TW201413846A - 製造經塗佈的銅柱 - Google Patents

製造經塗佈的銅柱 Download PDF

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Publication number
TW201413846A
TW201413846A TW102127502A TW102127502A TW201413846A TW 201413846 A TW201413846 A TW 201413846A TW 102127502 A TW102127502 A TW 102127502A TW 102127502 A TW102127502 A TW 102127502A TW 201413846 A TW201413846 A TW 201413846A
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Taiwan
Prior art keywords
copper
metal
tin
metal layer
silver
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TW102127502A
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English (en)
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TWI582870B (zh
Inventor
Thomas Beck
Gerhard Steinberger
Andreas Walter
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Atotech Deutschland Gmbh
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Publication of TW201413846A publication Critical patent/TW201413846A/zh
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Publication of TWI582870B publication Critical patent/TWI582870B/zh

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Abstract

本發明係關於一種在半導體基板上形成銅柱之方法，該銅柱具有包含相對銅較不貴重之金屬之凸塊底層金屬鍍層區及任選地位於頂部之焊料凸塊，及具有沉積於該銅柱之側壁上之選自錫、錫合金、銀、及銀合金之第二金屬之層。在沉積該第二金屬層之前將相對銅較貴重之第一金屬之層沉積於該銅柱之整個外表面上。該第二金屬層因而具有至少減少量之非所欲針孔且充作底層銅柱之保護層。

Description

製造經塗佈的銅柱
本發明係關於位於用於電子裝置(諸如半導體微晶片、中介片、及IC基板)領域之半導體基板上具有經保護之側壁之銅柱的製造。該等銅柱可具有位於頂部之焊料頂蓋層。
