TW201936987A - 半導體晶圓及其製造方法 - Google Patents
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Abstract
本發明之實施形態係提供一種半導體晶圓,於鈍化膜與無電解鎳鍍敷皮膜之界面產生的空穴受到抑制,且電極墊整面經無電解鎳鍍敷皮膜被覆。本發明之一態樣的半導體晶圓,係在基板上依序具有:電極墊(12);覆蓋基板上表面且具有使電極墊露出之開口部的鈍化膜(11);以及於電極墊(12)上之無電解鎳鍍敷皮膜(13)、無電解鈀鍍敷皮膜(14)及無電解金鍍敷皮膜(15);其中,關於存在於鈍化膜(11)與無電解鎳鍍敷皮膜(13)之界面的空穴,從空穴之前端起至電極墊表面為止之長度(x)為0.3μm以上,空穴之寬度(y)為0.2μm以下,且電極墊(12)整面經無電解鎳鍍敷皮膜(13)被覆。
Description
本發明係關於半導體晶圓及其製造方法。
本申請案係主張依據2017年12月19日申請之日本申請案第2017-242629號之優先權,且援用在前述日本申請案所記載之全部記載內容。
近年來,半導體裝置之輕薄短小化正在進展中,就將IC(Integrated Circuit;積體電路)與基板及IC彼此接合之方法而言係從以往之打線接合進展至覆晶化。
為了以覆晶將IC與基板及IC彼此接合,在已形成於IC上之Al、Cu、Au等之電極墊以蒸鍍或鍍敷而形成UBM(Under Bump Metallurgy;凸塊下冶金),並在其上以印刷、球粒搭載或鍍敷而形成Sn-Ag、Sn-Ag-Cu等無鉛焊料。可使用將其在同樣地形成之IC及基板上進行加熱接合之方法。
就UBM之形成方法而言,藉由可期盼低成本之無電解鍍敷(也稱為無電極鍍或化學鍍)法而形成之方法正逐漸增加。就藉由無電解鍍敷而形成UBM之方法而
言,首先為了使半導體晶圓上之被鍍敷部分(墊及配線)清淨化,而進行脫脂處理、軟蝕刻處理。其次,進行賦予觸媒之步驟。對於鋁系金屬表面係以鋅酸鹽處理為賦予觸媒之步驟,對於銅系金屬表面係以鈀處理為賦予觸媒之步驟。其後,藉由無電解鎳(Ni)鍍敷與置換型無電解金(Au)鍍敷而形成Ni/Au皮膜之UBM的方法為一般的方法。經鍍敷之晶圓曝露於高溫或高濕下之時,Ni會擴散至金皮膜中,並在表面析出而形成Ni氧化物,故對焊料潤濕性、打線接合(wire bonding)性造成不良影響。此時,一般係在無電解鎳鍍敷與置換型無電解金鍍敷之間進行屬於Ni擴散之阻隔層的無電解鈀(Pd)鍍敷,而設為Ni/Pd/Au皮膜。再者,在本發明中,「/」之記號係意指藉由各鍍敷處理步驟所形成之複數個鍍敷膜之構造,並以自基材側起之鍍敷的次序為各鍍敷膜之標記順位。
當在具有電極墊之基板上形成鈍化膜(PV膜),使電極墊露出,並在前述電極墊上形成無電解鎳鍍敷皮膜時,例如如同第4A圖所示,前述無電解鎳鍍敷皮膜13係以被覆前述鈍化膜11之表面的一部分之方式從電極墊12溢出而形成。
此時,無電解鎳鍍敷皮膜13與鈍化膜11之接著性低,其結果,有時會在鈍化膜11與無電解鎳鍍敷皮膜13之界面形成間隙。如第4B圖所示,在其後之無電解金鍍敷時,無電解金鍍敷液會在箭頭方向滲入鈍化膜11與形成於鈍化膜11上之無電解鎳鍍敷皮膜13之間隙,並腐蝕鎳,以
致產生空穴V而成為問題。特別是在形成Ni/Pd/Au皮膜時,容易產生空穴V,而空穴V之產生成為問題。
就防止此空穴產生之半導體裝置而言,專利文獻1揭示一種半導體裝置,係具有:形成於半導體晶片之上方的配線;形成於前述配線上且在前述配線上具有開口部之絕緣膜(鈍化膜)、以及形成於前述開口部上之凸塊電極;其中,前述凸塊電極之形成區域係比從前述開口部露出之前述配線之露出區域還小。該半導體裝置可藉由下述方式而得到,該方式為:藉由選擇性除去配線上之絕緣膜而使配線之墊區域露出,在前述絕緣膜上形成具有開口部的掩罩膜,其中該開口部在前述墊區域上且比前述墊區域還小,在前述開口部內形成凸塊電極。形成前述掩罩膜之後,藉由在前述開口部內形成無電解Ni鍍敷皮膜,而在比電極墊之露出區域還小的區域形成無電解Ni鍍敷皮膜,形成UBM之後除去前述掩罩膜,藉此設為絕緣膜與無電解Ni鍍敷皮膜不接觸之構造。
