TW202146710A - 用於金屬特徵部的無光阻形成的電流體動力噴射列印及電鍍 - Google Patents
用於金屬特徵部的無光阻形成的電流體動力噴射列印及電鍍 Download PDFInfo
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- 238000012360 testing method Methods 0.000 description 1
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- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
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Images
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- C25D21/12—Process control or regulation
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- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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Abstract
文中提供在半導體基板上形成金屬特徵部的方法、墨水、設備、及系統。有利地,文中之技術毋須使用光阻且可在毋須使用傳統處理流程中所用之許多處理及設備的情況下完成。而是使用電流體動力噴射列印沉積包含電鍍添加物如加速劑或抑制劑的墨水。接著可在先取沉積處理中電鍍經列印之基板,先取沉積處理在存在墨水的基板區域上達成第一沉積速率並在不存在墨水的基板區域上達成第二沉積速率,第一及第二沉積速率係彼此不同。在電鍍之後,可使用化學蝕刻使先取成長之金屬特徵部彼此空間隔離。
Description
文中之各種實施例係關於電流體動力噴射列印及電鍍用之方法、設備、系統、墨水、及電鍍電解液。
製造半導體裝置通常涉及一系列之用以形成精細內連線或其他金屬特徵部的步驟。在涉及許多不同半導體處理設備的數個處理步驟期間可形成此類特徵部。例如,在3D封裝領域,金屬化可涉及在基板上形成導電晶種層、在晶種層上形成一層光阻、曝光及顯影該層光阻以在其中定義圖案、對基板進行除渣以移除圖案化特徵部內任何剩餘的非所欲光阻、以金屬電鍍基板、剝除光阻、及化學蝕刻移除先前未受到光阻保護的任何裸露晶種層。
此處所提供的背景說明係用以大致上說明本發明之背景。在此背景段落中所提及之本發明人的作品以及在申請時不能算作是先前技術的說明並非為本發明人明示或暗示自認之與本發明相對的先前技術。
文中之各種實施例係關於電流體動力噴射列印及電鍍用之方法、設備、系統、墨水、及電鍍電解液。文中所述之技術能以無光阻的方式形成金屬特徵部,實質上簡化了形成此類特徵部的處理方案且最少化相關的資本支出與處理成本。一般而言,文中之技術使用包含一或多種電鍍添加物如電鍍加速劑或電鍍抑制劑的特別墨水。選擇性地以期望圖案將墨水列印至基板上,且添加物與基板表面反應而變得強吸附至表面。在墨水乾掉後,電鍍基板且來自經列印之墨水之強吸附的電鍍添加物繼續吸附於受到墨水列印的表面上造成在基板之經列印與未列印區域處提供不同電鍍速率的先取電鍍處理。不同的電鍍速率形成金屬特徵部。在電鍍之後,可藉由蝕刻使特徵部彼此電性及空間隔離。
在揭露實施例的一態樣中,提供一種在基板上沉積金屬的方法,該方法包含:(a)接收包含晶種層的基板,其中晶種層為導電的且在基板表面上受到暴露;(b)經由電流體動力噴射列印將墨水以一圖案列印至晶種層上,其中墨水包含溶解於溶劑中之電鍍添加物,其中電鍍添加物包含加速劑或抑制劑,其中電鍍添加物強吸附至晶種層上;(c)經由先取沉積將金屬電鍍至基板上,先取沉積在來自墨水之電鍍添加物存在的位置處提供第一沉積速率並在來自墨水之電鍍添加物不存在的位置處提供第二沉積速率,其中第一沉積速率係不同於第二沉積速率。
在某些實施例中,電鍍添加物包含加速劑且第一沉積速率係大於第二沉積速率俾使金屬優先沉積在來自墨水之加速劑存在的位置處。在此些或其他情況中,加速劑可包含具有至少一巰基及一磺酸基的烷鏈、或酸鹽。例如,加速劑可包含巰基丙烷磺酸或巰基乙烷磺酸。在此些或其他情況中,墨水中之溶劑可包含選自由下列者所構成之族群的至少一材料:水、松油醇、碳酸乙烯酯、碳酸丙烯酯、二甲基亞碸(DMSO)、乙二醇、及丙二醇。
