依照本發明可提供一種半導體裝置，其係具有：搭載於基板之半導體元件、以鋁為主成分、且設置於前述半導體元件之電極墊、設置於前述基板的將連接端子與前述電極墊予以連接、且以銅為主成分之銅線、以及密封前述半導體元件及前述銅線之密封樹脂；其中 前述銅線為含有從鈀及鉑中之任一者所選取之金屬， 在前述銅線和前述電極墊之接合部以外的部分，相對於前述銅線中之鈀及鉑的含量而言，在前述銅線與前述電極墊之前述接合部中之鈀及鉑的含量為大於1。
又，依照本發明可提供一種半導體裝置之製造方法，其係包括：將設置有以鋁為主成分的電極墊之半導體元件，搭載於設置有連接端子的基板之步驟； 藉由以銅為主成分之銅線，將前述連接端子與前述電極墊予以連接之步驟；及 以密封樹脂密封前述半導體元件及前述銅線之步驟；其中在以密封樹脂進行密封的前述步驟之後，於大氣中、以200℃加熱16小時之際，在前述銅線和前述電極墊之接合部，形成含有從鈀及鉑中之任一者所選取的金屬之阻障層。
依照本發明，由於製成一種在銅線與電極墊之接合部置於高溫高濕的環境之情況，形成含有從鈀及鉑中之任一者所選取的金屬之阻障層這樣的半導體裝置，因而能夠抑制銅線與電極墊之接合部中的Cu組成比為高於CuAl2的合金層之成長，進而可提高在高溫高濕環境下之連接可靠性。
又，依照本發明，藉由使得銅線為含有從鈀及鉑中之任一者所選取的金屬，並使得相對於在銅線與電極墊之接合部以外的部分之銅線中的鈀及鉑含量而言，銅線與電極 墊之接合部中的鈀及鉑含量為大於1，因而可以抑制銅線與電極墊之接合部中的Cu組成比高於CuAl2的合金層之成長，進而可以提高在高溫高濕環境下的連接可靠性。
1‧‧‧半導體元件
2‧‧‧固晶材硬化體
3‧‧‧引線框架
3a‧‧‧模墊部
3b‧‧‧內引線部
4‧‧‧銅線
4a‧‧‧銅球珠
5‧‧‧密封樹脂
6‧‧‧電極墊
7‧‧‧接合部
7a‧‧‧CuAl合金層
7b‧‧‧阻障層
8‧‧‧保護膜
10‧‧‧半導體裝置
有關上述之目的、及其他之目的、特徴及優點，藉由以下所述之合適的實施形態、以及所添附的以下之圖面而更為清楚明瞭。
圖1為模式化顯示實施形態相關的半導體裝置之剖面圖。
圖2為對於實施形態相關的半導體裝置中之銅線與電極墊之接合部的放大圖。
《用以實施發明之形態》
以下，使用圖面針對本發明之實施形態進行說明。另外，在全部的圖面中，對於同樣的構成要素附加同樣的符號，並適切地省略其說明。
圖1為模式化顯示本實施形態相關的半導體裝置10之剖面圖。此半導體裝置10為具備作為基板之具有模墊部3a與內引線部3b之引線框架3，並具有搭載於模墊部3a之半導體元件1、以鋁(Al)為主成分且設置於半導體元件1之電極墊6、設置於基板之將連接端子(內引線部3b)與電極墊6予以連接且以銅(Cu)為主成分之銅線4、以及密封半導體元件1及銅線4之密封樹脂5。此半導體裝置10在大氣中、以200℃加熱16小時之際，如圖2所示，在銅線 4與電極墊6之接合部7，更詳細而言為在銅線4與CuAl合金層7a之間，形成含有從鈀(Pd)及鉑(Pt)中之任一者所選取的金屬之阻障層7b。又，銅線為含有從鈀及鉑中之任一者所選取的金屬、且相對於銅線與電極墊之接合部以外的部分之銅線中的鈀及鉑含量而言，在銅線與電極墊之接合部中的鈀及鉑含量為大於1。
半導體元件1並末特別地加以限定，舉例來說，例如其可以是積體電路、大型積體電路、固體攝影元件等。
引線框架3沒有特別限制，也可以使用電路基板來代替引線框架3。具體來說，可以使用雙線內封裝組(DIP)、塑膠附引線晶片承座(PLCC)、四角平板封裝組(QFP)、低外形四角平板封裝組(LQFP)、小型外框J引線封裝組(SOJ)、薄型小型外框封裝組(TSOP)、薄型四角平板封裝組(TQFP)、帶承座封裝組(TCP)、球珠格狀陣列(BGA)、晶片尺寸級封裝組(CSP)、四角平板非引線封裝組(QFN)、小型外框非引線封裝組(SON)、引線框架BGA(LF-BGA)、模組陣列封裝組型的BGA(MAP-BGA)等之習用公知的半導體裝置所用的引線框架或電路基板。
半導體元件1也可以是由複數個半導體元件所積層而成者。在此情況下，第1段的半導體元件為透過薄膜接合劑、熱硬化性接合劑等之固晶材硬化體2而接合於模墊部3a。第2段以後的半導體元件，可以藉由絶緣性的薄膜接合劑等按照順序積層。然後，在各層的適當位置，預先以前置步驟而形成電極墊6。