[專利文獻1]日本特開2003-297868號公報
前述專利文獻1所記載之方法中係成為鈍化膜與凸塊電極不接觸之構造,故不會產生如上述之空
穴,但必須形成掩罩膜,增加製造步驟。又,配線之墊的形成有掩罩膜之部分係在除去掩罩膜時墊會露出。
本發明之實施形態之課題在於提供一種半導體晶圓,係在基板上形成有:鈍化膜;電極墊;以及在電極墊上之無電解鎳鍍敷皮膜、無電解鈀鍍敷皮膜及無電解金鍍敷皮膜,該半導體晶圓之於鈍化膜與無電解鎳鍍敷皮膜之界面產生的空穴受到抑制,且前述電極墊整面經前述無電解鎳鍍敷皮膜被覆。
本發明之實施形態包括下述構成。
(1)一種半導體晶圓,係在基板上具有:電極墊;覆蓋前述基板之上表面,且具有使前述電極墊露出之開口部的鈍化膜;形成於前述電極墊上之無電解鎳鍍敷皮膜,形成於前述無電解鎳鍍敷皮膜上之無電解鈀鍍敷皮膜,及形成於前述無電解鈀鍍敷皮膜上之無電解金鍍敷皮膜;其中,關於存在於前述鈍化膜與前述無電解鎳鍍敷皮膜之界面的空穴,從空穴之前端起至電極墊表面為止之長度為0.3μm以上,空穴之寬度為0.2μm以下,且前述電極墊之整面經前述無電解鎳鍍敷皮膜被覆。
(2)如前述(1)項所述之半導體晶圓,其中,前述無電解鎳鍍敷皮膜、無電解鈀鍍敷皮膜、及無電解金鍍敷皮膜之膜厚分別為0.5μm至15.0μm、0.02μm至0.50μm、0.01μm至
0.50μm。
(3)如前述(1)或(2)項所述之半導體晶圓,其中,前述無電解金鍍敷皮膜具有置換金鍍敷皮膜與還原金鍍敷皮膜,置換金鍍敷皮膜之厚度為0.01μm以下,還原金鍍敷皮膜之厚度為0.01μm以上。
(4)一種半導體晶圓之製造方法,係用以製造前述(1)至(3)項中任一項所述之半導體晶圓之方法,該製造方法係具有:在基板上形成電極墊之步驟;在形成有前述電極墊之基板的上表面形成鈍化膜之步驟;在前述鈍化膜形成使前述電極墊露出之開口部之步驟;在前述露出之電極墊上形成無電解鎳鍍敷皮膜之步驟,形成無電解鈀鍍敷皮膜之步驟,以及形成無電解金鍍敷皮膜之步驟;其中,前述形成無電解金鍍敷皮膜之步驟係具有形成無電解置換金鍍敷皮膜之步驟及形成無電解還原金鍍敷皮膜之步驟;關於前述形成無電解置換金鍍敷皮膜之步驟,就無電解置換金鍍敷液而言,使用當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而進行無電解置換金鍍敷;或者在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液時,以鍍
敷膜厚會成為20nm以下之鍍敷條件進行無電解置換金鍍敷。
若依據本發明之實施形態,可提供一種半導體晶圓,係在基板上形成有:鈍化膜;電極墊;以及於電極墊上之無電解鎳鍍敷皮膜、無電解鈀鍍敷皮膜及無電解金鍍敷皮膜;其中,該半導體晶圓之在鈍化膜與形成於電極墊上之無電解鎳鍍敷皮膜之界面產生的空穴受到抑制,且電極墊整面經無電解鎳鍍敷皮膜被覆。
11‧‧‧鈍化膜
12‧‧‧電極墊
13‧‧‧無電解鎳鍍敷皮膜
14‧‧‧無電解鈀鍍敷皮膜
15‧‧‧無電解金鍍敷皮膜
A‧‧‧無電解還原金鍍敷之區域
B‧‧‧無電解置換金鍍敷之區域
P‧‧‧還原金鍍敷與置換金鍍敷之界線
V‧‧‧空穴
第1圖係本發明之實施形態的半導體晶圓之一例的剖面圖,且係表示存在於鈍化膜與無電解鎳鍍敷皮膜之界面的空穴之從空穴之前端起至電極墊之表面為止的長度x、及空穴之寬度y的圖。
第2圖係本發明之實施形態的半導體晶圓之其他例的剖面圖。
第3A圖係表示半導體晶圓之AES縱深分析(depth profile)的圖,其中,該半導體晶圓係具有無電解鎳鍍敷皮膜、形成於前述無電解鎳鍍敷皮膜上之無電解鈀鍍敷皮膜、形成於前述無電解鈀鍍敷皮膜上之無電解置換金鍍敷皮膜與無電解還原金鍍敷皮膜。
第3B圖係第3A圖所示之AES縱深分析之部分放大圖。