該方法可更包含化學蝕刻基板以移除在(c)中沉積之金屬的一部分及晶種層的一部分,藉此在來自墨水之加速劑存在的位置處形成金屬特徵部,金屬特徵部係彼此空間隔離。在某些此類情況中,在(c)中於電解液中電鍍基板,電解液包含:介於約10-1000 ppm之間的電鍍抑制劑添加物、介於約10-60 g/L之間的銅離子、介於約5-180 g/L之間的酸、及介於約30-80 ppm之間的鹵素離子。在此類實施例中,電解液中的加速劑(若存在)將傾向於在來自墨水之加速劑不存在的區域(如未受列印之區域)中增加電鍍速率且將傾向於減少受到列印之區域與未受列印之區域之間的沉積速率對比。因此,在各種實施例中,電解液可不具有任何加速劑、或僅具有微量的加速劑。
在某些實施例中,電鍍添加物包含抑制劑。在此類實施例中,第一沉積速率係低於第二沉積速率俾使金屬優先沉積在來自墨水之抑制劑存在的位置處。
在某些實施例中,該方法可更包含化學蝕刻基板以移除在(c)中沉積之金屬的一部分、在(b)中列印的墨水、及晶種層的一部分,藉此在來自墨水之抑制劑不存在的位置處形成金屬特徵部,金屬特徵部係彼此空間隔離。在使用抑制劑墨水的某些情況中,在(c)中於電解液中電鍍基板,電解液包含:介於約0-1000 ppm之間的加速劑、介於約10-60 g/L之間的銅離子、及介於約5-180之間的g/L 酸。在各種實施例中,電解液可不具有任何抑制劑、或僅具有微量的抑制劑。在某些此類情況中,電解液亦可不具有任何電鍍抑制劑添加物、或僅具有微量之電鍍抑制劑添加物。
在某些實施例中,基板更包含位於晶種層下方的附著阻障層。該方法可更包含:(d)化學蝕刻基板以移除在(c)中沉積之金屬的一部分及晶種層的一部分,藉此形成金屬特徵部,金屬特徵部係彼此空間隔離;及(e)將第二金屬電鍍至基板上,其中第二金屬選擇性地沉積至在(d)中所形成的金屬特徵部上但實質上不形成在附著阻障層上。在某些此類情況中,第二金屬可形成擴散阻障層。該方法可更包含:(f)將焊接材料電鍍至擴散阻障層上,焊接材料選擇性地沉積在(e)中所形成的擴散阻障層上但實質上不形成在附著阻障層上。在各種實施例中,墨水中的電鍍添加物與基板上的晶種層反應並化學結合至晶種層。
在揭露實施例的另一態樣中,提供一種電流體動力噴射列印設備,其包含控制器,控制器係用以使文中所請求或說明之電流體動力列印步驟中的一或多者加以進行。
在某些實施例中,該電流體動力噴射列印設備可包含:具有尖端的噴嘴,該尖端具有直徑介於約50-5000 nm之間的開口;墨水儲槽,係與噴嘴流體連接;基板支撐件,係用以在列印期間支撐基板;及電源,係用以在噴嘴與基板支撐件之間、或噴嘴與基板之間施加電位。
在揭露實施例的另一態樣中,提供一種電鍍設備,其包含控制器,控制器係用以使文中所請求或說明之電鍍步驟中的一或多者加以進行。
在某些實施例中,該電鍍設備包含:腔室,用以容納電解液;基板支撐件,係用以在電鍍期間支撐基板;陽極;及電源,係用以在電鍍期間於陽極與基板之間施加電位。
在揭露實施例的另一態樣中,提供一種基板處理系統,該系統包含:電流體動力噴射列印設備;電鍍設備;及控制器,用以使文中所主張或說明之步驟中的任何一或多者加以進行。
在揭露實施例的更另一態樣中,提供一種基板處理系統,該系統 包含:電流體動力噴射列印設備包含:具有開 口之噴嘴,開口具有介於約50-5000 nm之間之直徑;墨水儲槽,與噴嘴流體連接;基板支撐件,用以在列印期間支撐基板;及電源,用以在噴嘴與基板支撐件之間或噴嘴與基板期間施加電位;電鍍設備包含:腔室,用以容納電解液;基板支撐件,用以在電鍍期間支撐基板;陽極;及電源,用以在電鍍期間於陽極與基板之間施加電位;及控制器,用以:利用電流體動力噴射列印設備使墨水以圖案列印至基板上,墨水包含溶解於溶劑中的電鍍添加物,電鍍添加物包含加速劑或抑制劑,且在將墨水列印至基板上之後利用電鍍設備將金屬電鍍至基板上,電鍍係經由先取沉積進行,先取沉積在來自墨水之電鍍添加物存在的位置處提供第一沉積速率且在來自墨水之電鍍添加物不存在的位置處提供第二沉積速率,其中第一沉積速率係不同於第二沉積速率。
在各種實施例中,系統更可包含用以在基板上沉積晶種層的設備。在某些實施例中,系統更可包含用以將晶種層沉積至基板上的物理汽相沉積設備。在某些實施例中,系統更包含用以將晶種層沉積至基板上的無電鍍模組。在某些實施例中,系統更包含無電鍍活化模組。在此些或其他實施例中,控制器可用以在墨水被列印至基板上之前使晶種層沉積至基板上。
在某些實施例中,系統更包含用以自基板移除金屬的化學蝕刻設備。在此些或其他實施例中,控制器可用以使電鍍至基板上之金屬的一部分受到移除及基板上之晶種層的一部分受到移除。在某些實施例中,可在一單一設備中共同提供電流體動力噴射列印設備及電鍍設備。
在揭露實施例的更另一態樣中,提供一種電流體動力噴射列印用之墨水,該墨水包含:溶劑,溶劑包含選自由下列者所構成之族群的至少一材料:水、松油醇、碳酸乙烯酯、碳酸丙烯酯、二甲基亞碸(DMSO)、乙二醇、及丙二醇;及溶解於溶劑中之電鍍添加物,其中電鍍添加物包含加速劑或抑制劑,其中電鍍添加物係以介於約0.1-10 g/L之間的濃度存在於溶劑中。
