TW201250883A - METHOD FOR MANUFACTURING Sn ALLOY BUMP - Google Patents

METHOD FOR MANUFACTURING Sn ALLOY BUMP Download PDF

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Publication number
TW201250883A
TW201250883A TW101102246A TW101102246A TW201250883A TW 201250883 A TW201250883 A TW 201250883A TW 101102246 A TW101102246 A TW 101102246A TW 101102246 A TW101102246 A TW 101102246A TW 201250883 A TW201250883 A TW 201250883A
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Taiwan
Prior art keywords
tin
layer
alloy
silver
bump
Prior art date
Application number
TW101102246A
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English (en)
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TWI536472B (zh
Inventor
Takeshi Hatta
Akihiro Masuda
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Mitsubishi Materials Corp
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Publication date
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Publication of TW201250883A publication Critical patent/TW201250883A/zh
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Publication of TWI536472B publication Critical patent/TWI536472B/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/11—Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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201250883 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適用於將電子零件安裝於基板的倒 裝晶片安裝等之際的錫合金凸塊之製造方法。 【先前技術】 目前，在將電子零件安裝於印刷基板等之情況下，大 多採用有藉由使用有凸塊的倒裝晶片安裝而進行表面安裝 的方法。就形成上述凸塊的方法而言，例如，藉由電解電 鍍來將焊錫層，形成於形成在基板上的光阻開口部內的電 極墊上，並在去除光阻之後進行回焊，以使焊錫層熔融而 形成略球狀的凸塊。 