TWI491767B - 高速銅電鍍槽 - Google Patents

高速銅電鍍槽 Download PDF

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TWI491767B
TWI491767B TW099113711A TW99113711A TWI491767B TW I491767 B TWI491767 B TW I491767B TW 099113711 A TW099113711 A TW 099113711A TW 99113711 A TW99113711 A TW 99113711A TW I491767 B TWI491767 B TW I491767B
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copper
plating bath
aqueous solution
copper plating
container
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TW201043735A (en
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蘇心琳
艾瑞克 韋伯
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莫斯萊克企業公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
    • H10P14/46—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials using a liquid
    • H10P14/47—Electrolytic deposition, i.e. electroplating; Electroless plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Description

高速銅電鍍槽
本發明係關於金屬電鍍領域，且更特定言之係關於新穎電鍍槽、電鍍水溶液及將銅電鍍於基板上之方法。
在微電子工業中，基於銅之材料係通常用作低電阻率之互連。除了用作IC互連外，使用銅電沈積在半導體晶片上產生高縱橫比結構(諸如通孔、支柱及凸塊)係用於3D封裝之一項關鍵技術。重要的是銅之電鍍程序應足夠快以容許處理大量基板且具有可接受之產率。此對於製造3D封裝所需之高縱橫比結構尤為重要，因為為此目的需要電鍍較大量的銅。然而，銅之電流電鍍程序係不夠快，因為銅電鍍速度通常受到電鍍水溶液中之銅離子在擴散層區域中的質量輸送之限制。僅高的銅離子濃度可在質量輸送受控制的條件下適應高速電鍍。然而，銅濃度受到銅鹽在周圍溫度下之溶解度限制，以容許將電解溶液從材料供應商輸送至生產商。因此，最大銅濃度係受到在正常輸送溫度下在任何選定電解溶液中之銅鹽溶解度的限制。
本發明揭示用於高速電鍍銅之電鍍槽及將銅電鍍於半導體晶片上之方法。特定言之，本發明揭示一種銅電鍍槽，其包含：水溶液，其包括銅鹽及至少一種酸；及一容器，其包括固態形式之銅鹽。該容器對該水溶液供應銅離子以將該水溶液之銅離子濃度維持在飽和程度，同時將固態形式之銅鹽保留在該容器內。此可實現對於在不使用較高成本及有毒高溶解度銅鹽的情況下將高縱橫比結構(諸如通孔、支柱及凸塊)電鍍於半導體晶片上尤為有用之高電鍍速度。