第4A圖係表示半導體晶圓之無電解鎳鍍敷皮膜以覆蓋鈍化膜之表面的一部分之方式形成的狀態之圖。
第4B圖係表示半導體晶圓之鈍化膜與鎳鍍敷皮膜之間的空穴之圖。
本發明之實施形態的半導體晶圓,係在基板上具有:電極墊;覆蓋前述基板之上表面,且具有使前述電極墊露出之開口部的鈍化膜;形成於前述電極墊上之無電解鎳鍍敷皮膜,形成於前述無電解鎳鍍敷皮膜上之無電解鈀鍍敷皮膜,及形成於前述無電解鈀鍍敷皮膜上之無電解金鍍敷皮膜;其中,關於存在於前述鈍化膜與前述無電解鎳鍍敷皮膜之界面的空穴,從空穴之前端起至電極墊表面為止之長度為0.3μm以上,空穴之寬度為0.2μm以下,且前述電極墊整面經前述無電解鎳鍍敷皮膜被覆。
於第1圖表示在電極墊上進行無電解鎳鍍敷時,在無電解鎳鍍敷皮膜以覆蓋前述鈍化膜之表面的一部分之方式溢出而形成的情形,在鈍化膜與鎳鍍敷皮膜之界面產生的空穴之一例。無電解鎳鍍敷皮膜13亦形成於鈍化膜11上,且從其前端起沿著鈍化膜11而產生空穴V。
在本發明之實施形態中,前述空穴之從空穴之前端起至電極墊之表面為止之長度為0.3μm以上,空穴之寬度為0.2μm以下。
前述空穴之從空穴的前端起至電極墊表面為止之長度、空穴之寬度可藉由以FIB切割剖面並以SEM觀察來測
定。於第1圖表示本發明中之空穴的從空穴之前端起至電極墊表面為止之長度、及空穴之寬度的測定方法。從空穴之前端起至電極墊之表面為止的長度係指空穴V之最接近電極墊12之前端與電極墊12表面之沿著鈍化膜11的距離x,亦即鈍化膜11之無空穴的部分之從電極墊12起的長度。又,所謂空穴之寬度係指從鈍化膜11之表面起至在垂直方向分離之無電解鎳鍍敷皮膜13為止的長度,所謂空穴之寬度為0.2μm以下係指從鈍化膜11之表面起的前述長度為最長的部分之空穴的長度y為0.2μm以下。
又,空穴V之觀察係至少進行5處,且必須所有的經測定之空穴之從空穴之前端起至電極墊之表面為止的長度皆為0.3μm以上,空穴之寬度皆為0.2μm以下。
若存在空穴,則有時會在空穴中殘存處理液,並對可靠性(特性)造成影響。藉由使空穴之從空穴之前端起至電極墊之表面為止的長度為0.3μm以上、空穴之寬度為0.2μm以下,即使在空穴中殘存處理液,亦不會對可靠性造成影響,可提升半導體晶圓之可靠性。
又,本發明之實施形態的半導體晶圓係電極墊整面經前述無電解鎳鍍敷皮膜被覆。若電極墊在表面露出,則可靠性會降低。
關於電極墊是否被無電解鎳鍍敷皮膜被覆整面,可藉由以FIB切割剖面並以SEM觀察來確認。
又,關於電極墊是否被無電解鎳鍍敷皮膜被覆整面之判斷係至少進行觀察5處,且必須所有被觀察者皆為電極
墊被無電解鎳鍍敷皮膜被覆整面。
又,從空穴之前端起至電極墊之表面為止的長度x若為0<x,則可判斷為電極墊整面經無電解鎳鍍敷皮膜被覆。
又,本發明之實施形態的半導體晶圓係如第2圖所示,前述無電解鎳鍍敷皮膜13亦可僅接觸前述鈍化膜11之側面而形成。此時亦會於鈍化膜11與無電解鎳鍍敷皮膜13之間產生空穴V。有關空穴V,係與上述之無電解鎳鍍敷皮膜13以覆蓋鈍化膜11之表面的一部分之方式溢出而形成之情形相同,從空穴之前端起至電極墊之表面為止的長度x為0.3μm以上、空穴之寬度y為0.2μm以下。
本發明之實施形態的半導體晶圓可藉由下述方式而製造,該方式係具有:在基板上形成電極墊之步驟;在形成有前述電極墊之基板的上表面形成鈍化膜之步驟;在前述鈍化膜形成使前述電極墊露出之開口部之步驟;在前述露出之電極墊上形成無電解鎳鍍敷皮膜之步驟,形成無電解鈀鍍敷皮膜之步驟,以及形成無電解金鍍敷皮膜之步驟;其中,前述形成無電解金鍍敷皮膜之步驟係具有形成無電解置換金鍍敷皮膜之步驟及形成無電解還原金鍍敷皮膜之步驟;關於前述形成無電解置換金鍍敷皮膜之步驟,就無電解置換金鍍敷液而言,使用當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而進行無