近年來，由於含有鉛（Pb)的焊錫材料對於環境面而 言較爲不利，因此於電子零件之接合中所使用的焊錫，係 邁向無鉛化，且針對凸塊的材料也對以錫爲主成分的錫-銀或者是錫-銅二元系焊錫或錫-銀-銅三元系焊錫等作 探討。 例如，於專利文獻1中，係記載有將錫一銀-銅三元 系薄膜形成於基材上的方法，其係將基材浸漬於含有錫化 合物、銀化合物以及銅化合物的電鍍浴中，並藉由電鍍而 形成的方法。 此外，於專利文獻2中，係提案有在進行錫-銀合金 電鍍’接著進行錫-銅合金電鍍之後，對所得之多層合金 電鏟層作回焊之形成錫一銀-銅焊錫合金的方法。 -5- 201250883 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開2006-291323號公報 〔專利文獻2〕日本特開2003-342784號公報 【發明內容】 〔發明所欲解決之課題〕 於上述先前技術中，仍存在有以下之課題。 亦即’於在近年來因微細化而被細節距化而成爲高縱 橫比圖案的光阻之開口部（洞）處形成合金電鍍的情況下 ，且於使用錫_銀一銅合金電鍍液的情況或者是以錫一銀 與錫-銅之電鍍液所進行的二層電鍍的情況中，由於在開 口部之底部銀或銅的析出會受到抑制，因而導致越底部銀 或銅越少而錫的析出越多之缺陷產生。因此，在開口部的 高度方向會產生組成之不均，結果產生了錫合金凸塊之組 成控制爲困難的問題。特別是，若多次反覆進行電解電鍍 ，則電鍍液中的酸性濃度會提高導致黏度上升，而使銀變 得更加難以在底部析出，因此，欲在回焊後得到安定的組 成係有困難。 本發明係鑑於前述之課題而完成者，其目的爲提供一 種於錫合金凸塊的高度方向之組成控制爲容易的錫合金凸 塊之製造方法。 〔用以解決課題之手段〕 -6- 201250883 本發明係爲了解決前述課題而採用了以下之構造。亦 即’本發明之錫合金凸塊之製造方法，係以錫與其他一種 或二種以上的金屬之合金所形成的錫合金凸塊之製造方法 ’其特徵爲具有：藉由電解電鍍來將錫層形成於形成在基 板上之光阻開口部內的電極上之工程；藉由電解電鍍來將 錫與前述其他金屬之合金層，層積於前述錫層上之工程； 以及在去除前述光阻之後，將前述錫層與前述合金層進行 熔融，而形成錫合金凸塊之工程。 於該錫合金凸塊之製造方法中，係藉由電解電鍍來將 錫層形成於電極上，且藉由電解電鍍來將錫與前述其他金 屬（前述其他一種或二種以上之金屬）之合金層，層積於 該錫層上’故藉由在電鍍合金層之際所預先形成的錫層， 而減輕開口部的深度，因此能夠抑制高度方向之其他金屬 的組成之不均。另外，於所層積的合金層中之其他金屬， 係因應於將錫層與合金層進行熔融並作成錫合金凸塊之際 的目標組成，而將組成設定成較僅有錫與其他金屬之合金 電鍍的情況更高，藉此可進行錫合金凸塊之組成控制。 此外，本發明之錫合金凸塊之製造方法，其中，前述 其他金屬爲銀，且該製造方法係具有：藉由電解電鍍來將 作爲前述合金層之錫-銀層形成於前述錫層上之工程；和 在去除前述光阻之後，將前述錫層與前述錫-銀層進行熔 融，而形成作爲前述錫合金凸塊之錫-銀凸塊之工程。 亦即，於該錫合金凸塊之製造方法中，係藉由電解電 鍍來將錫-銀層形成於錫層上，且使錫層與錫一銀層熔融 201250883 ，故可形成將由銀析出所致之高度方向的銀組成之不均作 了減低的錫-銀合金凸塊。 此外，本發明之錫合金凸塊之製造方法，其中，前述 其他金屬爲二種金屬，且該製造方法係具有：藉由電解電 鍍來將錫與前述二種之其中一種的合金層及錫與前述二種 之另一種的合金層之二層，層積於前述錫層上之工程；和 在去除前述光阻之後，將前述錫層與所層積的二層之前述 合金層進行熔融，而形成錫合金凸塊之工程。 