在一實施例中，本發明提供銅電鍍槽，其包括：水溶液，其包括銅鹽及至少一種酸；至少一種添加劑，其係用以加速該銅電鍍槽之銅沈積速率；及一容器，其包括固態形式之銅鹽，其中該容器係沉浸於該水溶液中且對該水溶液供應銅離子以將該水溶液之銅離子濃度維持在約飽和程度，同時將固態形式之銅鹽保留在該容器內。
在某些實施例中，該銅電鍍槽之該容器包括一密封盒，其具有用容許溶解之銅離子離開該容器而將固態形式之銅鹽保留在該容器內的一多孔膜覆蓋之複數個開口。
在額外實施例中，本發明提供將銅電鍍於基板上之方法，該方法包括：提供一基板；放置該基板使其與一銅電鍍槽接觸，其中該銅電鍍槽包括：包括銅鹽及至少一種酸之水溶液，及包括固態形式之銅鹽的一容器，其中該容器係沉浸於該水溶液中且對該水溶液供應銅離子以將該水溶液之銅離子濃度維持在約飽和程度，同時將固態形式之銅鹽保留在該容器內；及將銅電鍍於該基板上。
在其他態樣中，提供一種將銅電鍍於基板上之方法，且該方法可包含：將一基板沉浸於一銅電鍍槽中，及將固態形式之銅鹽安置於位於該銅電鍍槽中之一容器內。該容器之一腔室可與該銅電鍍槽流體連通。該方法可進一步包含：將銅電鍍於該基板上，及溶解該銅鹽以對該銅電鍍槽供應銅離子；及視需要將該銅電鍍槽之銅離子濃度維持在約飽和程度。
下文將參照附圖詳細描述本發明之較佳及替代實施例。
現參照圖1A，其顯示根據本發明之一實施例的例示性銅電鍍槽10之示意圖。銅電鍍槽10包含：水溶液20，其包括銅鹽及至少一種酸；及一容器30，其包括固態形式之銅鹽。視需要，銅電鍍槽10可包含各種其他材料，包含氯離子及一或多種添加劑以加速銅電鍍槽10之銅沈積速率。容器30係沉浸於水溶液20中且對水溶液20供應銅離子以將水溶液20之銅離子濃度維持在約飽和程度，同時將固態形式之銅鹽保留在容器30內。本文所使用之術語「銅離子」包含Cu2+ 及Cu+ 物種兩者。片語「在約飽和程度」指在系統所經受之環境條件下在其飽和值之約80%內的離子濃度。在其他實施例中，在系統所經受之環境條件下離子濃度可在相對於其飽和值之約85%、90%、95%、96%、97%、98%、99%或更高值或更小值內。
在所繪示之實施例中，容器30為一密封盒32，其具有用容許溶解之銅離子離開容器30而將固態形式之銅鹽保留在容器30內的多孔膜36(圖1B)覆蓋之複數個開口34。然而，應瞭解容器30可為對水溶液20供應銅離子以將水溶液20之銅離子濃度維持在約飽和程度同時將固態形式之銅鹽保留在容器30內之任何結構。例如，在一些實施例中，容器30可具有用一多孔膜覆蓋之一單一開口，及/或整個容器30可由容許溶解之銅離子離開容器30而將固態形式之銅鹽保留在容器30內的一多孔膜形成。圖1A亦顯示用於固持銅電鍍槽10之一貯槽40。
在本發明之銅電鍍槽10中可使用各種銅鹽。適於在水溶液20中使用之銅鹽及適於在容器30使用之固態形式的銅鹽包含(例如)硫酸銅、焦磷酸銅、胺基磺酸銅、氯化銅、甲酸銅、氟化銅、硝酸銅、氧化銅、四氟硼酸銅、三氟甲烷磺酸銅、三氟醋酸銅及甲烷磺酸銅，或任何前述化合物之水合物。在一實施例中，在水溶液20中所使用之銅鹽及在容器30所使用之固態形式的銅鹽為硫酸銅。水溶液20中所使用之銅鹽濃度將取決於所使用之特定銅鹽而改變，且可在約10克/升至約400克/升之範圍內。在硫酸銅之情況下，水溶液20中所使用之濃度可在約50克/升至約250克/升之範圍內。容器30中所使用之固態形式的銅鹽量將取決於所使用之特定銅鹽而改變，且在每升水溶液20約10克至約1000克之範圍內。在硫酸銅之情況下，容器30中所使用之量可在每升水溶液20約100克至約600克之範圍內。