電極墊6中的Al含量，相對於電極墊6全體而言，較佳者為98質量%以上。電極墊6中所含的Al以外之成分，舉例來說，例如銅(Cu)、矽(Si)等。電極墊6可以藉由在下層之銅電路端子的表面形成一般的鈦系阻障層，更進一步地以蒸鍍、濺鍍、無電解鍍敷等之適用於Al之一般的半導體元件的電極墊之形成方法來製作而得。
銅線4為被使用來用以電性連接引線框架3、與搭載於引線框架3的模墊部3a之半導體元件1。在銅線4之表面上，會自然地形成之氧化膜或者製程上不可避免的氧化膜。在本發明中，所謂銅線4也包括具備如此形成於線表面的氧化膜之物。
銅線4之線徑宜是30μm以下，更佳者為25μm以下且為15μm以上。只要是在此範圍內，銅線前端的球珠形狀就會安定，因而可以提高接合部分的連接可靠性。又，藉由銅線本身的硬度，可以減低線偏移。
銅線4中的銅含量，相對於銅線4全體而言，較佳者為98~99.9質量%，更佳者為98.5~99.7質量%，更理想者為98.7~99.3質量%。銅線4，較佳者為使用向電極墊之擴散速度慢的含有從Pd及Pt中之任一者所選取的金屬之銅線，更佳者為使用摻雜有從Pd及Pt中之任一者所選取的金屬之銅線。藉由向電極墊之擴散速度慢的Pd及Pt，可以抑制銅線4之Cu擴散至電極墊6，進而可得到良好的連接可靠性。
銅線4中之Pd及Pt之含量的合計值，相對於銅線4 全體而言，從良好的高溫保存特性之觀點來看，較佳者為0.1質量%以上，更佳者為0.3質量%以上，更理想者為0.5質量%以上。另一方面，為了抑制銅線4的硬度增加並控制連接性之減低，較佳者為2質量%以下，更佳者為1.5質量%以下，更理想者為1質量%以下。又，銅線4中之Pd及Pt的合計量之範圍，相對於銅線4全體而言，較佳者為0.1~2質量%，更佳者為0.3~1.5質量%，更理想者為0.5~1質量%。
銅線4中也可以含有Pd或Pt中之任一者，在此情況下，相對於銅線4全體而言，較佳者是：銅線4中的Pd含量為0.5~1質量%；或者相對於銅線4全體而言，較佳者是銅線4中之Pt含量為0.5~1質量%。藉由設定在前述之範圍，可以同時兼具優異的可靠性與連接作業性。
另外，摻雜在銅線4的從Pd及Pt中之任一者所選取的金屬，可以推斷其為以固溶於Cu中的狀態存在。
銅線4，其係可以經由在芯線之銅中摻雜0.001質量%~0.003質量%的Ba、Ca、Sr、Be、Al或稀土金屬，藉以更進一步地改善接合強度。
銅線4，其係可以使用：於熔解爐中鑄造摻雜有從Pd及Pt中之任一者所選取的金屬之銅合金，對該鑄塊施以輥壓延，更進一步使用模進行拉線加工，一邊連續地引拉線一邊實施加熱之後熱處理而得到之物。
在銅線4與電極墊6之接合部7中，於銅線4之前端形成有銅球珠4a。
半導體裝置10可以在銅線4與電極墊6之接合部7形成含有Cu及Al的CuAl合金層7a；也可以在大氣中、以200℃加熱16小時之際形成CuAl合金層7a。CuAl合金層7a為包括各種的Cu及Al之含量；Cu為銅線4所含的主成分；Al為電極墊6所含的主成分。CuAl合金層7a為藉由接合時之加熱或密封後之熱處理而致使電極墊6中的Al和銅球珠4a中的Cu一起發生擴散的區域，主要含有Cu與Al。此處，主要含有Cu和Al係指：相對於CuAl合金層7a全體而言，只要Cu含量與Al之含量的合計值為大於50質量%即可，較佳者為80質量%以上，更佳者為90質量%以上，更理想者為95質量%以上。
具體來說，CuAl合金層7a為包括CuAl2層、與Cu含量比CuAl2層多的層。在CuAl合金層7a中，較佳者為：在CuAl合金層7a中所占的比例，CuAl2層為比Cu含量多的層還高者。CuAl合金層7a的厚度，例如，可以設定為0.2~5μm。
阻障層7b為含有從Pd及Pt中之任一者所選取的金屬之層，也可以更進一步地含有Cu。具體而言，在阻障層7b中的Pd及Pt之質量比例，較佳者為銅線4中的Pd及Pt之質量比例的1.1~2倍，更佳者為1.2~1.8倍。
阻障層7b係如以下之作法而形成於銅線4與電極墊6之接合部7。
藉由熱處理銅線4與電極墊6之接合部7，使得銅線4中之擴散速度快的Cu擴散至電極墊6。另一方面，從銅線 4中之擴散速度慢的Pd及Pt中之任一者所選取的金屬，停留在CuAl合金層7a上而逐漸地被濃縮，然後成為阻障層7b。