電解置換金鍍敷;或者在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液時,以鍍敷膜厚會成為20nm以下之鍍敷條件進行無電解置換金鍍敷。
形成於電極墊上之無電解鎳鍍敷皮膜與鈍化膜(SiN、SiO2或聚醯亞胺樹脂膜等)之界面僅物理性密著,若有熱膨脹係數的差異等,則有時會在兩者之間產生間隙。
無電解金鍍敷之際,金鍍敷液會滲入該間隙,在腐蝕性(置換反應性)高之金鍍敷液的情形會產生空穴。
在無電解鎳鍍敷皮膜/無電解鈀鍍敷皮膜/無電解金鍍敷皮膜(Ni/Pd/Au)規格中,形成無電解金鍍敷皮膜時,當使用一般的Ni/Pd/Au用所使用的置換金鍍敷液,並以一般的條件進行無電解置換金鍍敷時,該金鍍敷液係置換反應性高,會產生空穴、或不僅在墊側甚至在表面產生Ni的孔蝕,Au皮膜之膜厚會隨時間變厚。
因此,關於本發明之實施形態的半導體晶圓之製造方法,在Ni/Pd/Au規格中,形成無電解金鍍敷皮膜之步驟係具有形成無電解置換金鍍敷皮膜之步驟及形成無電解還原金鍍敷皮膜之步驟,其中,關於前述形成無電解置換金鍍敷皮膜之步驟,就無電解置換金鍍敷液而言,使用當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之置換反應性低的無電解置換金鍍敷液而進行無電解置換金鍍敷;或者在使用當以鍍
敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液時,以鍍敷膜厚會成為20nm以下之鍍敷條件進行無電解置換金鍍敷。
在鈀鍍敷皮膜上,以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液係因金鍍敷之置換反應性不高,故即使金鍍敷液滲入鈍化膜與無電解鎳鍍敷皮膜之間隙,亦幾乎不產生空穴。使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而進行之無電解置換金鍍敷,較佳係以所得之鍍敷膜厚會成為20nm以下之條件進行。
又,在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之置換反應性高的無電解置換金鍍敷液時,係以鍍敷膜厚會成為20nm以下之鍍敷條件進行無電解置換金鍍敷。以鍍敷膜厚會成為20nm以下之弱鍍敷條件進行無電解置換金鍍敷,藉此,金鍍敷之置換反應性變弱,即使金鍍敷液滲入鈍化膜與無電解鎳鍍敷皮膜之間隙,亦幾乎不產生空穴。
鍍敷膜厚會成為20nm以下之鍍敷條件可舉例如降低鍍敷溫度、縮短鍍敷時間。較佳係鍍敷膜厚會成為15nm以下之條件,更佳係會成為10nm以下之條件。
鍍敷時間係以1分鐘至30分鐘為較佳,更佳係1分鐘至15分鐘。若鍍敷時間變長,則金鍍敷液會滲入鈍化膜與無電解鎳鍍敷皮膜之間隙而容易產生空穴。又,若鍍敷時
間過短,則有時會未充分形成金鍍敷皮膜。
鍍敷溫度雖依使用之無電解置換金鍍敷液的置換反應性而定,但在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液時,以在鍍敷溫度10℃至95℃使用為較佳,以50℃至85℃為更佳。在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液時,鍍敷溫度以低於80℃之溫度為較佳。
又,在上述之無電解置換金鍍敷中,在一定時間中鈀皮膜被金覆蓋而反應停止,金之膜厚不會再變厚。
在無電解鈀鍍敷皮膜上,在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而形成無電解置換金鍍敷皮膜時,或者在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液並以鍍敷膜厚會成為20nm以下之鍍敷條件形成無電解置換金鍍敷皮膜時,因金鍍敷皮膜之膜厚不會變厚,故以藉由進一步進行無電解還原金鍍敷,增加金之膜厚為較佳。
前述基板可舉例如具備使用於半導體晶圓之電極的基板。
形成於前述半導體基板之電極墊係以鋁系、銅系、銀系、或金系為較佳。