在本發明之銅電鍍槽10中可使用各種酸。合適之酸包含(例如)硫酸、甲磺酸、氟硼酸、鹽酸、氫碘酸、氫硼酸、硝酸、磷酸及其他合適之酸。在一實施例中，銅電鍍槽10中所使用之酸為硫酸。銅電鍍槽10中所使用之酸的濃度將取決於所使用之特定酸而改變且可在約10克/升至約300克/升之範圍內。在硫酸之情況下，銅電鍍槽10中所使用之濃度可在約20克/升至約200克/升之範圍內。
本發明之銅電鍍槽10中可視需要包含氯離子。合適之氯離子來源包含(例如)鹽酸、氯化鈉、氯化鉀及任何槽可溶氯鹽。銅電鍍槽10中所使用之氯離子濃度可在約10 ppm至約100 ppm之範圍內。
若需要，則本發明之銅電鍍槽10中可使用加速銅沈積速率之一或多種選用添加劑。合適之添加劑包含(例如)增亮劑，例如，有機硫化物化合物，諸如二硫化雙(鈉-磺丙基)、3-巰基-丙基磺酸鈉鹽、N,N-二甲基-二硫代胺甲醯基丙基磺酸鈉鹽及3-S-異硫脲鎓丙基磺酸鹽、或任何前述化合物之混合物。額外合適之加速劑包含(但不限於)硫脲、烯丙基硫脲、乙醯硫脲、嘧啶、任何前述化合物之混合物或其他合適之加速劑。
電鍍溶液亦可包含添加劑，諸如可改良電鍍溶液之某些電鍍特性之載體、調平劑或兩者。載體可為界面活性劑、抑制劑或濕潤劑。調平劑可為螯合劑、染料或展現任何前述功能之組合之添加劑。載體及調平劑可選自下列試劑：聚醚界面活性劑、非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑、嵌段共聚物界面活性劑、聚乙二醇界面活性劑、聚丙烯酸、聚胺、胺基羧酸、氫羧酸、檸檬酸、恩特普羅(entprol)、乙二胺四乙酸、酒石酸、四級化聚胺、聚丙烯醯胺、交聯聚醯胺、吩嗪偶氮染料(例如，Janus Green B)、烷氧基化胺界面活性劑、聚合物吡啶衍生物、聚乙烯亞胺、聚乙烯亞胺乙醇、咪唑啉與環氧氯丙烷之聚合物、苯甲基化聚胺聚合物、任何前述抑制劑之混合物或其他合適之抑制劑。在本發明之一更具體之實施例中，將一種加速劑、一種載體及一種調平劑之組合加入電鍍槽以改良某些電鍍特性。
可使用各種材料來建構在本發明之銅電鍍槽10中所使用之容器30。例如，在圖1A所繪示之實施例中，其中容器30係一密封盒32，其具有用一多孔膜36覆蓋之複數個開口34，且密封盒32可由塑膠(諸如高密度聚乙烯)建構，且多孔膜36可為纖維或由諸如PFA、PTFE、PVDF之材料或類似材料製成之過濾膜36。適於建構密封盒32之其他材料包含(例如)纖維袋，而適於多孔膜36之其他材料包含(例如)PFA或PTFE。一般而言，開口34之數量必須足夠高且多孔膜36之孔必須足夠大以容許含有銅離子之水溶液20通過多孔膜36而將固態形式之銅鹽保留在容器30內。在一實施例中，複數個開口34構成密封盒32之表面積的約50%至約90%，且多孔膜36之孔尺寸在約1微米至約10微米之範圍內或在約1微米至約100微米之範圍內。雖然圖1A所繪示之實施例中的密封盒32具有一矩形形狀，但應瞭解在不脫離本發明之範疇下密封盒可具有任何期望之形狀。