銅柱係用於用於將半導體微晶片與中介片、IC基板或印刷電路板電連接之高密度互連封裝中。視情況，銅柱具有附接於銅柱之頂部之焊料頂蓋層。
在該等應用中，銅柱正日益替代習知的焊料球凸塊，因為其在個別銅柱結構之間提供與間距(間距離)無關之定距。
圖1顯示一種根據先前技術製造銅柱之方法。銅柱通常係製於半導體基板(諸如微晶片，本文中稱為晶粒)之一側上。銅柱(13)係藉由使銅或銅合金電鍍於由圖案化光阻材料形成之開孔中及晶粒(11)之凸塊底層金屬鍍層區(12)來形成(圖1)。該凸塊底層金屬鍍層區為包含相對銅較不貴重之金屬之單一層、或由超過一層之相對銅較不貴重之金屬及/或金屬合金之個別層組成之多層。該凸塊底層金屬鍍層區的主要功能係作為銅及矽之間的障壁及防止此兩種元素之非所欲相互擴散。
視情況，焊接材料(諸如純的錫或錫合金(諸如錫-銀、錫-銀-銅或錫-銀-銅-鎳合金))沉積於銅柱之頂部且藉此形成焊料頂蓋層(14)。此 一方法揭示於(例如)US 2005/0077624 A1中。
銅柱之暴露側壁在晶粒及互連封裝之進一步製造步驟中易於非所欲氧化及/或其他腐蝕過程。
具有附接至頂部之焊料頂蓋層之該銅柱結構的另一缺點為熔融錫基焊接材料於銅柱之側壁上之良好可濕性。因此，熔融焊接材料可在迴焊操作期間流入個別銅柱間之間隙中且因而可能形成非所欲短路。
US 2009/0127708 A1中揭示一種製造已將焊接材料附接至頂部且具有經塗佈之側壁之銅柱的方法。揭示於其中之該方法包括於銅柱之頂部沉積錫或錫合金之焊料層且接著藉由浸入式電鍍於銅柱整個外表面上沉積薄保護層(15)之步驟(圖1)。
揭示於US 2009/0127708 A1中之該方法的主要缺點是：於銅柱上沉積薄保護層(15)時，在該等銅柱(13)之側壁上形成非所欲針孔(圖2)。
就銅柱(13)頂部不存在錫基焊接材料之焊料頂蓋層(14)之銅柱(13)而言，亦觀察到金屬(諸如錫或銀)之浸入式電鍍期間非所欲之針孔之形成。於此情況中，銅柱(13)亦在包含至少一層相對銅較不貴重之金屬或金屬合金之凸塊底層金屬鍍層區(12)上形成。
本發明之目標
本發明之目標係提供一種製造銅柱之方法及銅柱頂部具有一層錫基焊料之銅柱，該等銅柱具有附接至銅柱之側壁之緻密保護層。
該目標係藉由在半導體基板上製造經塗佈的銅柱之方法來解決，該方法依此順序包括以下步驟：a.使半導體基板具有銅柱陣列，該等銅柱具有包含相對銅較不貴重之金屬或金屬合金之凸塊底層金屬鍍層區及任選地已進一步 在頂部附接焊料頂蓋層，b.於該等銅柱之整個外表面上沉積包含相對銅較貴重之金屬之第一金屬層，及c.藉由浸入式電鍍於該第一金屬層上沉積選自由錫、錫合金、銀、及銀合金組成之群之第二金屬層。
所得的經塗佈的銅柱包括位於側壁上之緻密保護層。
11‧‧‧晶粒
12‧‧‧凸塊底層金屬鍍層區
13‧‧‧銅柱
14‧‧‧焊料頂蓋層
15‧‧‧保護層
21‧‧‧半導體基板
22‧‧‧凸塊底層金屬鍍層區
23‧‧‧銅柱
24‧‧‧焊料頂蓋層
25‧‧‧第一金屬層
26‧‧‧第二金屬層
圖1顯示根據先前技術所製得具有凸塊底層金屬鍍層區及附接至頂部之焊料頂蓋層之銅柱。
圖2顯示位於根據先前技術所製得具有凸塊底層金屬鍍層區及附接至頂部之焊料頂蓋層之銅柱之側壁上之保護層的掃描電子顯微圖。
圖3顯示藉由根據本發明之方法所製得具有凸塊底層金屬鍍層區及附接至頂部之焊料頂蓋層之銅柱。