在揭露實施例的另一態樣中,提供一種電流體動力噴射列印用之墨水,該墨水包含:電鍍添加物包含加速劑或抑制劑,其中電鍍添加物係以約0.1-10 g/L之間的濃度存在;及溶劑,溶劑在25°C下具有等於或小於約24 Torr的蒸氣壓及介於約40-90之間的介電常數,其中墨水具有介於約0.7-20 cP之間的黏度且電鍍添加物係完全溶解於溶劑中。
在某些實施例中,墨水中之氧的濃度約為1 ppm或更低。氧可隨著時間與某些墨水添加物反應,藉此減少墨水之關鍵電化學活性化合物的必要濃度。在某些實施例中,墨水包含可與氧反應且消耗氧的額外物種。可與氧反應且消耗氧的物種可以足以將墨水中之氧的濃度維持在約1 ppm或更低的濃度存在。此可改善墨水之保存期限。在某些實施例中,可與氧反應且消耗氧的物種為亞硫酸鹽化合物。一特定實例為亞硫酸鈉。在某些實施例中,墨水中的電鍍添加物包含加速劑。在某些其他實施例中,墨水中的電鍍添加物包含抑制劑。在許多實施例中,溶劑可包含選自由下列者所構成之族群的至少一材料 :水、松油醇、碳酸乙烯酯、碳酸丙烯酯、二甲基亞碸(DMSO)、乙二醇、及丙二醇。在某些實施例中,溶劑為有機的。在此些或其他實施例中,溶劑可具有介於約95-275°C之間的自然沸點。在此些或其他實施例中,溶劑可包含第一共溶劑及第二共溶劑。在此些或其他情況中,溶劑可包含潤濕劑。潤濕劑減少墨水與晶種層之間的接觸角。潤濕劑可避免不連續或滴狀之列印。在此些或其他情況中,墨水可包含鹽類。
下面將參考附圖更進一步說明此些及其他態樣。
在下面的敘述中將列舉各種特定細節以提供對所述實施例的全面瞭解。本發明之實施例可在缺乏部分或全部此些特定細節的情況下實施。在其他的情況下,不詳細說明習知的製程操作以免不必要地模糊本發明之實施例。雖然將利用特定實施例來說明本發明實施例,但應瞭解,其意不在限制本發明實施例。
圖1A之流程圖說明根據傳統方法在基板上形成精細內連線、墊、或其他金屬特徵部的一系統步驟。圖1B顯示用以進行圖1A之方法100之半導體處理設備的各種部件。圖1A中所示之步驟將在圖1B所示之設備的背景下加以說明。
在圖1A中,方法100始於操作101,在基板上沉積導電晶種層。此沉積在圖1B中所示的物理汽相沉積設備150中進行。接下來,將基板傳送至光阻沉積設備152並在操作103中將一層光阻形成至晶種層上。可經由濕式處理方法如旋塗形成光阻,或可經由乾式方法如在基板上方施加一捲預形成的光阻材料。
在形成光阻層之後,將基板傳送至光阻圖案化設備154,在操作105中經由將光阻層暴露至特定的光條件而圖案化光阻層。在操作105中亦將基板傳送至光阻顯影設備155,顯影在基板上已曝光之圖案。在一實例中,經由濕式化學處理顯影光阻,濕式化學處理涉及將基板暴露至其中具有具有溶解鹽的溶液如在水中的碳酸鉀溶液。此些圖案化操作共同形成光阻層中的凹陷特徵部。此些凹陷特徵部定義後續將沉積金屬的空間。
接下來,將基板傳送至電漿蝕刻設備156並在操作107處進行除渣處理以自特徵部之底部移除多餘的光阻材料。除渣處理通常涉及暴露至含氧電漿以燒去特徵部底部處的多餘光阻。
接著將基板傳送至電鍍設備158並在操作109處(例如經由電鍍或無電鍍)將金屬電鍍至定義在光阻層中的特徵部中。接著將基板傳送至光阻剝除設備160並在操作111中自基板剝除光阻層。可經由乾式電漿蝕刻技術(如將基板暴露至含氧電漿)或濕式技術(例如將基板暴露至光阻溶劑以溶解或膨脹光阻膜,之後可以高流、超音能力、或其他方法移除光阻)剝除光阻。在移除光阻層之後,將基板傳送至化學蝕刻設備162並在操作113中移除先前受到光阻層保護之區域中的晶種層。
在許多情況中,圖1B中所示之設備中的每一者皆為不同之設備,每一設備係用以進行圖1A中所述之處理流程中的一特定操作。圖1A與1B共同例示,用以形成金屬化特徵部如精細內連線之傳統處理流程為複雜、耗時、且昂貴的。需要許多不同的特用半導體處理設備且每一者必須適當地針對特定應用加以配置。由於每一處理及設備必須適當地調整,因此傳統處理流程所涉及之大量步驟及設備使吾人難以對基板處理技術(包含例如基板設計及佈局)進行任何改變或調整。這使吾人難以在一種基板類型或基板設計的製造與另一種基板類型或基板設計的製造之間切換。類似地,由於複雜的處理流程及涉及之大量設備,吾人難以運行測試、製造原型基板等。
文中所述之技術可在毋須圖1A及1B中所述之許多處理及設備的情況下形成精細內連線、墊、及其他類似的金屬化特徵部。因此,製造處理大幅簡化、處理設備的數目實質減少、且與處理相關的成本類似地降低(例如因為涉及較少之步驟且因為處理成本的實質部分係與獲取處理設備的資本支出直接相關)。
圖2A之流程圖說明根據文中之一實施例的一種精細內連線或類似之金屬化特徵部的形成方法。圖2B例示用以進行圖2A之方法200之處理設備。圖2A中所示之步驟可在圖2B所示之設備的背景下加以說明。