在另一實施例中，在本發明之銅電鍍槽10中所使用之容器可具有視需要可用一多孔膜覆蓋之一或多個開口。該一或多個開口可具有適於容許含有銅離子之水溶液20通過多孔膜而使該容器內之一腔室保留固態形式之銅鹽的任何尺寸及形狀。或者或另一方式為該容器可完全由一多孔膜(例如，包圍銅鹽之網狀框架或撓性袋)形成。在此類實施例中，該多孔膜可具有適於保留特定形狀(諸如矩形形狀或盒子形狀)之剛度。在其他實施例中，多孔膜可為足夠撓性使得其在水溶液20中時不保留一特定形狀。
亦欲包含一種將銅電鍍於基板上之方法，係使用上文詳細描述之本發明的銅電鍍槽。在描述此方法時，將參照圖2，其顯示使用本發明之銅電鍍槽將銅電鍍於基板上之例示性方法的方塊圖。
圖2之區塊100表示提供上文詳細描述之本發明之銅電鍍槽。該銅電鍍槽之pH及溫度係經選擇及維持以促進將銅有效率地電鍍於一基板上。關於pH，在一實施例中，銅電鍍槽之pH係低於7。若需要，可用酸(諸如硫酸)或鹼(諸如氫氧化鈉)來調整銅電鍍槽之pH。關於溫度，在一實施例中，銅電鍍槽之溫度在約24℃至約60℃之範圍內。在另一實施例中，銅電鍍槽之溫度為約45℃。
圖2之區塊110表示提供一待電鍍之基板。各種基板可使用根據本發明之銅來電鍍。一般而言，本文所使用之術語「基板」意指將在其上電鍍銅之任何材料。通常，基板為半導體材料，諸如矽晶圓。其他合適之基板包含(例如)具有大直徑及小直徑、高縱橫比之微通孔、穿矽通孔的電路板或具有大直徑及小直徑、高縱橫比之支柱、凸塊及其他孔隙的電路板。
圖2之區塊120及130分別表示：放置基板使其與銅電鍍槽接觸及將銅電鍍於該基板上。為使銅電鍍發生，使用一組電極(即，陽極與陰極)來施加電流至銅電鍍槽。為電鍍銅，陽極通常由銅板或摻雜磷之銅板製成，且陰極通常為該基板。施加至銅電鍍槽之電流量可廣泛變化，惟典型上電流密度在約10 mA/cm2 至約600 mA/cm2 之範圍內。在將期望量之銅電鍍於基板上後，從電鍍槽移除該基板。在一實施例中，該基板在銅電鍍槽中保持約1 min至約90 min之範圍內的一段時間。在其他實施例中，該基板在銅電鍍槽中保持約5 min至約25 min之範圍內的一段時間。
在另一實施例中，提供一種將銅電鍍於基板上之方法，且該方法可包含(例如)將一基板沉浸於一銅電鍍槽中。該基板可為矽晶圓或如前文提及之另一適當基板。固態形式之銅鹽可安置於位於該銅電鍍槽中之一容器內。該容器內之一腔室可與該銅電鍍槽流體連通使得來自銅鹽之銅離子與該銅電鍍槽流體連通而固態形式之銅鹽係保留在該容器中之該腔室內。如上文所描述，該基板可用銅電鍍，且銅鹽可經溶解以對銅電鍍槽供應銅離子使得該銅電鍍槽之銅離子濃度係維持在約飽和程度。
本發明及相關方法之銅電鍍槽可實現高銅電鍍速度。在一實施例中，電鍍速度為約每分鐘6微米或更高。此等高電鍍速度對於將高縱橫比之結構(即，具有高度：直徑比率大於1:1之結構)電鍍於基板上尤為有用。此等高縱橫比之結構包含(例如)銅支柱、銅凸塊、銅穿矽通孔、銅微通孔及溝渠等等。
下列實例說明本發明之某些實施例且不應視為限制本發明。
實例
實例1
使用含有240 g/L之硫酸銅、60 g/L之硫酸、50 ppm之氯化物的電鍍槽及含有固態硫酸銅(每升電鍍槽180 g)之籃子來電鍍測試晶圓使其具有銅支柱，該等銅支柱具有70 μm厚度及0.78：1之縱橫比(高度：直徑)。添加劑包含40 ppm之加速劑二硫化雙(鈉-磺丙基)、100 ppm之載體聚乙二醇：聚丙二醇單丁基醚嵌段共聚物(分子量=750)及100 ppm之調平劑RALUPLATE CL 1000(德國，Ludwigshafen,Raschig GmbH)。在45℃之電鍍槽溫度下，獲得6 μm/min及7 μm/min之電鍍速度。圖3為使用6 μm/min之電鍍速度(電鍍時間為11分鐘)而獲得之電鍍結果的一SEM影像。