圖4顯示位於藉由根據本發明之方法所製得具有凸塊底層金屬鍍層區及附接至頂部之焊料頂蓋層之銅柱之側壁上之保護層的掃描電子顯微圖。
作為基板(21)應用於根據本發明方法中之材料為半導體材料，較佳係矽晶圓材料。銅柱(23)係藉由電鍍於圖案化光阻材料開孔中形成。
銅柱(23)沉積於包括(例如)障壁層之凸塊底層金屬鍍層區(22)上，該障壁層係由藉由物理氣相沉積所沉積之鉭、鈦、或鈦-鎢合金、或藉由無電電鍍所沉積之鎳合金(諸如鎳-磷合金、鎳-硼合金、三元鎳-鉬-磷合金)及三元鈷合金(諸如鈷-鎢-磷合金及鈷-鉬-磷合金)製成。該障壁層可用來防止銅自該等柱擴散至半導體基板中。
凸塊底層金屬鍍層區(22)可由上述金屬或金屬合金之障壁層及除 此之外之藉由物理氣相沉積法或無電電鍍沉積於充作連續電鍍銅之電鍍基底之該障壁層上之銅薄層組成。凸塊底層金屬鍍層區(22)亦可由三層不同金屬及/或金屬合金層組成。
因此，凸塊底層金屬鍍層區(22)包含至少一層相對銅較不貴重之金屬或金屬合金。
銅柱(23)較佳具有在10至200μm範圍內(更佳係40至100μm)之高度，及具有圓形或矩形形狀。圓形銅柱(23)直徑之範圍較佳係自10至200μm，更佳係自20至100μm。具有矩形形狀之銅柱(23)較佳具有在10至200μm範圍內(更佳係20至100μm)之基底邊長。
該等銅柱(23)通常係呈若干根銅柱(23)之陣列配置於半導體基板(21)上。該陣列可為(例如)銅柱(23)之一維陣列或二維陣列。
本文中亦稱為焊料凸塊之焊料頂蓋層(24)視情況係(例如)藉由電鍍沉積於銅柱(23)之頂部。焊料頂蓋層較佳包含錫及可選自目前使用作為錫-鉛焊料替代品之純的錫及錫合金(諸如錫-銀合金、錫-銀-銅合金、及錫-銀-銅-鎳合金)。
於US 2009/0127708 A1中揭示一種製造包括具有附接至頂部之焊料頂蓋層(24)之銅柱(23)之半導體基板之方法及在本發明之一實施例中充作計劃藉由根據本發明之方法處理之基板。
視情況，第二障壁層係在沉積可選焊料頂蓋層(24)之前沉積於銅柱(23)之頂部。用於可選第二障壁層之適宜材料較佳係選自鎳合金(諸如鎳-磷合金及鎳-硼合金)、三元鎳合金(諸如鎳-鉬-磷合金)及三元鈷合金(諸如鈷-鎢-磷及鈷-鉬-磷合金)。可選第二障壁層可藉由無電電鍍沉積。相關技藝中已知適宜之電鍍浴液組合物及電鍍參數。該可選第二障壁層抑制銅及焊料頂蓋層(24)之材料之非所欲相互擴散。
提供包括銅柱(23)陣列之半導體基板(21)，該等銅柱具有包含相對銅較不貴重之金屬或金屬合金之凸塊底層金屬鍍層區(22)。視情 況，焊料頂蓋層(24)附接於該等銅柱(23)之頂部。
接著，將銅柱(23)之暴露表面清潔。較佳地，使用包含酸及任選地進一步包含界面活性劑及/或氧化劑之蝕刻清潔組合物來清潔銅柱(23)之表面。一種特別適宜之蝕刻清潔組合物包含水、硫酸及過氧化氫。
視情況，於蝕刻清潔之後在酸(諸如硫酸)水溶液中進行沖洗。
於本發明之另一實施例中，應用電漿處理來清潔銅柱(23)之表面。
可應用蝕刻清潔及電漿處理之組合來清潔銅柱(23)之表面。
視情況，除了蝕刻清潔及/或電漿處理之外，還應用用於自銅柱(23)之表面移除非所欲顆粒之處理。此類型之一種特別適宜之處理為標準清潔1(SC1)處理，該處理包括以包含氫氧化鋁及過氧化氫之水溶液處理銅柱(23)之表面之步驟。相關技藝中已知此類型之組合物及處理條件。