在圖2A中,方法200始於操作201,在晶種層沉積設備250中於基板上形成導電晶種層。在某些情況中,晶種層可在物理汽相沉積設備中經由物理汽相沉積所形成。如此領域中所知,亦可藉由其他方法如無電鍍形成晶種層。在某些實施例中,無電鍍始於無電活化步驟(其可涉及例如將基板暴露至錫離子)、接著以含鈀離子之電解液將錫(II) 置換/活化為錫(IV)。這會在基板表面上留下鈀電催化劑且允許許多介電材料之金屬化。在某些情況中,無電鍍可藉由包含還原劑及欲沉積作為晶種層之期望金屬的金屬離子的溶液而加以進行。適合用以產生銅之晶種層之還原劑的實例包含二甲基胺硼烷(DMAB)及次磷酸鉀。
在各種實施例中,在操作201中形成晶種層之後及在操作203中進行電流體動力噴射列印之前可選擇性地預處理基板。可進行此預處理以移除晶種層上的表面氧化物。預處理可經由濕式方法或乾式方法進行。例如,濕式方法可涉及將稀釋的酸如H2
SO4
或還原劑如二甲基胺硼烷(DMAB)施加至基板。乾式方法可涉及在還原環境如形成氣體中將基板加熱至約100-200°C的溫度。在操作201中沉積晶種層之後且在操作203中進行電流體動力噴射列印之前基板被暴露至大氣條件(或其他含氧環境)的實施例中,此類預處理尤其有利。
無論在形成及選擇性預處理晶種層中所用的特殊方法為何,將基板提供至電流體動力噴射列印設備252並在操作203中經由電流體動力噴射列印將墨水選擇性地列印至基板上。如下所述,墨水為電化學活性之墨水。可用將墨水沉積至基板上的其他方法,但電流體動力噴射列印尤其適合需要極高解析度液體轉移的應用(尤其是線、空間、及結構之關鍵尺寸大致上小於約50 μm更常小於10 μm或甚至小於2 μm的半導體內連線及封裝應用)。
利用電流體動力噴射列印處理選擇性沉積電化學活性之墨水亦涉及研發具有下列適合特性的墨水:適於儲存、傳送、輸送至基板表面、及活化化學成分如與此處理共同使用之適當之溶劑及活化化學品的溶解度。在文中之各種實施例中,墨水包含一或多種溶解於溶劑中的電鍍添加物。如下面所討論的,電鍍添加物的實例包含加速劑及抑制劑。下面將更進一步討論可存在於墨水中的適當溶劑及其他物種。
在基板表面上的墨水乾燥後,墨水中的電鍍添加物及任何其他非揮發性材料留在基板表面上。此時,例如可以去離子水選擇性地沖洗基板。雖然不欲受限於任何特定模型或理論,但一般相信,若功能上有用的電鍍添加物與基板金屬晶種層化學反應且變得強附接及固定於表面處,則根據文中實施例使功能上有用的電鍍添加物留在其列印之處是最有效的。換言之,電鍍添加物可與基板上之晶種層反應並化學結合至晶種層。硫醇終端基團(如R-S-H終端基團)巰基化合物為能結合至銅晶種層(及某些其他金屬晶種層或其他表面)並表現出期望之停滯特性的一例示性材料種類。此類化合物的特定實例包含巰基丙烷磺酸(例如其可作為加速劑)及巰基己醇(抑制劑)。強金屬結合化合物的另一例示性種類為三唑。苯并三唑為可作為抑制劑之有用三唑的一實例。苯并三唑-5-磺酸及苯并三唑-5-羧酸為可作為加速劑之三唑的實例。在沖洗後,可使基板受到旋轉乾燥或其他乾燥方法以移除任何非所欲之材料。沖洗可移除源於墨水的某些或所有非揮發性材料,此些非揮發性材料排除電鍍添加物。在選擇性的沖洗之後,例如由於上述的停滯,因此大部分或所有電鍍添加物應留在基板表面上。
接下來,將基板傳送至電鍍設備254且在操作205中經由先取沉積將金屬電鍍至基板上以形成特徵部。沉積處理為先取的,因為相較於墨水/電鍍添加物不存在之區域,墨水中所包含的至少一電鍍添加物可促進(例如加速劑)或遲緩(如抑制劑)電鍍。
例如,在墨水包含電鍍加速劑的情況中,相較於墨水不存在的基板區域,墨水存在的基板區域將經歷優先電鍍。相對地,在墨水包含電鍍抑制劑的情況中,相較於墨水存在的基板區域,墨水不存在的基板區域將經歷優先電鍍。下面將參考圖3A-3D及4A-4D更進一步說明每一此些實例。在任一實例中,在基板之經列印及未經列印區域處皆可發生某些量(例如非零之量)的沉積。然而,在經列印與未經列印區域中所達到的不同沉積速率可導致圖案化特徵部的成長。特徵部係位於經歷較高金屬沉積速率之區域中。換言之,除非特別指出並非如此,否則文中所用之「特徵部」一詞係指正向/舉升之特徵部而非負向/凹陷之特徵部。
在經由先取沉積處理電鍍金屬之後,將基板傳送至化學蝕刻設備256中並在操作207中化學蝕刻基板以移除多餘的電鍍金屬及晶種層。可部分移除存在特徵部之區域中之經電鍍的金屬。由於在蝕刻之前(相對於存在特徵部的區域)特徵部之間之區域中有相對少的金屬,因此可實質或完全移除特徵部之間之區域中之經電鍍的金屬及晶種層。此蝕刻的作用在於使金屬特徵部彼此空間及電性隔離。