半導體晶圓之晶圓可使用矽晶圓,並藉由
通常之步驟,在基板上形成電極墊,在形成有前述電極墊之基板的上表面形成鈍化膜,在前述鈍化膜形成使前述電極墊露出之開口部。前述電極墊之最表面係以設為銅系或鋁系表面,並在電極墊進行無電解鎳鍍敷為較佳。
又,晶圓亦可使用GaAs基板。此時,以將電極表面之最表面設為金表面,並進行無電解鎳鍍敷為較佳。
上述電極表面之銅系可為被使用來作為半導體晶圓之電極的公知之銅系者,例如可使用純銅、磷青銅等銅及銅合金。鋁系可為被使用來作為半導體晶圓之電極的公知之鋁系者,例如可使用純鋁、AlCu(0.5%)、AlSi(1%)等鋁合金等。金系可為被使用來作為半導體晶圓之電極的公知之金系者,可舉例如Ti/Pt/Au等。
前述電極墊之形成方法可使用已知之方法、條件。
前述鈍化膜可為一般所使用者,可舉例如氮化矽(SiN)、氧化矽、聚醯亞胺等。又,關於各別之膜厚,氮化矽(SiN)或氧化矽較佳為1μm以下,聚醯亞胺較佳為0.5μm至15μm。
前述鈍化膜之形成方法可使用已知的方法、條件。
又,在前述鈍化膜形成使前述電極墊露出之開口部的方法亦可使用已知的方法、條件。
在電極墊形成無電解鎳鍍敷皮膜。
例如,電極為銅系表面,並進行無電解鎳鍍敷時,會成為以下之製程。
脫脂→蝕刻→酸浸漬→致活(賦予觸媒)
→無電解鎳鍍敷
又,電極為鋁系表面,並進行無電解鎳鍍敷時,會成為以下之製程。
脫脂→酸浸漬→一次鋅酸鹽→酸浸漬→二次鋅酸鹽→無電解鎳鍍敷
鋁系之電極為AlSi時,在脫脂步驟之後設置蝕刻步驟。又,電極為AlCu時,在脫脂步驟之後,可依殘渣之程度而設置蝕刻步驟。
又,電極為銀系表面,並進行無電解鎳鍍敷時,會成為以下之製程。
脫脂→致活(賦予觸媒)→無電解鎳鍍敷
電極為金系表面,並進行無電解鎳鍍敷時,會成為以下之製程。
脫脂→活化→致活(賦予觸媒)→無電解鎳鍍敷
前述「脫脂」、「酸浸漬」、「致活(賦予觸媒)」、「一次鋅酸鹽」、「二次鋅酸鹽」、「活化」之步驟可依已知的方法、條件進行。又,墊之殘渣殘留時,若在脫脂之前進行電漿清潔(plasma cleaning),則鍍敷性會提升。
又,形成前述無電解鎳鍍敷皮膜後,形成無電解鈀鍍敷皮膜。
前述無電解鎳鍍敷、無電解鈀鍍敷所使用之鍍敷液、鍍敷方法可使用半導體晶圓之UBM形成用所
使用的公知之鍍敷液、鍍敷方法。
為了獲得本發明之實施形態的半導體晶圓,前述無電解鎳鍍敷所用之鍍敷液較佳係使用次磷酸鈉作為還原劑之中磷型無電解鎳鍍敷液,前述無電解鈀鍍敷液較佳係使用次磷酸鈉作為還原劑之無電解鈀鍍敷液。
各鍍敷之鍍敷皮膜的膜厚雖依晶圓之用途、要求特性而改變,但無電解鎳鍍敷皮膜之膜厚以0.5μm至15.0μm之範圍為較佳。但進行焊接時,從防止焊料之擴散的觀點而言,以1.5μm以上為較佳,更佳係1.5μm至10μm。
又,從防止鎳擴散的觀點而言,鈀鍍敷皮膜之膜厚係以0.02μm以上為較佳,更佳係0.02μm至0.50μm,再更佳係0.03μm至0.20μm。
又,從焊接時之潤濕性的觀點而言,金鍍敷皮膜係以0.01μm以上之膜厚為較佳,更佳係0.01μm至0.50μm,再更佳係0.02μm至0.20μm。
無電解鎳鍍敷皮膜、無電解鈀鍍敷皮膜、無電解金鍍敷皮膜之膜厚可藉由FIB切割出鍍敷皮膜之剖面,並藉由SEM或STEM觀察而測定。又,以使用市售之螢光X射線膜厚計進行測定為簡便且較佳。以螢光X射線膜厚計測定時,最初以與上述之FIB/SEM(或STEM)的剖面之實測值一致之方式將螢光X射線膜厚計之測定值乘以修正係數,則會成為正確的膜厚。
鍍敷皮膜之膜厚測定係測定電極墊中央附近之鍍敷皮
膜表面/界面會成為與電極墊平行之面的部分之膜厚。
本發明之實施形態的半導體晶圓較佳係無電解金鍍敷皮膜具有置換金鍍敷皮膜及還原金鍍敷皮膜,且置換金鍍敷皮膜之厚度為0.01μm以下,還原金鍍敷皮膜之厚度為0.01μm以上。
置換金鍍敷會成為產生空穴之主要原因,故愈薄(鍍敷時間愈短)愈佳。但,若置換金鍍敷皮膜未充分到某種程度,則還原金鍍敷不會成長。置換金鍍敷之下限值以0.002μm以上為較佳。