接著使銅柱(23)之清潔表面接觸包含相對銅較貴重之金屬之離子之溶液且因而第一金屬層(25)藉由其中銅被氧化及相對銅較之之金屬之金屬離子還原為金屬狀態且藉此沉積於銅表面上之浸入式反應沉積於銅柱(23)之暴露外表面上。相關技藝中已知該等浸入式電鍍浴液及適宜之電鍍條件。
相對銅較貴重之金屬之金屬離子較佳係選自由銀、鈀、鉑、銠、釕、金、及其合金組成之群。
更佳地，較貴重金屬之金屬離子為鈀離子。
包含相對銅較貴重之金屬之金屬離子之溶液較佳為水溶液。
該溶液可進一步包含至少一種酸或其鹽。
用於沉積鈀層作為第一金屬層(25)之一尤佳水溶液包含鈀離子、至少一種酸或其鹽。
鈀離子源可選自包括硫酸鈀、氯化鈀、乙酸鈀及過氯酸鈀之群。水溶液中之鈀離子濃度之範圍較佳係自2至200ppm，更佳係自5至50ppm。
該至少一種酸或其鹽較佳係選自包括硫酸、硝酸、及鹽酸之群。用於至少一種酸之鹽之適宜相對離子可選自包括鈉、鉀、及銨之群。該至少一種酸或其鹽之濃度較佳係經調整以獲得在1至7(更佳1至4)範圍內之浸入式鈀電鍍浴液之電鍍浴液pH。
浸入式電鍍浴液於第一金屬層(25)之沉積期間之溫度之範圍較佳係自20至90℃，更佳係自20至40℃。
由包括具有包含相對銅較不貴重之金屬或金屬合金之凸塊底層金屬鍍層區(22)及任選地已進一步於頂部附接焊料頂蓋層(24)之銅柱(23)陣列之基板(21)接觸用於較佳藉由浸塗或噴塗沉積第一金屬層(25)之浸入式電鍍浴液。
詞句「層」就第一金屬層(25)而論必須在寬廣意義上來理解：藉由浸入式電鍍獲得之相對銅較貴重之金屬之層並非相對銅較貴重之該金屬之緻密層。取決於(例如)用於浸入式電鍍之溶液中金屬離子之濃度、電鍍期間該溶液之溫度、及電鍍時間，相對銅較貴重之金屬之不同大小島狀體沉積於銅柱(23)上。其不被視為層總成之不同層而是形成金屬接種層之活化層。此接種層之厚度通常為幾埃。
此外，相對銅較貴重之金屬亦沉積在位於銅柱(23)頂部之可選焊料頂蓋層(24)上。
於銅柱(23)之側壁上沉積第二金屬層(26)時亦需要非緻密第一金屬層(25)，因為第二金屬層(26)較佳係藉由浸入式電鍍沉積之故。因此，來自該浸入式電鍍浴液之金屬離子需要可及底層銅柱(23)之部分以沉積第二金屬層(26)。
接著，將第二金屬層(26)沉積於包括第一金屬層(25)之銅柱(23) 之表面上，在沉積期間無需對基板(21)施加外部電流。較佳地，第二金屬層(26)係藉由浸入式電鍍來沉積。
第二金屬層(26)較佳係選自錫、錫合金、銀及銀合金。
最佳地，第二金屬層(26)係選自錫及錫合金。
於本發明之一實施例中，於第一金屬層(25)係選自銀及銀合金之情況中，不選擇銀或銀合金用於第二金屬層(26)。
銀及銀合金可從包含銀離子源(諸如甲磺酸銀)、任選地於計劃沉積銀合金之情況中之第二金屬離子源(諸如鈀離子)、及其他添加劑(諸如咪唑或苯并咪唑及/或酸(諸如甲磺酸))之水性浸入式電鍍浴液沉積。
用於銀或銀合金之沉積之適宜水性浸入式電鍍浴液可進一步包含表面活性劑及針對於銅離子(於浸入式電鍍期間衍生自銅表面)之錯合劑(諸如2,2'-聯吡啶)。
銀離子濃度之範圍較佳係自0.5至5克/升，更佳係自0.75至2克/升。可選酸濃度之範圍較佳係0.1至2莫耳/升。第二金屬之可選離子濃度之範圍較佳係自1至100毫克/升，更佳係自15至50毫克/升。