藉此，可以抑制銅線4中的Cu擴散電極墊6。又，由於更進一步地抑制擴散至CuAl合金層7a，因而可以減低在CuAl合金層7a中的Cu含量比CuAl2層多的層之成長。更且，可以進一步地減低：Cu含量比CuAl2層多的層會因從密封樹脂5所產生的鹵素導致腐蝕而生成的斷線。
阻障層7b，只要是在大氣中、以200℃對半導體裝置10加熱16小時之際，被形成於CuAl合金層7a與銅線4之間即可，也可以預先在半導體裝置10形成阻障層7b。
形成阻障層7b的理由，其詳細內容雖然不是很明瞭，然而推測如下。
由於在銅線4中擴散速度慢的Pd及Pt之濃度提高，因而在銅線4與電極墊6之接合後，可以增加停留在接合部7附近的Pd及Pt之量，以致容易形成阻障層7b；或者由於密封樹脂5的175℃之彈性率為500MPa以上15000MPa以下，可以減低在密封之際及密封後對銅線4與電極墊6之界面所施加應力，並且可以適度地拘束銅線4之行動，所以能防止因接合部之應力所引起的破壞而導致更容易形成阻障層，或者推斷認為是兩者之組合所引起的等等之理由。
阻障層7b之厚度較佳為0.01~3μm，更佳為者0.05~2μm。
接合部7較佳為在與電極墊6之界面中的底面是平坦的。
又，在半導體裝置10中，接合部7之Pd及Pt的含量為比在銅線4之接合部7以外的部分之Pd及Pt的含量還高。具體而言，相對於在銅線4與電極墊6之接合部7以外的部分之銅線4中的Pd及Pt之含量而言，在銅線4與電極墊6之接合部7中的Pd及Pt之含量較佳為大於1，從高溫保存特性的觀點來看，更佳者為1.3以上。所謂「接合部7中的Pd及Pt之含量」，雖然可以是接合部7之任何的區域；然而更佳者為在銅線4與電極墊6之界面附近的Pd及Pt之含量。
將接合部7中的Pd及Pt之含量提高成為比在銅線4之接合部7以外的部分之Pd及Pt的含量還高之方法，舉例來說，例如，可以使用Pd及Pt之濃度高的銅線4之方法、使用175℃的彈性率為500MPa以上15000MPa以下的密封樹脂之方法等。其機轉之詳細內容雖然不是很明瞭，然而推測是由於Pd及Pt向電極墊6之擴散速度慢的緣故，以致在銅線4與電極墊6之接合後，從銅線4向電極墊6擴散的Pd及Pt變得容易停留在接合部7。又，推斷是由於上述彈性率之密封樹脂5，可以減低在密封之際及密封後施予銅線4與電極墊6之界面的應力、並且可以適度地拘束銅線4之行動的緣故，所以能夠防止因接合部之應力所引起的破壞，進而可以提高Pd及Pt之含量。
密封樹脂5為硬化性樹脂的硬化體；具體而言，更佳 者為使含有(A)環氧樹脂及(B)硬化劑之環氧樹脂組成物硬化而成之物。
密封樹脂5的175℃之彈性率較宜是500MPa以上15000Mpa以下，更佳者是800以上5000以下。藉此，可以減低施予銅線4與電極墊6之界面的應力並且可以適度地拘束銅線4之行動的緣故，所以能夠更容易地形成阻障層，進而可以增加高溫保存特性。
(A)環氧樹脂係在1分子內具有2個以上的環氧基之單體、寡聚物、聚合物之全部，且其分子量、分子構造未特別加以限定，舉例來說，例如其可以是聯苯基型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、四甲基雙酚F型環氧樹脂等之雙酚型環氧樹脂、芪型環氧樹脂；苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂；三酚甲烷型環氧樹脂、烷基改性三酚甲烷型環氧樹脂等之多官能環氧樹脂；具有伸苯基骨架之苯酚芳烷基型環氧樹脂、具有聯伸苯基骨架之苯酚芳烷基型環氧樹脂等之芳烷基型環氧樹脂；二羥基萘型環氧樹脂、二羥基萘之2聚物予以縮水甘油醚化而得到的環氧樹脂等之萘酚型環氧樹脂；三縮水甘油基三聚異氰酸酯、單烯丙基二縮水甘油基三聚異氰酸酯等之含三嗪核環氧樹脂；二環戊二烯改性苯酚型環氧樹脂等之有橋環狀烴化合物改性苯酚型環氧樹脂；此等可以1種類單獨使用，也可以併用2種類以上。
另外，前述聯苯基型環氧樹脂、雙酚A型環氧樹脂、 雙酚F型環氧樹脂、四甲基雙酚F型環氧樹脂等之雙酚型環氧樹脂、芪型環氧樹脂，較佳者為具有結晶性之物。
較佳者為可以使用：含有以下述式(1)所表示的環氧樹脂、以下述式(2)所表示的環氧樹脂、及以下述式(3)所表示的環氧樹脂構成群組中所選取的至少1種之物來作為環氧樹脂(A)。
〔式(1)中，Ar1表示伸苯基或伸萘基，在Ar1為伸萘基的情況，縮水甘油醚基可以是鍵結於α位、β位中之任何位置；Ar2表示伸苯基、聯伸苯基及伸萘基中之任何1個基；R5及R6各自獨立地表示碳數1~10的烴基；g為0~5的整數；h為0~8的整數；n3表示聚合度，其平均值為1~3〕