亦即，於該錫合金凸塊之製造方法中，係藉由電解電 鍍來將錫與前述二種之其中一種的合金層及錫與前述二種 之另一種的合金層之二層，層積於該錫層上，故藉由在電 鍍二層之合金層之際所預先形成的錫層，而減輕開口部的 深度，因此能夠抑制高度方向之二種金屬的組成之不均。 進而，本發明之錫合金凸塊之製造方法，其中，前述 二種之其中一種金屬爲銀且另一種金屬爲銅，且該製造方 法係具有：藉由電解電鍍來將錫-銀層與錫-銅層之二層 ，形成於前述錫層上之工程；和在去除前述光阻之後，將 前述錫層、前述錫-銀層以及前述錫-銅層進行熔融，而 形成作爲前述錫合金凸塊之錫-銀-銅凸塊之工程》 亦即，於該錫合金凸塊之製造方法中，係藉由電解電 鍍來將錫-銀層與錫-銅層之二層形成於錫層上，且使錫 層、錫-銀層以及錫-銅層熔融，故可形成將由銀或銅之 析出所致之高度方向的銀或銅的組成之不均作了減低的錫 —銀一銅合金凸塊。 -8- 201250883 〔發明效果〕 依據本發明，可達成下述之效果。 亦即’依據本發明之錫合金凸塊之製造方法，由於係 藉由電解電鍍來將錫層形成於電極上，且藉由電解電鑛來 將錫與其他金屬的合金層層積於該錫層上，故可抑制高度 方向之其他金屬的組成之不均’且可控制將各層熔融而形 成的凸塊之組成。 因此’依據本發明之錫合金凸塊之製造方法，可得到 與高縱橫比圖案相對應之組成均一性高的錫合金凸塊，且 使對應於細節距化一事成爲可能。 【實施方式】 以下，針對本發明之錫合金凸塊之製造方法的第1實 施形態，參照第1圖來進行說明。 於第1實施形態中’本發明之錫合金凸塊之製造方法 ，係以錫與銀等之其他一種或二種以上的金屬之合金所形 成的錫合金凸塊之製造方法，如第1圖所示，其係具有： 藉由電解電鍍來將錫層4a形成於形成在基板1上之光阻2 的開口部2a內的電極墊3上之工程；藉由電解電鍍來將 錫與前述其他金屬之合金層4b，層積於錫層4a上之工程 :以及在去除光阻2之後，藉由回焊處理來將錫層4a與 所層積的合金層4b進行熔融，而形成錫合金凸塊5之工 程。 -9- 201250883 例如，針對前述其他金屬爲銀的情況進行說明時，如 第1圖（a)所示，首先，藉由電解電鍍來將錫層4a形成 於形成在基板1上之光阻2的開口部2a內之電極墊3上 。該錫層4a，係被形成爲直至例如開口部2a之深度的一 半爲止。 上述基板1，係半導體晶圓、印刷基板或者是散熱基 板等，且於表面上將光阻2圖案化，並以1.0以上之高縱 橫比圖案設置凸塊用的開口部2a。 此外，上述電極墊3，係將例如銅電鍍膜3a與鎳電鍍 膜3b作層積而成之金屬膜。 上述開口部2a，係例如將深度設爲120μιη、開口直徑 設爲7〇μπι，且將縱橫比設爲1.7之高縱橫比的圖案。另 外，凸塊節距，係亦可爲1 00數十μηι之細節距。 接著，如第1圖（b)所示，藉由電解電鍍來將身爲 錫-銀層之合金層4b形成於錫層4a上。該身爲錫-銀層 之合金層4b，係被形成爲：與錫層4a具有相同的高度且 將開口部2a剩餘的另一半作塡埋。亦即，以塡埋因錫層 4a而被墊高且實質上縱橫比變小之開口部2a的方式，來 形成合金層4b (錫—銀層）。 另外，於所層積的合金層4b中之前述其他金屬，係 因應於將錫層4a與合金層4b進行熔融而作成錫合金凸塊 之際的目標組成，而將組成設定成較僅有錫與其他金屬之 合金電鍍的情況更高，藉此可進行錫合金凸塊之組成控制 -10- 201250883 亦即，於第1實施形態中，身爲錫一銀層之合金層4b ’係與回焊處理後之錫層4a與已熔融的錫合金凸塊的銀 組成相對應，而相較於僅以錫-銀電鍍來形成錫合金凸塊 的情況’將其銀組成設定成較高。