置換金鍍敷皮膜與還原金鍍敷皮膜之膜厚可藉由AES縱深分析來確認。
將在無電解鎳鍍敷皮膜上形成有無電解鈀鍍敷皮膜、無電解置換金鍍敷皮膜及無電解還原金鍍敷皮膜之半導體晶圓的AES縱深分析之一例表示於第3A圖,將第3A圖所示之AES縱深分析的部分擴大圖表示於第3B圖。第3A圖所示之例中濺鍍速率以約25nm/分鐘(以SiO2換算而言為10nm/分鐘)進行。可知在濺鍍時間2.8分鐘以後鈀的濃度高於金之濃度,故直至濺鍍時間2.8分鐘為止為金,且金之膜厚約為70nm。在第3A圖及第3B圖中,P所示之處為開始檢測出鈀之時點,且成為還原金鍍敷與置換金鍍敷之界線。咸認直至檢測出鈀之濺鍍時間1.0分鐘為止的A所示之區域為還原金鍍敷皮膜,其以後之B所示之區域為置換金鍍敷皮膜。因此,還原金鍍敷皮膜之膜厚成為25nm,置換金鍍敷皮膜之膜厚成為45nm。
又,上述之例係為了容易瞭解而舉出置換金鍍敷皮膜之膜厚為45nm之例來說明,但在本發明中,較佳係置換金鍍敷皮膜之膜厚為0.01μm以下。又,較佳係還原金鍍敷皮膜之厚度為0.01μm以上。
一般,就在無電解鈀鍍敷之後進行之無電解置換金鍍敷所用的鍍敷液而言,使用作為Ni/Pd/Au用而販售之置換金鍍敷液,在無電解鎳鍍敷之後進行無電解置換金鍍敷時,使用作為Ni/Au用而販售之置換金鍍敷液。
在Ni上與在Pd上就Au之反應性(置換能力)而言有差異,若為在Pd上,則難以置換。Ni/Pd/Au用之置換金鍍敷相較於Ni/Au用者,需要會引起更強的置換之組成,且鍍敷藥品製造商分成Ni/Au用與Ni/Pd/Au用之置換金鍍敷而販售。
在本發明中,就在無電解鈀鍍敷之後進行之無電解置換金鍍敷所用的鍍敷液而言,可使用當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而形成金鍍敷皮膜。就當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而言,可舉例如Ni/Au用之置換金鍍敷液。前述無電解置換金鍍敷液係因反應性弱,故在Ni/Pd上進行鍍敷時,幾乎不產生空穴、或即使產生空穴亦變小。但,因屬於反應性弱之液體,故相較於Ni/Pd/Au用之置換金鍍敷,鍍敷之膜厚變薄。
又,在本發明中,就在無電解鈀鍍敷後進行之無電解置換金鍍敷所用的鍍敷液而言,雖可使用當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液,但此時係以鍍敷膜厚會成為20nm以下之鍍敷條件進行無電解置換金鍍敷。就當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液而言,可舉例如Ni/Pd/Au用之置換金鍍敷液。
Ni/Pd/Au用之置換金鍍敷因反應性強,故若以一般的鍍敷條件進行置換金鍍敷,則鍍敷膜厚會超過20nm,但藉由以鍍敷膜厚會成為20nm以下之反應性弱的條件進行置換金鍍敷,可抑制因從側面浸入之液體而Ni腐蝕及空穴的產生。
就無電解置換金鍍敷所用之當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而言,較佳係含有非氰系水溶性金化合物、及焦亞硫酸化合物。例如,可使用被用來作為Ni/Au用之公知的無電解置換金鍍敷液。
非氰系水溶性金化合物若為非氰系之金化合物則無特別限定,但較佳可使用亞硫酸金、硫代硫酸金、硫氰酸金、氯金酸、或此等之鹽。鹽可使用鹼金屬鹽、鹼土金屬鹽、銨鹽等,以鈉鹽、鉀鹽、銨鹽等為較佳。
前述無電解置換金鍍敷液較佳係在鍍敷液中含有以金
濃度而言為0.1g/L至100g/L之此等金化合物,更佳係含有0.5g/L至20g/L。若金濃度為未達0.1g/L,則金之置換速度明顯變慢,即使超過100g/L,效果亦會飽和而無益。