〔式(2)中，複數個存在的R9為各自獨立表示氫原子 或碳數1~4的烴基；n5表示聚合度，其平均值為0~4〕
〔式(3)中，複數個存在的R10及R11為各自獨立地表示氫原子或碳數1~4的烴基；n6表示聚合度，其平均值為0~4〕
(A)環氧樹脂的含量，相對於環氧樹脂組成物全體而言，較佳者為3質量%以上，更佳者為5質量%以上，更理想者為8質量%以上。藉由如此設定，可以減少因黏度上昇而導致引起斷線之疑慮。又，環氧樹脂(A)的含量，相對於環氧樹脂組成物全體而言，較佳者為18質量%以下，更佳者為13質量%以下，更理想者為11質量%以下。藉由如此設定，可以減少因吸水率增加而引起的耐濕可靠性之降低等之疑慮。
(B)硬化劑，例如，大致可以分類成加成聚合型之硬化劑、觸媒型之硬化劑、縮聚型之硬化劑的3種型態。
加成聚合型之硬化劑，舉例來說，例如，可以是二乙三胺(DETA)、三乙四胺(TETA)、間二甲苯二胺(MXDA)等之脂肪族多胺、二胺基二苯基甲烷(DDM)、m-伸苯基二胺(MPDA)、二胺基二苯基碸(DDS)等之芳香族多胺，除此之外，包括二氰二醯胺(DICY)、有機酸二肼等之多胺化合物；六氫酞酸酐(HHPA)、甲基四氫酞酸酐(MTHPA)等之脂 環族酸酐、偏苯三酸酐(TMA)、均苯四甲酸酐(PMDA)、二苯甲酮四羧酸(BTDA)等之包括芳香族酸酐之酸酐；酚醛清漆型苯酚樹脂、聚乙烯基苯酚等之苯酚樹脂系硬化劑；聚硫化物、硫酯、硫醚等之聚硫醇化合物；異氰酸酯預聚物、嵌段化異氰酸酯等之異氰酸酯化合物；含羧酸聚酯樹脂等之有機酸類等。
觸媒型之硬化劑，舉例來說，例如，可以是苄基二甲基胺(BDMA)、2,4,6-參二甲基胺基甲基苯酚(DMP-30)等之3級胺化合物；2-甲基咪唑、2-乙基-4-甲基咪唑(EMI24)等之咪唑化合物；BF3錯合物等之路易士酸等。
縮聚型之硬化劑，舉例來說，例如，可以是可溶酚醛型苯酚樹脂；含羥甲基脲樹脂這樣的脲樹脂；含羥甲基蜜胺樹脂這樣的蜜胺樹脂等。
在此等之中，從耐燃性、耐濕性、電氣特性、硬化性、保存安定性等之平衡的觀點來看，較佳者為苯酚樹脂系硬化劑。苯酚樹脂系硬化劑為一分子內具有2個以上的苯酚性氫氧基之單體、寡聚物、聚合物之全部，雖然其分子量、分子構造未特別加以限定，然而，舉例來說，例如，可以是苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆等之酚醛清漆型樹脂；三酚甲烷型苯酚樹脂等之多官能型苯酚樹脂；萜改性苯酚樹脂、二環戊二烯改性苯酚樹脂等之改性苯酚樹脂；具有從伸苯基骨架及聯伸苯基骨架中之任一者所選取的骨架之苯酚芳烷基樹脂、具有從伸苯基及聯伸苯基骨架中之任一者所選取的骨架之萘酚芳烷基樹脂 等之芳烷基型樹脂；雙酚A、雙酚F等之雙酚化合物等；此等可以1種類單獨使用，也可以併用2種類以上。
較佳者為可以使用：從以下述式(4)表示的化合物構成群組中所選取的至少1種之硬化劑來作為(B)硬化劑。
〔式(4)中，Ar3表示伸苯基或伸萘基，在Ar3為伸萘基的情況下，氫氧基可以鍵結於α位、β位中的任何位置；Ar4表示伸苯基、聯伸苯基及伸萘基之中的任何1個的基；R7及R8為各自獨立地表示碳數1~10之烴基；i為0~5之整數；j為0~8之整數；n4表示聚合度，其平均值為1~3〕
(B)硬化劑之含量，在環氧樹脂組成物中，較佳者為2質量%以上，更佳者為3質量%以上，更理想者為6質量%以上。藉由如此設定，可以得到充分的流動性。又，(B)硬化劑的含量，在環氧樹脂組成物中，較佳者為15質量%以下，更佳者為11質量%以下，更理想者為8質量%以下。藉由如此設定，可以減少因吸水率增加而引起的耐濕可靠性之減低等之疑慮。
又，在使用苯酚樹脂系硬化劑來作為(B)硬化劑的情況下之環氧樹脂與苯酚樹脂系硬化劑之摻混比率，全環氧樹 脂之環氧基數(EP)、與全苯酚樹脂系硬化劑之苯酚性氫氧基數(OH)之當量比(EP)/(OH)較佳為0.8~1.3。在當量比為於此範圍時，則引起環氧樹脂組成物的硬化性之減低、或樹脂硬化物的物性之減低等之疑慮就會變少。
又，在形成密封樹脂5之環氧樹脂組成物中，也可以含有(C)填充材、及視需要亦可含有(D)中和劑、(E)硬化促進劑。