例如，在以錫合金凸塊 爲目標的銀組成爲2.5wt%的情況下，於與錫層4a具有相 同高度的錫-銀層（合金層4b )中，將銀組成設定爲5wt %。 接著，去除上述光阻2，如第1圖（c)所示，藉由回 焊處理來將錫層4a與合金層4b (錫一銀層）進行熔融， 而形成略球狀之作爲錫合金凸塊5的錫-銀凸塊。另外， 就回焊處理而言，係在使用例如熱風式回焊爐，並於凸塊 表面塗佈有用以去除氧化膜的助焊劑之狀態下，在氮氣環 境下進行加熱。 於這樣的第1實施形態之錫合金凸塊之製造方法中， 係藉由電解電鍍來將錫層4a形成於電極墊3上，且藉由 電解電鍍來將錫與其他金屬之合金層4b，層積於該錫層 4a上，故而，藉由在電鑛合金層4b之際所預先形成的錫 層4a，來減輕開口部2a的深度，而能夠抑制高度方向之 前述其他金屬的組成之不均》因此，回焊處理後之錫合金 凸塊5的組成控制會變得容易。 特別是，於第1實施形態中，係藉由電解電鍍來將身 爲錫一銀層之合金層4b形成於錫層4a上，且使錫層4a 與合金層4b (錫-銀層）熔融，故可減低由銀析出所致之 高度方向的銀組成之不均，且形成將銀組成作了控制的錫 -11 - 201250883 _銀合金凸塊。 接著，針對本發明之錫合金凸塊之製造方法的第2實 施形態’係參照第2圖進行說明。另外，於以下之實施形 態的說明中’對於已在上述實施形態中作了說明的相同之 構成要素，係標示相同的符號，並省略其說明。 第2實施形態與第1實施形態不同之處在於：於第1 實施形態中’係將錫與一種金屬（銀）之合金層4b形成 於錫層4a上’並藉由回焊處理而形成錫合金凸塊，相對 於此’於第2實施形態中，前述其他金屬係爲二種金屬， 且其係以錫與二種金屬之合金所形成之錫合金凸塊之製造 方法，如第2圖所示，藉由電解電鍍來將錫與前述二種之 其中一種的第1合金層24b及錫與前述二種之另一種的第 2合金層24c之二層’層積於錫層4a上，並將其進行回焊 處理。 例如’以針對前述二種之其中一種金屬爲銀且另一種 金屬爲銅的情況作爲第2實施形態來進行說明時，如第2 圖（a)所示，首先’藉由電解電鍍來將錫層4a形成於形 成在基板1上之光阻2的開口部2a內之電極墊3上。 接著，如第2圖（b)所示，藉由電解電鍍來將身爲 錫-銅層之第1合金層24b與身爲錫-銀層之第2合金層 24c之二層，層積於錫層4a上。 此等身爲錫-銅層之第1合金層2 4b及身爲錫-銀層 之第2合金層24c’係被形成爲：將開口部2a之剩餘的一 半作塡埋。 -12- 201250883 例如’上述各層的厚度，係以錫層4 a :第1合金層 24b (錫—銅層）：第2合金層24c (錫一銀層）=1: 1: 3之比率而形成。 另外，於第1合金層24b及第2合金層24c中之前述 二種金屬，係因應於將錫層4a、第1合金層24b、以及第 2合金層24c進行熔融並作成錫合金凸塊25之際的目標之 組成’而將組成設定成較僅有錫與前述二種金屬之合金電 鍍的情況更高’藉此可進行錫合金凸塊之組成控制。 亦即，於第2實施形態中，第1合金層24b (錫-銅 層）及第2合金層24c (錫-銀層），係對應於在回焊處 理後與已熔融的錫合金凸塊之銀組成及銅組成，而相較於 僅以錫-銀-銅電鑛來形成錫合金凸塊的情況，將銀組成 及銅組成設定成較高。例如，在以錫合金凸塊25爲目標 之組成爲錫-3銀-0.5銅（質量％)的情況中，將第1合金 層2 4b (錫—銅層）之銅組成設定爲2.5 wt%，且將第2 合金層24c (錫一銀層）之銀組成設定爲5wt%。 接著，去除上述光阻2，如第2圖（c)所示，藉由回 焊處理來將錫層4a、第1合金層24b以及第2合金層24c 進行熔融，而形成略球狀之作爲錫合金凸塊2 5的錫-銀 —銅凸塊。 