可以各種方式組合處理設備之各種部件。在一實例中,一系統包含物理汽相沉積設備、電流體動力噴射列印設備、電鍍設備、及化學蝕刻設備,且每一設備係彼此不同且分離。在另一實施例中,可在進行複數處理之一較大設備的一模組中提供圖2B中所示之設備的一或多者。例如,物理汽相沉積設備可為一分離之設備,但可在一統一之處理設備中以模組形式提供基於液體之大氣處理設備如電流體動力噴射列印設備、電鍍設備、及化學蝕刻設備。在另一實例中,物理汽相沉積設備及化學蝕刻設備中的每一者可為分離的不同設備,但可在一較大的統一處理設備內以模組形式提供電流體動力噴射列印設備及電鍍設備中的每一者。在另一實例中,化學蝕刻設備為分離的不同設備,但可在一較大的統一處理設備內以模組形式提供物理汽相沉積設備、電流體動力噴射列印設備、及電鍍設備中的每一者。在另一實例中,可在一較大的統一處理設備內以模組形式提供物理汽相沉積設備及電流體動力噴射列印設備中的每一者,但電鍍設備及化學蝕刻設備為分離的不同設備或共同成為第二個統一處理設備。在更另一實施例中,可修改物理汽相沉積設備及/或電鍍設備中的一或多者以包含用以進行電流體動力噴射列印的硬體。在電鍍設備受到修改以包含用以進行電流體動力噴射列印之硬體的情況中,應注意確保電流體動力噴射列印處理中所用之墨水無法污染電鍍溶液。可提供可移動之檔板或其他限制硬體。圖2B中所示之設備有許多可行的組態,且應認為任何此類組合皆落在文中之實施例的範疇內。以此方式組態之設備可為線性的、多層的輪盤、輸送帶、叢集設備、或其他大體的設備設計,且每一種處理用的模組數目可實質上大於1(如10),其中基於設備之生產能力/輸出最佳化平行操作之每一類型處理模組的數目的混合。
圖3A-3D顯示根據一實施例之在其上形成特徵部時部分製造完成之半導體基板。在圖3A-3D的實施例中,電流體動力噴射列印處理中所用之墨水包含電鍍加速劑。是以,此實例中的墨水被稱為「加速劑墨水」。下面將參考圖2A 及2B中所述的操作及設備解釋圖3A-3D。圖3A例示其上具有晶種層301的基板300。在一特定實例中,基板300包含在矽晶圓上方的一層二氧化矽 ,但可使用許多不同的基板及材料。晶種層301包含導電材料如銅、鉭、或其組合。在另一實例中,晶種層301包含鎳。晶種層可使用各種材料及材料之組合。在晶種層301包含複數材料之組合的某些情況中,晶種層之最上層裸露部分係與欲電鍍之金屬結構的金屬相同(如銅線用之銅晶種),然而,不必總是此情況。大致而言,若使用水性電鍍,則晶種層301之裸露表面應為水性溶液中可電鍍的金屬(如可使用鎳晶種層電鍍銅線,而非大致上因抑制性氧化表面層W、Ta、Ti等而無法電鍍之金屬的裸露表面)。參考圖2A及2B,可在操作201中於晶種層沉積設備250(在某些情況中例如物理汽相沉積設備或無電鍍沉積設備)內形成晶種層301。在提供晶種層301之後,如圖3B中所示, 將加速劑墨水302列印至晶種層301上。此列印可在操作203中於電流體動力噴射列印設備252內完成。加速劑墨水302係以對應至期望金屬特徵部之圖案的圖案列印。
在晶種層301上列印加速劑墨水302之後,將金屬303電鍍至晶種層301上及加速劑墨水302上。此電鍍在操作205中於電鍍設備254內進行。雖然如圖3C中所示,金屬303形成在經列印及未經列印的兩種區域上方,但金屬303在印有加速劑墨水302的區域上方成長較快因此較多。事實上,存在於加速劑墨水302中的加速劑以及電鍍溶液中的額外電鍍添加物(如能減緩未印有加速劑之區域之相對電鍍速率的抑制劑 、及選擇性的整平劑)共同促進在經列印之區域中的較高電鍍速率(相對於未經列印之區域中的電鍍速率)。在此實例中,金屬303在經列印之區域中的優先電鍍速率為未經列印之區域的電鍍速率的三倍。在許多文中的實施例中,金屬303在經列印之區域中的優先電鍍速率為未經列印之區域的電鍍速率的至少四倍、或至少10倍、或至少20倍。相對沉積速率取決於某些因素如列印所沉積之添加物的濃度、所施加之電壓或總施加電流、溫度、及酸及/或銅濃度之選擇、及電鍍電解液中任何選定電鍍添加物(如抑制劑及/或整平劑)的化學特性。由於不同之沉積速率,加速劑墨水302所提供之圖案經由金屬303轉移。在電鍍之後,將基板300傳送至化學蝕刻設備256並如圖3D中所示在操作207中受到化學蝕刻以移除一部分之金屬303及一部分之晶種層301。尤其,蝕刻基板300至特定程度俾以完全移除未經列印之區域(如加速劑墨水302不存在之區域)中的金屬303及晶種層301但使金屬303及晶種層301仍留在經列印之區域(如加速劑墨水302存在之區域)。圖3D中的參考標號303d代表在操作207中之化學蝕刻之後仍留在基板300上的金屬特徵部。在此蝕刻操作之後,金屬特徵部303d係彼此空間及電性隔離。
圖4A-4D顯示根據另一實施例之其上形成特徵部時部分製造完成之半導體基板。在圖4A-4D之實施例中,電流體動力噴射列印處理中所用之墨水包含電鍍抑制劑。是以,此實例中的墨水被稱為「抑制劑墨水」。下面將參考圖2A 及2B中所述的操作及設備解釋圖4A-4D。圖4A例示其上具有晶種層401的基板400。晶種層401係類似於圖3A之晶種層301。可在操作201中於晶種層沉積設備250內形成晶種層401。在提供晶種層401之後,如圖4B中所示, 將抑制劑墨水402列印至晶種層401上。此列印可在操作203中於電流體動力噴射列印設備252內完成。抑制劑墨水402係以對應至期望金屬特徵部之相反圖案的圖案列印。換言之,將抑制劑墨水402提供至不期望形成金屬特徵部的區域中。