(C)填充材，例如，可以使用在一般的半導體密封用環氧樹脂組成物所使用之物。舉例來說，例如，可以是熔融球狀矽石、熔融破碎矽石、結晶矽石、滑石、氧化鋁、鈦白、氮化矽等之無機填充材、有機聚矽氧粉末、聚乙烯粉末等之有機填充材；其中，特佳者為熔融球狀矽石。此等之填充材，可以1種單獨使用，即使併用2種以上也沒有關係。又，(C)填充材之形狀，為了抑制環氧樹脂組成物的熔融黏度之上昇、以及更進一步地提高填充材的含量，則較佳者為盡可能是真球狀，而且粒度分布是廣的。又，填充材也可以是經由以偶合劑進行表面處理過的。更且，也可以按照需要而以環氧樹脂或苯酚樹脂等預先處理填充材來使用；處理之方法，有使用溶劑予以混合之後再除去溶劑之方法、直接添加於填充材並使用混合機進行混合處理之方法等。
從環氧樹脂組成物之填充性、半導體裝置之可靠性的觀點來看，相對於環氧樹脂組成物全體而言，(C)填充材之含量較佳為65質量%以上，更佳者為75質量%以上，更 理想者為80質量%以上。藉由如此設定，可以減少因得到低吸濕性、低熱膨張性而導致耐濕可靠性不足的疑慮。又，(C)填充材之含量，當考慮成形性時，相對於環氧樹脂組成物全體而言，較佳者為93質量%以下，更佳者為91質量%以下，更理想者為86質量%以下。藉由如此設定，可以減少在流動性降低而於成形時發生填充不良等、以及可以減少因高黏度化而導致產生半導體裝置內的線偏移等之不合適之疑慮。
(D)中和劑，其係可以使用用以中和因環氧樹脂組成物、或其硬化體之密封樹脂5之加熱所引發之酸性的腐蝕性氣體之物。藉此，可以抑制在銅線4與半導體元件1之電極墊6間之接合部7的腐蝕(氧化劣化)。具體而言，可以使用鹼性金屬鹽，特別是從含有鈣元素之化合物、含鋁元素之化合物、及含鎂元素之化合物構成群組中所選取的至少1種來作為(D)中和劑。
上述之含鈣元素的化合物，舉例來說，例如，可以是碳酸鈣、硼酸鈣、矽酸酸鈣等；其中，從不純物之含量、耐水性及低吸水率的觀點來看，較佳者為碳酸鈣，更佳者為藉由碳酸氣體反應法所合成的沈降性碳酸鈣。
上述之含鋁元素化合物，舉例來說，例如，可以是氫氧化鋁、勃姆石等；其中，較佳者為氫氧化鋁，更佳者為該氫氧化鋁為以2階段拜耳法所合成的低鹼氫氧化鋁。
上述之含鎂元素化合物，舉例來說，例如，可以是水滑石、氧化鎂、碳酸鎂等；其中，從不純物的含量及低吸 水率的觀點來看，較佳者為以下述式(5)所表示的水滑石。
MaAlb(OH)2a+3b-2c(CO3)c．mH2O (5)
〔式(5)中，M表示至少含有Mg的金屬元素；a、b、c分別表示滿足2≦a≦8、1≦b≦3、0.5≦c≦2的數；m為0以上的整數〕
具體的水滑石，舉例來說，例如，其可以是Mg6Al2(OH)16(CO3)．mH2O、Mg3ZnAl2(OH)12(CO3)．mH2O、Mg4.3Al2(OH)12.6(CO3)．mH2O等。
(D)中和劑之含量，相對於環氧樹脂組成物全體而言，較佳者為0.01~10質量%。藉由將(D)中和劑之含量設定為0.01質量%以上，可以充分地發揮中和劑之添加效果，並可以更確實地防止銅線4與電極墊6之接合部7的腐蝕(氧化劣化)，且可以增加半導體裝置之高溫保存特性。又，由於經由將(D)中和劑之含量設定於10質量%以下可以減低吸濕率的緣故，所以就會有耐焊龜裂性提高的傾向。特別是在使用碳酸鈣、水滑石來作為腐蝕防止劑的情況，從上述同樣的觀點來看，其含量相對於環氧樹脂組成物全體而言，較佳者為0.05~2質量%。
(E)硬化促進劑，只要是能夠促進環氧樹脂之環氧基與硬化劑(例如，苯酚樹脂系硬化劑之苯酚性氫氧基)間之交聯反應之物即可，可以使用在一般的半導體密封用環氧樹脂組成物所使用之物。舉例來說，例如，可以是1、8-二氮雜雙環(5、4、0)十一烯-7等之二氮雜雙環烯及其衍生物；三苯基膦、甲基二苯基膦等之有機膦類；2-甲基咪唑 等之咪唑化合物，四苯基鏻．四苯基硼酸鹽等之四取代鏻．四取代硼酸鹽；膦化合物與醌化合物之加成物等；此等可以1種類單獨使用，即使併用2種以上也沒有關係。
(E)硬化促進劑之含量，相對於環氧樹脂組成物全體而言，較佳者為0.05質量%以上，更佳者為0.1質量%以上。藉由如此設定，可以減少引起硬化性減低之疑慮。又，(E)硬化促進劑的含量，相對於環氧樹脂組成物全體而言，較佳者為1質量%以下，更佳者為0.5質量%以下。藉由如此設定，可以減少引起流動性之減低之疑慮。