焦亞硫酸化合物可使用焦亞硫酸、或其鹼金屬鹽、鹼土金屬鹽、銨鹽等,以焦亞硫酸鈉、焦亞硫酸鉀、焦亞硫酸銨等為較佳。較佳係在鍍敷液中含有0.1g/L至200g/L之焦亞硫酸化合物,以含有1g/L至100g/L為更佳。焦亞硫酸化合物之濃度未達0.1g/L,則防止基底鎳之不均勻的腐蝕之效果低,即使超過200g/L,效果亦會飽和而無益。
又,前述無電解置換金鍍敷液以含有硫代硫酸化合物為較佳。
硫代硫酸化合物可使用硫代硫酸之鹼金屬鹽、鹼土金屬鹽、銨鹽等,以硫代硫酸鈉、硫代硫酸鉀、硫代硫酸銨等為較佳。硫代硫酸化合物係以在鍍敷液中被含有1mg/L至10g/L為較佳,以被含有10mg/L至1000mg/L為更佳。硫代硫酸化合物之濃度未達1mg/L,則提升焊料接著強度之效果低,即使超過10g/L,效果亦會飽和而無益。
又,前述無電解置換金鍍敷液較佳係含有亞硫酸化合物作為安定劑,亞硫酸化合物可舉例如亞硫酸、或其鹼金屬鹽、鹼土金屬鹽、銨鹽等。鍍敷液中之亞硫酸化合物的濃度以0.1g/L至200g/L為較佳,更佳係1g/L至100g/L。若未達0.1g/L,則未顯現作為安定劑之效果,即使超過200g/L,效果亦會飽和而無益。
又,前述無電解置換金鍍敷液可進一步含有胺基羧酸化合物作為錯合劑,胺基羧酸化合物可舉例如乙二胺四乙酸、羥基乙基乙二胺三乙酸、二羥基乙基乙二胺二乙酸、丙烷二胺四乙酸、二乙三胺五乙酸、三乙四胺六乙酸、甘胺酸、甘胺醯基甘胺酸、甘胺醯基甘胺醯基甘胺酸、二羥基乙基甘胺酸、亞胺基二乙酸、羥基乙基亞胺基二乙酸、氮基三乙酸、氮基三丙酸、或此等之鹼金屬鹽、鹼土金屬鹽、銨鹽等。鍍敷液中之胺基羧酸化合物的濃度以0.1g/L至200g/L為較佳,更佳係1g/L至100g/L。若胺基羧酸化合物之濃度未達0.1g/L,則缺乏作為錯合劑之效果,即使超過200g/L,效果亦會飽和而無益。
又,前述無電解置換金鍍敷液可依需要而添加磷酸系化合物作為pH緩衝劑。
磷酸系化合物可舉例如磷酸、焦磷酸、或此等之鹼金屬鹽、鹼土金屬鹽、銨鹽、磷酸二氫鹼金屬鹽、磷酸二氫鹼土金屬鹽、磷酸二氫銨、磷酸氫二鹼金屬鹽、磷酸氫鹼土金屬、磷酸氫二銨等。鍍敷液中之磷酸系化合物的濃度以0.1g/L至200g/L為較佳,更佳係1g/L至100g/L。
前述無電解置換金鍍敷液之pH係以使用上述之化合物作為pH緩衝劑並調整至pH4至10為較佳,以調整至pH5至9為更佳。
又,前述無電解置換金鍍敷液係以在浴溫10℃至95℃使用為較佳,以50℃至85℃為更佳。
當鍍敷液之pH、及浴溫為上述範圍外時,會有鍍敷速
度慢、或容易引起浴分解等之問題。
就無電解置換金鍍敷所用之當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液而言,可使用被用來作為Ni/Pd/Au用之公知的無電解置換金鍍敷液。
進行前述無電解置換金鍍敷後,進行無電解還原金鍍敷。
無電解還原金鍍敷液可為市售者。無電解還原金鍍敷皮膜係以0.01μm以上、0.50μm以下為較佳。若為未達0.01μm,則焊料特性、打線接合特性會隨著膜厚變小而逐漸降低。又,即使超過0.50μm,亦無特性上之變化,就成本而言以0.50μm以下為較佳。更佳係0.02μm至0.20μm。
本發明係不受限於各實施形態,可在不超出其要旨之範圍內變更構成要素並具體化。又,可藉由各實施形態所揭示之複數個構成要素之適當組合而形成各種發明。例如,亦可從實施形態所示之全構成要素中刪除一些構成要素。亦可進一步適當組合相異之實施形態的構成要素。
以下,雖表示本發明之實施形態的具體例,但此等實施例係為了更充分理解本發明及其優點而說明者,並非意圖限定發明者。
[實施例1]至[實施例7]、[比較例1]、[比較例2]
使用在基板上具有以下之電極墊及鈍化膜的8英吋Si晶圓,依據下述表1-1、及表1-2所記載之製程及條件實施無電解鍍敷。
Si晶圓(8英吋)
電極:AlCu墊、膜厚5μm、墊開口直徑300μm圓形
鈍化膜:記載於表1。
在表1中,「○」表示進行該處理。