在晶種層401上列印抑制劑墨水402之後,將金屬403電鍍至晶種層401上及抑制劑墨水402上。此電鍍在操作205中於電鍍設備254內進行。雖然如圖4C中所示,金屬403形成在經列印及未經列印的兩種區域上方,但金屬403在不存在抑制劑墨水402的區域上方成長較快因此較多。事實上,存在於抑制劑墨水402中的抑制劑以及電鍍溶液中的額外電鍍添加物(如加速劑及選擇性的抑制劑及/或整平劑)共同促進在未經列印之區域中的較高電鍍速率(相對於經列印之區域中的電鍍速率)。在此實例中,金屬403在未經列印之區域中的優先電鍍速率為經列印之區域的電鍍速率的三倍。在許多文中的實施例中,金屬403在未經列印之區域中的優先電鍍速率為經列印之區域的電鍍速率的至少四倍、或至少10倍、或至少20倍。如參考圖3A-3D所述,相對沉積速率取決於某些因素如列印所沉積之添加物的濃度、所施加之電壓或總施加電流、溫度、及酸及/或銅濃度之選擇、及電鍍電解液中任何選定電鍍添加物(如加速劑、抑制劑及/或整平劑)的化學特性。由於不同之沉積速率,抑制劑墨水402所提供之圖案的相反圖案經由金屬403轉移。在電鍍之後,將基板400傳送至化學蝕刻設備256並如圖4D中所示在操作207中受到化學蝕刻以移除一部分之金屬403及一部分之晶種層401。尤其,蝕刻基板400至特定程度俾以完全移除經列印之區域(如抑制劑墨水402存在之區域)中的金屬303及晶種層301但使金屬403及晶種層401仍留在未經列印之區域(如抑制劑墨水402不存在之區域)。圖4D中的參考標號403d代表在操作207中之化學蝕刻之後仍留在基板400上的金屬特徵部。在此蝕刻操作之後,金屬特徵部403d係彼此空間及電性隔離。
圖9A-9D例示可用於某些實施例中的例示性處理流程。圖9A-9D之處理流程可與圖3A-D及4A-D中所示者結合。換言之,在利用電化學活性之墨水(如加速劑墨水或抑制劑墨水)先取電鍍特徵部之後可使用此處理流程。圖9A-9D中所示之實施例能形成包含不同類型之金屬的堆疊。此類實施例在所形成之特徵部包含不同金屬之膜層的情況下尤其有用。一實例為形成內連線柱,其可包含例如其上具有擴散阻障層及焊接層的金屬特徵部。在一特定實例中,金屬特徵部為銅、擴散阻障為鎳、且焊接材料為錫或錫銀。另一實例為形成相對寬但薄的導電連接墊。在各種實施例中,形成的堆疊可包含銅、鎳、錫、銦、銀、金等的任何組合。
如圖9A中所示基板900開始。基板900包含位於附著阻障層911上方的晶種層901。晶種層901係類似於文中所述的其他晶種層。附著阻障層911可包含材料如鎢、鈦、鉭、鈦鎢、鉭鎢等。將金屬903電鍍至晶種層上以形成舉升特徵部。此電鍍可利用文中所述之技術完成,例如使用電流體動力噴射列印設備252在基板表面上提供電化學活性之墨水、然後在電鍍設備254進行先取電鍍以形成舉升特徵部。雖然圖9A-9D未顯示墨水,但如參考圖3C及4C所解釋及所示,應瞭解此類已乾燥之墨水可存在於晶種層901與金屬903之間。又,雖然圖9A未顯示相鄰特徵部之間的任何金屬903,但應瞭解,如圖3C及4C中所示,此類金屬可存在。
在將金屬903電鍍至晶種層901上之後,將基板900傳送至蝕刻室如圖2B之化學蝕刻設備256。在此處,如圖9B中所示蝕刻晶種層901及金屬903以移除晶種層901受到暴露之區域中的晶種層901。此蝕刻係類似於圖2A之化學蝕刻操作207。蝕刻處理為選擇性的,其目標在於移除受到裸露之晶種層901 但使附著阻障層911實質上無損。
接下來,基板回到電鍍設備254且如圖9C中所示將擴散阻障層912選擇性地電鍍至金屬903上但實質上不沉積至附著阻障層911上。應瞭解, 某些量的擴散阻障層912可能會形成在附著阻障層911上例如晶種層901/金屬903接觸附著阻障層911的角落處。對於此應用的目的而言,此類沉積不應被認為是實質的。又,應瞭解,由於此類沉積僅因為晶種層901/金屬903的存在而發生,因此擴散阻障層912不會形成在已自晶種層901/金屬903所形成之特徵部移除之位置處的附著阻障層911上。
擴散阻障層用的一例示性材料為鎳,但依期望可使用其他材料。雖然不欲受限於任何理論或作用機制,但一般相信,擴散阻障層912不會形成在附著阻障層911上,因為在晶種層901被移除且附著阻障層911暴露至氧/水氣之後附著阻障層911已經氧化。此暴露至氧/水氣可在基板於蝕刻室與電鍍室之間傳送之時發生。附著阻障層911的氧化材料對於電鍍金屬的直接成核及成長而言具有高度抑制性,意即金屬(如擴散阻障層912)不會電鍍至氧化材料上。又,雖然附著阻障層911的上裸露表面已經氧化,但附著阻障層911仍能在金屬903的相鄰特徵部之間提供某些程度的電連接,是以能致使金屬903上的更進一步電鍍。是以,當電鍍擴散阻障層912時,其選擇性地沉積在金屬903上但不沉積於附著阻障層911上。擴散阻障層912沉積在金屬903的所有裸露側上(以及仍存在於金屬903下方之晶種層901的裸露部分上)。