在用以形成密封樹脂5之環氧樹脂組成物中，也可以更進一步地按照需要而適當地摻混：氫氧化鋯等之鋁腐蝕防止劑；氧化鉍水合物等之無機離子交換體；γ-環氧丙基丙基三甲氧矽烷、3-巰基丙基三甲氧矽烷、3-胺基丙基三甲氧矽烷等之偶合劑；碳黑、氧化鐵紅等之著色劑；聚矽氧橡膠等之低應力成分；巴西棕梠蠟等之天然蠟、合成蠟、硬脂酸鋅等之高級脂肪酸及其金屬鹽類、或者鏈烷烴等之脫模劑；氫氧化鋁、氫氧化鎂、硼酸鋅、鉬酸鋅、磷腈等之難燃劑、抗氧化劑等之各種添加劑。
用以形成密封樹脂5之環氧樹脂組成物，可以使用：例如，使用混合機等將前述的各成分於15℃~28℃混合而成之物，然後更進一步地以輥、揑和機、押出機等之混練機予以熔融混練、冷卻後粉碎而成之物等，視需要而適當地調整分散度及流動性等而成之物。
接著，針對本實施形態相關的半導體裝置10之製造方 法的一例子，進行說明。
首先，藉由公知的半導體製造方法，對於半導體元件1的最上層之保護膜8的一部分進行開口，並形成電極墊6。保護膜8為由SiN等之絶緣膜所形成。其次，更進一步地藉由公知的後步驟方法，將具備有電極墊6的半導體元件1設置於引線框架3上的模墊部3a，經由以銅線4對於電極墊6與內引線部3b進行線連接。
連接係例如按以下的順序來進行。首先，在銅線4之前端形成指定的徑之銅球珠4a(但，圖2為圖示在連接後的形狀)。其次，相對於電極墊6上面而言為實質垂直地降下銅球珠4a，一邊使銅球珠4a與電極墊6接觸，一邊施加超音波振動。
藉此，銅球珠4a的底部乃與電極墊6接觸而形成接合面。
另外，引線框架3的內引線部3b與半導體元件1也可以是以線的逆連接(reverse bond)來實施接合。於逆連接，首先，接合半導體元件1的電極墊6、與形成於銅線4的前端之球珠，切斷銅線4而形成針腳式(stitch)接合用的凸狀體(bump)。其次，對於引線框架3的金屬鍍敷的內引線部3b，接合被形成於線的前端球珠，將之與半導體元件的凸狀體予以針腳式接合。逆連接由於可以比正連接還更能降低半導體元件1上的線高度，所以能夠降低半導體元件1的接合高度。
接著，以轉移成形、壓模成形、注射成形等之以往習 用的成形方法，硬化成形硬化性樹脂(例如，上述的環氧樹脂組成物)，密封半導體元件1、銅線4及內引線3b，於80℃~200℃左右的溫度，以10分鐘~24小時左右的時間進行後硬化。後硬化更佳者為於150℃~200℃進行2~16小時。然後，經以密封樹脂5密封的半導體元件1，就可以搭載在電子機器等。
如此所製造的半導體裝置10，相對於銅線4中的Pd及Pt之含量而言，在接合部7中的Pd及Pt之含量乃變成大於1。又，半導體裝置10在以密封樹脂5密封的步驟之後，於大氣中以200℃加熱16小時之際，在銅線4與電極墊6之接合部7，形成含有從Pd及Pt中之任一者所選取的金屬之阻障層7b。亦即，相對於銅線4中的Pd及Pt之含量而言，在接合部7之Pd及Pt的含量為大於1；又，在形成有阻障層7b這樣的半導體裝置10，在製造程序、使用時因接合部7之熱導致Cu優先地從銅球珠4a擴散至電極墊6，而於接合部7形成CuAl合金層7a，並且銅球珠4a中的Pt、Pd或此等兩者不擴散至電極墊6而殘留於CuAl合金層7a上。因此，可以防止銅線4中的Cu更進一步地向著CuAl合金層7a擴散，並可以抑制CuAl合金層7a之成長。從而，依照本發明，即使是在連接後採用高溫高熱製程的情況、及使用環境為高溫的情況(例如，設置在汽車等之引擎周邊的情況)，也能夠維持高的連接可靠性。
以上，雖然而參照圖面記述本發明之實施形態，然而此等僅是本發明的例示而已，也可以採用上述以外的各式 各樣的構成。
例如，本發明是關於一種半導體裝置，其係具有：搭載於基板的半導體元件、以鋁為主成分且設置於前述半導體元件的電極墊、設置於前述基板的將連接端子與前述電極墊予以連接且以銅為主成分之銅線、以及密封前述半導體元件及前述銅線之密封樹脂；並且前述銅線中的鈀及鉑之合計量，相對於前述銅線全體而言為0.1重量%以上2重量%以下。
〔實施例〕
以下，基於實施例及比較例而更具體地說明本發明，然而本發明絕非限定於以下的實施例而已。
《製造例1~5》
使用混合機，於15~28℃將表1所示的各成分予以混合，其次於70℃~100℃進行輥混練。在冷卻後，進行粉碎而得到環氧樹脂組成物。另外，在表1中的各成分之詳細為如下所述。又，表1中之單位為質量%。
<(A)環氧樹脂>
環氧樹脂-OCN：EOCN-1020-55、日本化藥股份有限公司製、環氧基當量為200