無電解置換金鍍敷所用之鍍敷液「FA500(JX金屬製)」係屬於當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為15nm之鍍敷液,「FA210(JX金屬製)」係屬於當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為30nm之鍍敷液。
對於已進行無電解置換金鍍敷與無電解還原金鍍敷之半導體晶圓,藉由AES分析,而求出置換金鍍敷膜與還原金鍍敷膜各自的膜厚。
又,為了確認所得之無電解鍍敷的析出性及空穴之狀態,進行鍍敷後之顯微鏡觀察及以螢光X射線膜厚計測定鍍敷膜厚。
為了觀察空穴(測定上述x及y之長度),而觀察墊端之剖面SEM。對於1試樣,觀察5處之剖面,測定從空穴之前端起至電極墊之表面為止的長度x為最短之值、及空穴之寬度y為最長之值。
將上述測定結果一併記載於表1中。
焊料特性評估
在鍍敷皮膜上搭載Sn-Ag-Cu焊球(150μm徑),以下述之條件回焊(5次)而形成焊料凸塊後,實施焊料剪切試驗,從破壊界面評估鍍敷之密著性。
回焊加熱條件
溫度:峰頂265℃、在260℃以上加熱40秒
環境:氮環境(氧濃度:600ppm至800ppm)
使用焊球:Sn-3%Ag-0.5%Cu(150μm徑)
焊料剪切試驗條件
焊料剪切速度:100μm/秒
焊料剪切高度:離鍍敷/焊料接合面為10μm
可靠性試驗
在鍍敷皮膜上與上述焊料特性評估同樣地搭載Sn-Ag-Cu焊球(150μm徑),其後,在HAST試驗(在120℃、85%RH放置96hr)後,對各試樣進行5處之墊端的剖面觀察。針對水會從空穴浸透且Al腐蝕之個數一併記載於表1。(HAST:High Accelerated Stress Test)
如表1所示,可確認在本發明例中無電解鍍敷良好地析出,由焊料剪切試驗所得之破壊界面全部皆為焊料面,就連HAST試驗亦為良好。
Claims (4)
- 一種半導體晶圓,係在基板上具有:電極墊;覆蓋前述基板之上表面,且具有使前述電極墊露出之開口部的鈍化膜;形成於前述電極墊上之無電解鎳鍍敷皮膜,形成於前述無電解鎳鍍敷皮膜上之無電解鈀鍍敷皮膜,以及形成於前述無電解鈀鍍敷皮膜上之無電解金鍍敷皮膜;其中,關於存在於前述鈍化膜與前述無電解鎳鍍敷皮膜之界面的空穴,從空穴之前端起至電極墊表面為止之長度為0.3μm以上,空穴之寬度為0.2μm以下,且前述電極墊之整面經前述無電解鎳鍍敷皮膜被覆。
- 如申請專利範圍第1項所述之半導體晶圓,其中,前述無電解鎳鍍敷皮膜、無電解鈀鍍敷皮膜、及無電解金鍍敷皮膜之膜厚分別為0.5μm至15.0μm、0.02μm至0.50μm、0.01μm至0.50μm。
- 如申請專利範圍第1或2項所述之半導體晶圓,其中,前述無電解金鍍敷皮膜具有置換金鍍敷皮膜與還原金鍍敷皮膜,置換金鍍敷皮膜之厚度為0.01μm以下,還原金鍍敷皮膜之厚度為0.01μm以上。
- 一種半導體晶圓之製造方法,係用以製造申請專利範圍第1至3項中任一項所述之半導體晶圓之方法,該製造方法係具有: 在基板上形成電極墊之步驟;在形成有前述電極墊之基板的上表面形成鈍化膜之步驟;在前述鈍化膜形成使前述電極墊露出之開口部之步驟;在前述露出之電極墊上形成無電解鎳鍍敷皮膜之步驟,形成無電解鈀鍍敷皮膜之步驟,以及形成無電解金鍍敷皮膜之步驟;其中,前述形成無電解金鍍敷皮膜之步驟,係具有形成無電解置換金鍍敷皮膜之步驟及形成無電解還原金鍍敷皮膜之步驟;關於前述形成無電解置換金鍍敷皮膜之步驟,就無電解置換金鍍敷液而言,係使用當在鈀鍍敷皮膜上以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會成為20nm以下之無電解置換金鍍敷液而進行無電解置換金鍍敷;或者在使用當以鍍敷溫度80℃、鍍敷時間15分鐘進行鍍敷時鍍敷膜厚會超過20nm之無電解置換金鍍敷液時,以鍍敷膜厚會成為20nm以下之鍍敷條件進行無電解置換金鍍敷。
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