接下來,如圖9D中所示,選擇性地將焊接層913沉積至擴散阻障層912上但不實質上沉積至附著阻障層911上。基於與上述擴散阻障層912之沉積相同的原因,此沉積亦為選擇性的。圖9D中所示之特徵部例如可為覆有焊接材料的柱或連接墊。提供圖9A-9D 所述之特定結構及材料作為例示形成包含多層不同材料之特徵部的目的。實施例不應限制至此段落中所述的特定結構或材料。依照特定應用之期望,可形成各種結構及材料包含文中所述之金屬的組合。
可使用電流體動力噴射列印產生先前以替代性列印方法如噴墨列印無法達成的極精細、小尺寸圖案。例如,噴墨列印可產生特徵部如直徑小至約50-100 μm的點。對比之下,可使用電流體動力噴射列印形成尺寸<0.5 μm的點、線、或其他特徵部。若期望較大的特徵部,可使用電流體動力噴射列印以極精準的方式如<0.5 μm的解析度形成特徵部。換言之,電流體動力噴射列印不僅僅在形成極小尺寸特徵部時有用,其在以高精準度形成較大特徵部時亦為有用的。下面將參考圖5解釋電流體動力噴射列印的原理。
圖5例示電流體動力噴射列印處理期間之基板500。以墨水502填充噴嘴501。又,噴嘴501係與墨水儲槽(未顯示)流體連接,墨水儲槽依所需將墨水502提供至噴嘴501中。噴嘴尖端503係位於噴嘴501的底部處。使噴嘴尖端503處於基板500附近。在噴嘴501與基板500之間施加大電位504時,墨水502內的溶劑分子與基板500表面的偶極矩位向重新排列,導致形成與基板表面之空間電荷相反符號的液相表面空間電荷。這會將墨水502朝向基板500的表面牽引,在噴嘴尖端503處形成泰勒錐,最終墨水502自噴嘴尖端503噴射為墨水液滴505。墨水液滴505包含剩餘電荷並在電位504所產生的電場中朝向基板500的表面加速。在撞擊基板500之表面時,墨水液滴505中的電荷受到中和。 由於此基於液滴的流體流,電流間歇性地流至噴嘴 501與基板500之間所產生的「電路」中。在撞擊基板500之後,墨水液滴505中的溶劑乾燥,留下墨水502中的任何非揮發性物質。在文中之各種實施例中,此類非揮發性物質可為電鍍添加物如加速劑或抑制劑。
雖然圖5顯示單一噴嘴,但應瞭解,電流體動力噴射列印處理可使用大量成列、成行、成陣列、或其他方式配置之可獨立控制的噴嘴。可獨立偏差每一此類噴嘴使其依期望噴射或不噴射粒子。又,噴嘴及基板可彼此相對移動俾使每一噴嘴可依期望於各種位置處和基板互動。在某些情況中,噴嘴為可移動的。在另一情況中,基板(如基板支撐件)是可移動的。在更另一情況中,噴嘴與基板兩者皆為可移動的。雖然圖5將噴嘴501顯示為相對長之向下突出的窄桿,但亦可使用其他噴嘴設計。在另一實施例中,用以輸送墨水的噴嘴可為較簡單的設計如包含與墨水儲槽流體交流的孔口。在此類實施例中,孔口係類似於噴嘴尖端503處的開口。除非特別指出並非如此,否則文中所用之孔口及開口等詞可交換使用。
在某些實施例中,噴嘴尖端503處之開口的寬度可介於約50至5000 nm之間。在許多情況中,液滴的尺寸約為噴嘴尖端開口的三分之一。例如,可使用直徑約300 nm的噴嘴尖端開口形成直徑約100 nm的液滴。一般而言,噴嘴尖端開口的寬度應相對小以列印出小尺寸之特徵部。例如,在許多情況中可使用寬度落在上述範圍內的噴嘴產生直徑落在約20-1500 nm之間之範圍的墨水液滴。可使用此範圍內的液滴尺寸形成極高解析度如<0.5 μm之範圍的圖案(最終成為經電鍍之金屬特徵部)。在某些實施例中,噴嘴尖端503與基板500之表面之間的距離506可介於約0.05至5 mm之間。
設備亦可包含圖5中未顯示之支援整體列印處理的複數特徵部如噴嘴及/或用以調節噴嘴/列印頭相對於基板之3D位置的基板定位裝置。例如,設備可包含光學位置及返回原點用之硬體。此類硬體可用以偵測晶圓上的基準,藉此在噴嘴/列印頭與基板之間進行精確對準,俾使列印發生在基板上相對於基板上之下方結構、基板上之缺口及/或其他基準、及/或基板邊緣的期望位置處。設備可包含用以控制列印墨水自大量儲存容器至噴嘴頭之輸送的硬體(如泵浦、管線、濾件等)。設備可包含支援複數噴嘴在多噴嘴頭內同時獨立定位的特徵部。 可提供複數獨立的壓電定位裝置,其每一者皆能使多噴嘴頭組件之一或多個噴嘴相對於彼此移動,藉此致能可變之線與線之間的平行列印操作空間。設備可包含用以控制噴嘴頭移除或添加的元件及用以控制墨水、基板、或兩者之溫度的元件。
可設計設備俾使列印頭及工作件上方的區域為實質密封的(如形成環境腔室),以控制噴嘴頭附近之空間及/或列印頭與晶圓之間之間隙中的大氣環境的溫度及/或氣體存在。例如,可使用環境腔室移除非所欲之氣體(如氧或濕氣)。在此些或其他實例中,可將一或多種氣體(如反應性氣體或惰性氣體)添加至腔室例如與墨水或基板反應、或產生惰性氣氛(如氮氣、氬氣)。在此些或其他實例中,設備可包含用以調節氣氛的硬體以容納經控制之量的蒸發墨水溶劑及/或在真空條件(如其可協助溶劑之蒸發)下進行列印。在此些或其他實例中,設備可具有一或多個前開口標準艙(FOUP),其為設計用來在受控環境中穩固安全地支撐基板的密閉空間。如下面參考圖7討論,例如藉由設有適當負載接口及機器搬運系統的設備可自FOUP移除基板。在基板分別在設備中受到處理之前及/或之後,可使用FOUP儲存進入及/或離開的基板。