Br化環氧基：EPICLON 152-S、大日本油墨化學工業股份有限公司製、環氧基當量為359
環氧樹脂-2：NC3000P、日本化藥股份有限公司製、環氧基當量為276
環氧樹脂-3：YX4000K、三菱化學股份有限公司製、 環氧基當量為185
<(B)硬化劑>
硬化劑-PN：PR-HF-3、住友電木股份有限公司製、氫氧基當量105
<(C)填充材>
熔融球狀矽石：FB-820、電氣化學工業股份有限公司製、平均粒徑26.5μm、105μm以上的粒子為1%以下
<(D)中和劑>
水滑石：DHT-4A(註冊商標)(在上述式(5)中之a為4.3，b為2，c為1的水滑石)、協和化學工業股份有限公司製
<(E)硬化促進劑>
三苯基膦：TPP、北興化學工業股份有限公司製
<其他成分>
偶合劑：γ-環氧丙基丙基三甲氧矽烷
著色劑：碳黑
脫模劑：巴西棕梠蠟
藉由下述之方法，測定在製造例1~5所得到的環氧樹脂組成物之物性。將其結果表示於表1。
<螺旋流動(SF)>
使用低壓轉印成形機(上瀧精機股份有限公司製「KTS-15」)，以EMMI-1-66為準據，於模型溫度為175℃、注入壓力為6.9MPa、硬化時間為120秒之條件下，於螺旋流動測定用的模型中分別注入製造例1~4的環氧樹脂組成物，測定流動長度(單位：cm)。
<凝膠時間(GT)>
在加熱至175℃的熱板上，將製造例1~4的環氧樹脂組成物分別予以熔融後、一邊以刮板進行混練，一邊測定直到其硬化為止的時間。
<不純物量之測定>
使用低壓轉印成型機(上瀧精機股份有限公司製「KTS-15」)，於模型溫度175℃、注入壓力7.5MPa、硬化時間2分鐘而成形得到50mmφ×3mm的試驗片。於175℃、8小時後，於硬化之後進行微粉碎，添加50ml的蒸餾水於5g之粉碎品，裝入經以鐵弗龍(註冊商標)襯裡的容器內，於125℃、進行20小時的處理；藉由以離子色譜分析處理後的上澄液進行定量。
《實施例1~11、比較例1~6》
將具備鋁製電極墊(Al純度為99.9質量%、厚度為1μm的鋁墊)的TEG(TEST ELEMENT GROUP)晶片(3.5mm×3.5mm)，接合於352pin(針)BGA(基板之厚度為0.56mm、雙馬來醯亞胺．三嗪樹脂/玻璃纖維布基板、封裝尺寸為30mm×30mm、厚度為1.17mm)之模墊部，使用表2、3所示之銅線，以線間距(pitch)80μm，按照使TEG晶片的電極墊與基板的電極墊構成菊鏈(daisy chain)連接的方式進行線連接。使用低壓轉印成形機(TOWA製「Y系列」)，於模型溫度175℃、注入壓力6.9MPa、硬化時間2分鐘之條件下，使用如表2、3所示的製造例1~5之任一種環氧樹脂組成物，將它予以密封成形，而製作成352pin BGA封裝組。以175℃、4小時的條件，對此封裝組進行後硬化之 後而得到半導體裝置。
另外，在表2、3中，銅線之詳細內容為如下所述。
Pd摻雜1：銅純度為98.99質量%、Pd含量為1質量%之銅線(徑25μm)
Pd摻雜2：銅純度為99.49質量%、Pd含量為0.5質量%之銅線(徑25μm)
Pt摻雜：銅純度為98.99質量%、Pt含量為1質量%之銅線(徑25μm)
裸銅：銅純度為99.99質量%、不含Pd及Pt中的任一者之銅線(徑25μm)
Pd被覆：於銅純度為99.99質量%之表面被覆有50nm的Pd之銅線(徑25μm)
<TEM分析>
對於實施例1~11及比較例1~6之半導體裝置，以穿透型電子顯微鏡(TEM)，解析銅線與電極墊之接合部的構造。
在實施例1~11、比較例1~6之半導體裝置中，可確認在銅線與鋁墊之間，形成有厚度為0.3μm的只由CuAl2層構成之CuAl合金層。
在實施例1~11、比較例1~6之半導體裝置中，不能確認在銅線與鋁墊之間有阻障層，然而以穿透型電子顯微鏡(TEM)之元素分析進行解析時，可確認：在實施例1~11中，相對於銅線中的Pd、Pt之質量比例而言，銅線與CuAl合金層之間的Pd、Pt之質量比例提高至1.02~1.08倍。
又，對於實施例1~11及比較例1~6之半導體裝置，於大氣中、以200℃加熱16小時，以TEM解析銅線與電極墊之接合部的構造時，可確認：在實施例1~6、11的半導體裝置中，於厚度為0.3μm的CuAl2層之銅線之間，形成有厚度為0.05~0.2μm的由Cu/Pd構成之阻障層。另外，於TEM之元素分析中，可確認：該阻障層中的Pd質量比例，相對於銅線中的Pd質量比例而言為增加1.2~1.3倍。