於銀或銀合金之沉積期間之銀或銀合金浸入式電鍍浴液溫度之範圍較佳係自15至45℃，更佳係自15至35℃及最佳係自20至35℃。
錫可從包含Sn(II)離子及硫脲及/或其衍生物之水性浸入式電鍍浴液沉積。在錫或錫合金藉由浸入式電鍍法沉積於銅或銅合金上之情況下，需要添加錯合劑(諸如硫脲及/或其衍生物)。硫脲及/或其衍生物之作用係藉由在與Sn(II)離子之浸入反應期間形成Cu(I)硫脲錯合物來支援銅之溶解。因銅相對錫較貴重故需要此支援反應來氧化銅從而還原Sn(II)離子。
很久之前就熟知用於錫及錫合金之沉積之包含硫脲及/或其衍生物之酸性浸入式電鍍浴液(錫及其合金之電沉積(The Electrodeposition of Tin and its Alloys)，M.Jordan，Eugen G.Leuze出版社，1995年，第89至90頁及其中所引用之參考文獻)。
浸入式電鍍浴液中Sn(II)離子之來源僅受限於水溶性化合物。Sn(II)化合物之較佳來源係選自包括Sn(II)之有機磺酸鹽(諸如甲磺酸錫)、硫酸錫及氯化錫之群。
浸入式電鍍浴液中之Sn(II)離子含量範圍較佳係自1至30克/升，更佳係自5至15克/升。
用於沉積錫之浸入式電鍍浴液進一步包含至少一種酸或其鹽，諸如烷基磺酸或芳族磺酸。用於該至少一種酸之鹽之適宜相對離子係選自包括鈉、鉀、及銨之群。
浸入式電鍍浴液中之酸及/或其鹽總濃度之範圍較佳係自0.1至1.5莫耳/升，更佳係自0.3至1.2莫耳/升及最佳係自0.5至1.0莫耳/升。
浸入式電鍍浴液中之該至少一種錯合劑係選自由硫脲及/或其衍生物組成之群。硫脲衍生物較佳係選自包括具有C1至C3烷基之單-及二-烷基硫脲之群。最佳之錯合劑為硫脲。
該至少一種選自硫脲及/或其衍生物之錯合劑較佳係以50至150克/升含量、更佳係以90至120克/升含量添加至電鍍浴液。
視情況，浸入式電鍍浴液進一步包含第二金屬之離子，諸如Ag(I)離子。藉由添加第二金屬之離子，獲得錫合金。第二金屬之可選離子較佳係以0.1至500毫克/升、更佳0.5至250毫克/升及最佳1至50毫克/升濃度添加至該電鍍浴液。
Ag(I)離子源可為任何水溶性Ag(I)鹽。Ag(I)離子源較佳係選自由硫酸銀及烷基或芳族磺酸之銀鹽組成之群。藉由浸入式電鍍沉積之錫-銀合金對可能為銅柱間非所欲短路之另一來源之晶鬚生長較不敏感。
視情況，浸入式電鍍浴液進一步包含至少一種選自由單羧酸、 多羧酸、羥基羧酸、胺基羧酸及其鹽組成之群之第二錯合劑。在使用鹽之情況中，適宜之陽離子為(例如)鈉、鉀、及銨。
其中單羧酸定義為每分子具有一個羧基部分之化合物。多羧酸為每分子具有超過一個羧基部分之羧酸。羥基羧酸為每分子具有至少一個羧基及至少一個羥基部分之羧酸。胺基羧酸為具有至少一個羧基及至少一個胺基部分之羧酸。該胺部分可為一級、二級或三級胺部分。
作為可選第二錯合劑之較佳多羧酸係選自由草酸、丙二酸及琥珀酸組成之群。
作為可選第二錯合劑之較佳羥基羧酸係選自具有C1至C6烷基之脂族羥基羧酸。作為可選第二錯合劑之最佳羥基羧酸係選自由乙醇酸、乳酸、檸檬酸、酒石酸及其鹽組成之群。
作為可選第二錯合劑之較佳胺基羧酸係選自由甘胺酸、乙二胺四乙酸(EDTA)、二伸乙三胺五乙酸(DTPA)及三伸乙四胺六乙酸(TTHA)組成之群。
可選第二錯合劑之濃度之範圍較佳係自0.1至100克/升，更佳係自40至70克/升。