實例2
使用與實例1相同之電鍍電解槽條件但不同之添加劑來電鍍測試晶圓使其具有銅支柱，該等銅支柱具有120 μm厚度及1.2：1之縱橫比(高度：直徑)。添加劑包含40 ppm之加速劑二硫化雙(鈉-磺丙基)、100 ppm之載體聚乙二醇及100 ppm之調平劑RaluMer 11(德國，Ludwigshafen，Raschig GmbH)。圖4為使用45℃之電鍍槽溫度及6 μm/min之電鍍速度(電鍍時間為20分鐘)而獲得之電鍍結果的一SEM影像。
應瞭解本發明並不限於本文中所揭示之特定方法、裝置及材料，因為此等方法、裝置及材料在一定程度上可改變。例如，此等銅電鍍槽可用其他金屬之電鍍來實施，其中來自可溶金屬鹽之其他金屬離子可在如本文所述之槽的容器內傳輸。亦應瞭解本文所使用之術語係僅為描述特定實施例而使用，且並不意欲具限制性，因為本發明之範疇僅由隨附申請專利範圍及其等效物而限制。
10．．．銅電鍍槽
20．．．水溶液
30．．．容器
32．．．密封盒
34．．．開口
36．．．多孔膜
40．．．貯槽
圖1A為根據本發明之一實施例的例示性銅電鍍槽之示意圖；
圖1B為在根據本發明之一實施例的例示性銅電鍍槽中所使用之容器一部分的示意性放大圖；
圖2為繪示根據本發明之一實施實例之將銅電鍍於基板上之例示性方法的一方塊圖；
圖3為根據本發明之一實施實例之具有70微米厚度且已電鍍於半導體晶圓上之若干銅支柱的掃描電子顯微鏡影像，其中顯示樣品I.D.(003203)、電子束能量(2.0 kV)、影像放大倍數(×449)及對應於66.8微米之距離的虛線；及
圖4為根據本發明之一實施實例之具有120微米厚度且已電鍍於半導體晶圓上之若干銅支柱的掃描電子顯微鏡影像，其中顯示樣品I.D.(003246)、電子束能量(2.0 kV)、影像放大倍數(×147)及對應於204微米之距離的虛線。
10．．．銅電鍍槽
20．．．水溶液
30．．．容器
32．．．密封盒
34．．．開口
40．．．貯槽

Claims (36)

  1. 一種銅電鍍槽，其包括：水溶液，其包括銅鹽及至少一種酸；及一容器，其包括固態形式之銅鹽，其中該容器係沉浸於該水溶液中且對該水溶液供應銅離子以將該水溶液之銅離子濃度維持在約飽和程度，同時將固態形式之銅鹽保留在該容器內。
  2. 如請求項1之銅電鍍槽，其中該銅鹽係選自由下列組成之群：硫酸銅、甲烷磺酸銅、氟硼酸銅、醋酸銅、硝酸銅、氧化銅、氫氧化銅及氯化銅。
  3. 如請求項2之銅電鍍槽，其中該銅鹽為硫酸銅。
  4. 如請求項3之銅電鍍槽，其中該水溶液之該硫酸銅濃度為約50克/升至約250克/升之範圍內。
  5. 如請求項1之銅電鍍槽，其中該酸係選自由下列組成之群：硫酸、甲磺酸、氟硼酸、氫硼酸、鹽酸、氫碘酸、磷酸及硼酸。
  6. 如請求項5之銅電鍍槽，其中該酸為硫酸。
  7. 如請求項1之銅電鍍槽，其中該水溶液之該酸濃度為約10克/升至約250克/升之範圍內。
  8. 如請求項6之銅電鍍槽，其中該水溶液之該硫酸濃度為約20克/升至約100克/升之範圍內。
  9. 如請求項1之銅電鍍槽，其中該水溶液進一步包括氯離子。
  10. 如請求項9之銅電鍍槽，其中該水溶液之該氯離子濃度 為約10ppm至約100ppm之範圍內。