又，可確認：在實施例7~10的半導體裝置中，於厚度為0.3μm的CuAl2層與銅線之間，形成有厚度為0.1~0.2μm的由Cu/Pt構成的阻障層。於TEM之元素分析中，確認：該阻障層中的Pt質量比例，相對於銅線中的Pt質量比例而言為增加至1.2~1.4倍。
又，可確認：在比較例1~6的半導體裝置中，於銅線與鋁墊之間所形成的CuAl2層之厚度為0.4μm，於CuAl2層與銅線之間，更進一步地形成有厚度為0.1μm之Cu9Al4層。不摻雜於銅線中而僅被覆於表面時，可明瞭於大氣中、以200℃加熱16小時之際並未形成阻障層。
<耐濕性及高溫保存特性>
對於實施例1~11、比較例1~6之半導體裝置，進行半導體裝置之HAST(不飽和耐濕性試驗)及HTSL(高溫保存試驗)。將其結果表示於表2、3。表2、3中之單位為時間(hour)。
具體而言，HAST為以IEC68-2-66準據來實施的。試驗條件是：溫度設為130℃及140℃；85%RH、施加電壓 20V，調查不良發生的時間。
又，HTSL係於175℃進行處理，調查發生不良之時間。
另外，在HAST及HTSL中，不良之判定為使用所製作的封裝組10個進行評價，以相對於初期電阻計之處理後的電阻值超過1.2倍的封裝組之產生時間來作為不良時間。
在實施例的半導體裝置中，可看出優異的高溫耐濕特性及高溫保存特性，特別是顯示出：藉由使用Pd或Pt的摻雜量為在較佳的範圍之0.1~2質量%、更佳的範圍之 0.3~1.5質量%、更理想的範圍之0.5質量%以上1質量%以下的銅線，可以不受形成密封樹脂的環氧樹脂組成物之鹵素量的影響，並且可以同時兼具安定的可靠性與連接作業性。
本申請案為以2012年3月22日所申請的日本專利申請案特願2012-066161為基礎而主張優先權，其全部揭示均納入本案中參考。
1‧‧‧半導體元件
2‧‧‧固晶材硬化體
3‧‧‧引線框架
3a‧‧‧模墊部
3b‧‧‧內引線部
4‧‧‧銅線
4a‧‧‧銅球珠
5‧‧‧密封樹脂
6‧‧‧電極墊
8‧‧‧保護膜
10‧‧‧半導體裝置

Claims (8)

  1. 一種半導體裝置，其係具有：搭載於基板之半導體元件、以鋁為主成分且設置於前述半導體元件之電極墊、設置於前述基板的將連接端子與前述電極墊予以連接且以銅為主成分之銅線、及密封前述半導體元件及前述銅線之密封樹脂；於大氣中、以200℃加熱16小時之際，於前述銅線與前述電極墊之接合部形成含有從鈀及鉑中之任一者所選取的金屬之阻障層。
  2. 如請求項1所記載之半導體裝置，其中於大氣中、以200℃加熱16小時之際所形成的前述阻障層之厚度為0.01~3μm。
  3. 如請求項1或2所記載之半導體裝置，其中於大氣中、以200℃加熱16小時之際，於前述阻障層與前述電極墊之間形成有銅及鋁之合金層。
  4. 一種半導體裝置，其係具有：搭載於基板之半導體元件、以鋁為主成分且設置於前述半導體元件之電極墊、設置於前述基板之將連接端子與前述電極墊予以連接且以銅為主成分之銅線、及密封前述半導體元件及前述銅線之密封樹脂；前述銅線為含有從鈀及鉑中之任一者所選取的金屬， 相對於前述銅線中之鈀及鉑的含量而言，在前述銅線與前述電極墊之接合部中的鈀及鉑含量為大於1。
  5. 如請求項1或4所記載之半導體裝置，其在前述銅線中之銅含量，相對於前述銅線全體而言為98~99.9質量%。
  6. 如請求項1或4所記載之半導體裝置，其中前述基板為引線框架或電路基板。
  7. 一種半導體裝置之製造方法，其係包括：將設置有以鋁為主成分的電極墊之半導體元件，搭載於設置有連接端子的基板之步驟；藉由以銅為主成分之銅線，連接前述連接端子與前述電極墊之步驟；及以密封樹脂密封前述半導體元件及前述銅線之步驟；在以密封樹脂進行密封的前述步驟之後，於大氣中、以200℃加熱16小時之際，在前述銅線與前述電極墊之接合部形成含有從鈀及鉑中之任一者所選取的金屬之阻障層。
  8. 如請求項7所記載之半導體裝置之製造方法，其係在以前述密封樹脂進行密封的前述步驟中，於使用環氧樹脂組成物予以密封成形之後，再於150℃~200℃進行2~16小時的後硬化。
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