視情況，浸入式電鍍浴液進一步包含至少一種芳族磺酸，諸如苯磺酸及/或甲苯磺酸。
視情況，浸入式電鍍浴液進一步包含次磷酸鹽化合物。較佳之次磷酸鹽化合物為次磷酸鈉、次磷酸鉀及次磷酸銨。
可選次磷酸鹽化合物之濃度之範圍較佳係自0.1至200克/升，更佳係自1至150克/升及最佳係自10至120克/升。
使用期間浸入式錫或錫合金電鍍浴液之溫度之範圍係自20至85℃。於浸入式錫電鍍浴液中之基板浸入時間在1至60分鐘範圍內。
藉由將包括視情況在頂部具有焊料頂蓋層(24)之銅柱(23)陣列之 半導體基板(21)浸入填充該浸入式電鍍浴液之電鍍槽或藉由將該浸入式電鍍浴液噴至基板上，使該基板與該浸入式電鍍浴液接觸。
視情況，使半導體基板(21)接觸可包含除了金屬離子外與浸入式錫或錫合金電鍍浴液相同或類似組分之水性預處理組合物。
附接至銅柱(23)表面之第二金屬層(26)之厚度之範圍較佳係自0.05至2μm，更佳係自0.1至0.5μm。
金屬間銅-錫相(諸如η-Cu6Sn5及ε-Cu3Sn相)可於包含錫之第二金屬層(26)之沉積期間及甚於迴焊操作期間形成。在沉積於銅柱(23)表面上之包含錫之第二金屬層(26)厚度足夠薄的情況中，第二金屬層(26)改為包含該等金屬間銅-錫相之表面替代純的錫表面。
於本發明之一實施例中，包含錫之第二金屬層(26)在沉積之後係足夠地薄，以致於電鍍及/或迴焊操作期間形成包含銅-錫金屬間相之表面。
已知包含該等金屬間相之表面針對於熔融錫基焊接材料具有低可濕性。因此，銅柱(23)陣列中個別銅柱(23)間之間隙較不易受熔融錫基焊接材料污染。
總言之，在選自由錫、錫合金、銀及銀合金組成之群之第二金屬層(26)之沉積之前沉積包含相對銅較貴重之金屬之第一金屬層(25)至少導致銅柱側壁上非所欲針孔數量減少。因此，第二金屬層(26)對銅柱(23)側壁之保護性能改善。
實例
現將參照以下非限制性實例說明本發明。
所有實例中均使用包括位於包含相對銅較不貴重之金屬之凸塊底層金屬鍍層區頂部之銅柱陣列、及附接至該等銅柱頂部之包含錫之焊料頂蓋層之矽基板。
在包含錫之第二金屬層之沉積之後藉由掃描電子顯微鏡探究銅 柱之側壁。
實例1(對照)
利用水性蝕刻清潔液(Xenolyte®清潔液D，Atotech Deutschland GmbH產品)清潔銅柱。
接著，將基板浸漬於35℃下包含Sn(II)離子源、硫脲及甲磺酸之浸入式錫電鍍浴液中維持5分鐘。獲得具有0.2μm厚度之錫層作為第二金屬層(26)。
獲得具有根據圖1之銅柱陣列之矽基板，該矽基板在錫沉積於銅柱上作為第二金屬層之該等區域中包含非所欲針孔(圖2)。
實例2
利用水性蝕刻清潔液(Xenolyte®清潔液D，Atotech Deutschland GmbH產品)清潔銅柱。
接著，將基板浸入包含10ppm Pd離子及硫酸及具有pH值為1之水溶液中。
然後將該基板浸漬於35℃下包含Sn(II)離子源、尿素及甲磺酸之浸入式錫電鍍浴液中維持5分鐘。獲得具有0.2μm厚度之錫層作為第二金屬層(26)。
獲得包括根據圖3之銅柱陣列之基板，該基板包括不含非所欲針孔之保護層(圖4)。
21‧‧‧半導體基板
22‧‧‧凸塊底層金屬鍍層區
23‧‧‧銅柱
24‧‧‧焊料頂蓋層
25‧‧‧第一金屬層
26‧‧‧第二金屬層

Claims (18)