另外，於錫層4a上，雖依序層積有第1合金層2 4b ( 錫—銅層）、第2合金層24c (錫—銀層），但反過來依 序層積第2合金層24c (錫一銀層）、第1合金層24b ( 錫一銅層）亦無妨。 -13- 201250883 於這樣的第2實施形態之錫合金凸塊之製造方法中， 係藉由電解電鍍來將錫與前述二種之其中一種的第1合金 層2 4b及錫與前述二種之另一種的第2合金層24c之二層 ，層積於錫層4a上，故藉由在電鍍第1合金層24b之際 所預先形成的錫層4a，而減輕開口部2a的深度，並進一 步藉由在電鍍第2合金層24c之際所預先形成的第1合金 層24b，而更加減輕開口部2a的深度，因此能夠抑制高度 方向之前述二種金屬的組成之不均。 特別是，於第2實施形態中，係藉由電解電鍍來將錫 —銀層之第1合金層24b與錫-銅層之第2合金層24c之 二層形成於錫層4a上，且使錫層4a '第1合金層24b以 及第2合金層24c熔融，故可減低由銀或銅之析出之所致 之高度方向的銀或銅的組成之不均，且形成將銀組成及銅 組成作了控制的錫-銀一銅合金凸塊。 〔實施例〕 接著，針對本發明之錫合金凸塊之製造方法，對藉由 根據上述實施形態所製作出的實施例所評價的結果進行說 明。 就基板而言，係使用直徑12英吋（30.48cm)的晶圓 ，且於其表面圖案形成有厚度爲12 0μιη之光阻，該光祖， 係以200μιη節距形成有開口直徑爲80μηι之高縱橫比圖案 的開口部。 首先，就與第1實施形態相對應的實施例1而言，係 -14- 201250883 使用錫電鎪液及錫-銀電鍍液的新液’並在以下之條件下 進行電解電鍍。 亦即，以錫電鍍爲厚度60μιη、錫一銀電鍍爲厚度 60μιη來進行二層電鍍，且將錫層與合金層（錫—銀層） 作層積。此時，以使回焊後之錫合金凸塊中之銀組成成爲 2.5wt%的方式來設定條件並進行電解電鍍。亦即，將電 鍍液中之銀濃度調整成僅以錫-銀電鍍來形成錫合金凸塊 之情況的2倍》 進而，在去除光阻後進行回焊處理，而形成實施例1 之錫合金凸塊。此時之回焊處理，係藉由熱風式之回焊爐 來實施，且爲了去除凸塊表面之氧化膜而在凸塊表面塗佈 助焊劑，並在氮氣環境下（氧濃度lOOppm以下），在第 3圖所示之回焊溫度曲線條件下作實施。 此外，比較例1，係僅以錫-銀電鍍而於與實施例1 具有相同的高縱橫比圖案的開口部，形成厚度爲120μΓη且 爲單層的錫一銀層，並藉由與實施例1相同的回焊處理而 形成錫合金凸塊。此時，以使回焊後之錫合金凸塊中之銀 組成成爲2.5 wt %的方式來設定條件並進行電解電鍍。 進而，實施例2及比較例2，係使用對約1 0 0 0枚晶圓 進行了電鍍處理之後的錫-銀電鍍液，且分別在與實施例 1及比較例1相同的條件下實施電解電鍍，並藉由與上述 相同的回焊處理而形成錫合金凸塊。另外，此等之液中的 銀濃度，係設定成與實施例1及比較例1之條件相等的濃
nV 度。 -15- 201250883 針對上述實施例1、2及比較例1、2之錫合金凸塊， 利用XRF (螢光X射線分析）來測定銀組成的結果：平均 凸塊組成爲實施例1 : 2.5wt%、比較例1 : 2.5wt%、實施 例2 : 2.4wt%、比較例2 : 2.0wt%。如上所述，於使用有 新液的電鍍液之實施例1及比較例1中，係得到目標之銀 組成，相對於此，於使用有相當於1 000枚晶圓之電鍍處 理後的電鍍液之情況下，在比較例2中，其銀組成會變得 較目標之組成更低，相反地，在實施例1中，其目標之銀 組成係被大致維持。 接著，就與第2贲施形態相對應的實施例3而言，係 使用錫電鍍液、錫-銅電鍍液及錫-銀電鍍液的新液，並 在以下之條件下進行電解電鍍。 