  11. 如請求項1之銅電鍍槽，其中該水溶液進一步包括至少一種添加劑以加速該銅電鍍槽之銅沈積速率。
  12. 如請求項11之銅電鍍槽，其中該添加劑為硫化物化合物。
  13. 如請求項1之銅電鍍槽，其中該水溶液進一步包括至少一種抑制劑添加劑。
  14. 如請求項13之銅電鍍槽，其中該抑制劑添加劑係選自由下列組成之群：界面活性劑、螯合劑、調平劑及濕潤劑。
  15. 如請求項1之銅電鍍槽，其中該固態形式之銅鹽係選自由下列組成之群：硫酸銅、甲烷磺酸銅、氟硼酸銅、醋酸銅、硝酸銅、氧化銅、氫氧化銅及氯化銅。
  16. 如請求項15之銅電鍍槽，其中該固態形式之銅鹽為硫酸銅。
  17. 如請求項16之銅電鍍槽，其中固態形式之硫酸銅量為每升水溶液約100克至約300克之範圍內。
  18. 如請求項1之銅電鍍槽，其中該容器包括一膜，其容許溶液中之銅離子離開該容器而將固態形式之該銅鹽保留在該容器內。
  19. 如請求項1之銅電鍍槽，其中該容器包括含有具有自約1μm至約100μm範圍之孔徑之多孔膜材料之封閉件。
  20. 如請求項1之銅電鍍槽，其中該容器包括形成於其中之一或多個開口，該一或多個開口經組態以容許該水溶液 及銅離子流經其中。
  21. 如請求項20之銅電鍍槽，其中該一或多個開口係由一多孔膜覆蓋。
  22. 一種於基板上電鍍銅之方法，該方法包括：將一基板沉浸於一銅電鍍槽中；將固態形式之銅鹽安置於位於該銅電鍍槽中之一容器內，該容器之一腔室係與該銅電鍍槽流體連通；將銅電鍍於該基板上；及溶解該銅鹽以對該銅電鍍槽供應銅離子。
  23. 如請求項22之方法，其中溶解該銅鹽將該銅電鍍槽維持在約飽和程度。
  24. 一種於基板上電鍍銅之方法，該方法包括：提供一銅電鍍槽，其中該銅電鍍槽包括：包括銅鹽及至少一種酸之水溶液，及包括固態形式之銅鹽的一容器，其中該容器係沉浸於該水溶液中且對該水溶液供應銅離子以將該水溶液之銅離子濃度維持在約飽和程度，同時將固態形式之銅鹽保留在該容器內；提供一基板；放置該基板使其與該銅電鍍槽接觸；及將銅電鍍於該基板上。
  25. 如請求項22、23或24中任一項之方法，其中該銅鹽為硫酸銅。
  26. 如請求項25之方法，其中該水溶液之該硫酸銅濃度為約50克/升至約250克/升之範圍內。
  27. 如請求項24之方法，其中該酸為硫酸。
  28. 如請求項27之方法，其中該水溶液之該硫酸濃度為約20克/升至約100克/升之範圍內。
  29. 如請求項24之方法，其中該水溶液進一步包括氯離子。
  30. 如請求項29之方法，其中該水溶液之該氯離子濃度為約10ppm至約100ppm之範圍內。
  31. 如請求項22、23或24中任一項之方法，其中該固態形式之銅鹽為硫酸銅。
  32. 如請求項31之方法，其中固態形式之硫酸銅量為每升水溶液約100克至約300克之範圍內。
  33. 如請求項22、23或24中任一項之方法，其中該銅電鍍槽之溫度在約30℃至約60℃之範圍內。
  34. 如請求項22、23或24中任一項之方法，其中電鍍速度為約每分鐘4微米或更高。
  35. 如請求項22、23或24中任一項之方法，其中於該基板上電鍍一或多個高縱橫比率之銅結構。
  36. 如請求項35之方法，其中該高縱橫比率之結構係選自由下列組成之群：銅支柱、銅凸塊及銅穿矽通孔。
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