  1. 一種在半導體基板上製造經塗佈的銅柱之方法，該方法依此順序包括以下步驟：a.向半導體基板提供銅柱陣列，該等銅柱具有包含相對銅較不貴重之金屬或金屬合金之凸塊底層金屬鍍層區、及附接至其表面之頂部之焊料頂蓋層，b.於該等銅柱之整個外表面上沉積包含相對銅較貴重之金屬之第一金屬層，及c.藉由浸入式電鍍於該第一金屬層上沉積選自由錫、錫合金、銀、及銀合金組成之群之第二金屬層。
  2. 如請求項1之製造經塗佈的銅柱之方法，其中該半導體基板為矽基板。
  3. 如請求項1或2之製造經塗佈的銅柱之方法，其中該焊料頂蓋層包含錫。
  4. 如請求項1或2之製造經塗佈的銅柱之方法，其中該相對銅較貴重之金屬係選自由銀、鈀、鉑、銠、釕、金及其合金組成之群，但限制條件為在該第二金屬層包含銀或銀合金之情況下，不選擇銀及銀合金作為第一金屬層。
  5. 如請求項1或2之製造經塗佈的銅柱之方法，其中該相對銅較貴重之金屬為鈀。
  6. 如請求項1及2之製造經塗佈的銅柱之方法，其中該第二金屬層為錫或錫合金。
  7. 如請求項1及2之製造經塗佈的銅柱之方法，其中該第二金屬層係從包含錫離子源、硫脲及/或其衍生物、及任選地包含第二金屬源之水性電鍍浴液沉積。
  8. 如請求項1或2之製造經塗佈的銅柱之方法，其中該第二金屬層進一步包含呈銅-錫合金形式之銅。
  9. 如請求項1或2之製造經塗佈的銅柱之方法，其中該包含錫之第二金屬層進一步包含銀。
  10. 一種在半導體基板上製造經塗佈的銅柱之方法，該方法依此順序包括以下步驟：a.向半導體基板提供銅柱陣列，該等銅柱具有包含相對銅較不貴重之金屬或金屬合金之凸塊底層金屬鍍層區、及附接至其表面之頂部之焊料頂蓋層，b.於該等銅柱之整個外表面上沉積包含相對銅較貴重之金屬之第一金屬層，其中該第一金屬層係藉由浸入式電鍍來沉積，及c.藉由浸入式電鍍於該第一金屬層上沉積選自由錫、錫合金、銀、及銀合金組成之群之第二金屬層。
  11. 如請求項10之製造經塗佈的銅柱之方法，其中用於沉積該第一金屬層之該浸入式電鍍浴液包含相對銅較貴重之金屬之金屬離子源及至少一種酸及/或其鹽。
  12. 如請求項10或11之製造經塗佈的銅柱之方法，其中該第二金屬層為錫或錫合金。
  13. 如請求項10或11之製造經塗佈的銅柱之方法，其中該第二金屬層係從包含錫離子源、硫脲及/或其衍生物、及任選地包含第二金屬源之水性電鍍浴液沉積。
  14. 如請求項10或11之製造經塗佈的銅柱之方法，其中該第二金屬層進一步包含呈銅-錫合金形式之銅。
  15. 如請求項10或11之製造經塗佈的銅柱之方法，其中該包含錫之第二金屬層進一步包含銀。
  16. 一種位於半導體基板上之銅柱，該銅柱具有包含相對銅較不貴重之金屬之凸塊底層金屬鍍層區及由第一金屬層及第二金屬層組成之側壁保護層，其中該第一金屬層包含相對銅較貴重之金屬及其中該第二金屬層包含選自由錫、錫合金、銀、及銀合金組成之群之金屬，但限制條件為在該第一金屬層包含銀或銀合金情況下，不選擇銀及銀合金作為第二金屬層。
  17. 如請求項16之位於半導體基板上之銅柱，其中該相對銅較貴重之金屬係選自由銀、鈀、鉑、銠、釕、金、及其合金組成之群。
  18. 如請求項16或17之位於半導體基板上之銅柱，其中該第二金屬層進一步包含呈錫-銅合金形式之銅。
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