亦即，使用與實施例1相同的晶圓，以錫電鍍成爲厚 度24 μιη、膜中銅組成成爲2.5 wt%的條件，並以錫一銅電 鍍成爲厚度24μπι、膜中銀組成成爲5wt%的條件，而使錫 -銀電鍍成爲厚度72μηι地來進行三層電鍍，再以使回焊 處理後之錫合金凸塊之組成成爲錫-3銀-0.5銅的方式實施 電解電鍍。進而，在去除光阻後進行回焊處理，而形成實 施例2之錫合金凸塊。 進而’在經過相當於約1 000枚之晶圓電鍍處理後的 電解之後，在相同的條件下實施上述的電鍍處理。利用 XRF來測定上述之回焊處理後的錫合金凸塊中之銀組成， 平均凸塊組成係不受電解所影響，而爲固定。 另外，本發明之技術範圍，並不受限於上述實施形態 -16- 201250883 及上述實施例，且在不脫離本發明之主旨的範圍內可加以 各種變更。 例如’雖以如上述第2實施形態般，將第1合金層 24b (錫一銅層）與第2合金層2 4c (錫—銀層）之二層， 層積於錫層上，並將此等藉由回焊處理來進行熔融，而形 成錫-銀-銅三元系凸塊者較爲理想，但將以錫_銀一銅 層作爲錫與身爲二種金屬之銀及銅的合金層而層積於錫層 上’並將此等藉由回焊處理來進行熔融，而形成錫一銀一 銅三元系之凸塊亦無妨》 【圖式簡單說明】 〔第1圖〕係依工程順序展示：於本發明之錫合金凸 塊之製造方法的第1實施形態中製造工程的槪略性重要部 分剖面圖。 〔第2圖〕係依工程順序展示：於本發明之錫合金凸 塊之製造方法的第2實施形態中製造工程的槪略性重要部 分剖面圖。 〔第3圖〕係展示：於本發明之錫合金凸塊之製造方 法的實施例中回焊溫度曲線的圖表。 【主要元件符號說明】 1 :基板 2 :光阻 2a :開口部 -17- 201250883 3 :電極墊（電極） 4a :錫層 4b :合金層 5、25 :錫合金凸塊 24b :第1合金層 24c:第2合金層

Claims (1)

  1. 201250883 七、申請專利範園： 1·—種錫合金凸塊之製造方法，其係以錫與其他一種 或二種以上的金屬之合金所形成的錫合金凸塊之製造方法 ，其特徵爲具有： 藉由電解電鍍來將錫層形成於形成在基板上之光阻開 口部內的電極上之工程； 藉由電解電鍍來將錫與前述其他金屬之合金層，層積 於前述錫層上之工程：以及 在去除前述光阻之後，將前述錫層與前述合金層進行 熔融，而形成錫合金凸塊之工程。 2. 如申請專利範圍第1項所記載之錫合金凸塊之製造 方法，其中， 前述其他金屬爲銀，且 該製造方法係具有： 藉由電解電鍍來將作爲前述合金層之錫-銀層形成於 前述錫層上之工程；和 在去除前述光阻之後，將前述錫層與前述錫一銀層進 行熔融，而形成作爲前述錫合金凸塊之錫-銀凸塊之工程 〇 3. 如申請專利範圍第1項所記載之錫合金凸塊之製造 方法，其中， 前述其他金屬爲二種金屬’且 該製造方法係具有： 藉由電解電鍍來將錫與前述二種之其中一種的合金層 -19- 201250883 及錫與前述二種之另一種的合金層之二層，層積於前述錫 層上之工程；和 在去除前述光阻之後，將前述錫層與所層積的二層之 前述合金層進行熔融，而形成錫合金凸塊之工程。 4.如申請專利範圍第3項所記載之錫合金凸塊之製造 方法，其中， 前述二種之其中一種金屬爲銀且另一種金屬爲銅，且 該製造方法係具有： 藉由電解電鍍來將錫一銀層與錫一銅層之二層，形成 於前述錫層上之工程；和 在去除前述光阻之後，將前述錫層、前述錫一銀層以 及前述錫-銅層進行熔融，而形成作爲前述錫合金凸塊之 錫'銀一銅凸塊之工程。 -20-
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