在某些實施例中,設備可包含彼此平行操作之兩或更多模組。每一模組可如文中所述的方式配置,例如在基板表面上提供電流體動力噴射列印 。或者或此外,如下面參考圖7及8所更進一步說明的,可配置一或多個模組以進行其他功能。此類其他功能可包含但不限於,在列印前預處理基板、在列印之後及電鍍之前沖洗基板、在沖洗之後乾燥基板、及電鍍基板。在某些實例中,用以在列印之前預處理基板的模組可操作以自晶圓移除表面氧化物。此移除可在濕式預處理站中利用濕式方法完成、或在乾式預處理站中利用乾式方法完成。濕式方法可涉及將稀釋之酸如H2
SO4
或還原劑如二甲基胺硼烷(DMAB)施加至基板表面。乾式方法可涉及在還原環境如形成氣體中加熱基板(如加熱至介於約100-200°C的溫度)。在各種實施例中,如下面參考圖7及8將更進一步討論的,設備可包含用以在各種模組之間支撐及輸送晶圓的系統(如機器人搬運系統)。
其他共同的設備特徵可包含流體條件輸送控制設備(如加熱器/冷卻裝置及熱交換器、位準控制器等)、及例如用以調節噴嘴位置(如使用電流反饋及被綁定至電流體動力電流的噴嘴高度)及流體輸送(如使用基板上之液體薄膜的光學分析)的反饋控制量測設備。亦可考慮多通道功率及/或功率切換裝置以開關控制電流體動力噴射列印頭的陣列,使其在較大的「列印頭」內獨立操作。
在電流體動力噴射列印期間可控制之一因素為施加至一或多個噴嘴501中之每一者與基板500之間的電位(或相關的電流)的強弱。當電場超過特定限制值時,來自泰勒錐之頂點處之表面電荷排斥的應力會超過表面張力,因此墨水液滴505朝向基板500噴射。電場電位504應低於會造成墨水原子化或在多方向上缺乏控制地噴灑的電位。在某些實施例中,施加至噴嘴 501與基板500之間之電位504的大小可介於約0.5-10 kV之間、或介於約1.5-4 kV之間。電位的大小可取決於多個特徵如墨水502中之溶劑的種類及特性、墨水502中的電鍍添加物的種類及特性、墨水502中之任何額外物種(若存在任何物種)的種類及特性、噴嘴尖端503與基板500之間的距離506、及列印圖案中之特徵部的期望尺寸及解析度。
在各種實施例中,墨水及/或墨水液滴可具有特定的特性。在文中的實施例中,墨水包含溶解於溶劑中的至少一電鍍添加物。為了確保墨水液滴到達基板表面,墨水液滴可具有特定尺寸且墨水中之溶劑可具有特定的揮發性。在各種實施例中,液滴尺寸可至少約為20 nm、至少約為50 nm、或至少約為100 nm。在此些或其他情況中,液滴尺寸可至少約為1500 nm或更小、至少約為1000 nm或更小、至少約為400 nm或更小、至少約為200 nm或更小、至少約為100 nm 或更小、或至少約為50 nm或更小。在某些特定的實例中,液滴尺寸可介於約 20-1000 nm之間、或可介於約100-400 nm之間。在此些或其他實施例中,墨水中的溶劑所具有之正常沸點可介於約90-275°C之間、或介於約100-225°C之間。在某些情況中,溶劑所具有之正常沸點可至少約為95°C、至少約為100°C、至少約為125°C、至少約為150°C、或至少約為175°C。在此些或其他實施例中,溶劑所具有之正常沸點可約為275°C或更低、例如約為225°C或更低、例如約為150°C或更低。在此些或其他實施例中,墨水中的溶劑在25o
C下可具有介於約0.05-30 Torr之間(如介於約6 - 4000 Pa之間)、或介於約0.1-25 Torr之間(如介於約13-3300 Pa之間)的蒸氣壓。在許多情況中,溶劑在25°C下所具有的蒸氣壓約可等於或小於水的蒸氣壓。在25°C下,水具有約23.8 Torr(如約3175 Pa)的蒸氣壓。是以,在各種實施例中,溶劑在25°C下所具有之蒸氣壓係等於或小於約24 Torr (如小於或等於約3200 Pa)。雖然考慮在25°C下之蒸氣壓,但應瞭解,在使用期間溶劑可處於不同溫度下。揮發性較高的溶劑可在到達基板表面之前便乾燥,在該點處自由電荷在空氣中分解溶劑。若此情況為真,則無法有效地將圖案列印至基板表面。相對地,揮發性較低的溶劑一旦存在於基板上後可能無法充分快速地乾燥。若此情況為真,則墨水可能會呈塗抹狀而濕得超出期望圖案的目標尺寸。在許多情況中,期望液滴到達基板表面後的100 ms內完全乾燥。
和墨水相關的另一考量是溶劑應充分地溶解電鍍添加物。在許多情況中,電鍍添加物為極性有機電鍍添加物。在此類情況中,溶劑可能也是極性的,有助於溶解極性有機電鍍添加物。可使用之極性有機電鍍添加物的一實例為加速劑巰基丙烷磺酸。在某些情況中,溶劑可具有特定的介電常數,其可反應在其溶解電鍍添加物的能力上。在某些情況中,溶劑可具有大致上類似於水的介電常數,此介電常數係介於約40與90之間。大體而言,溶劑及電鍍添加物應具有相當的極性。
可符合上述標準的例示性溶劑包含水、松油醇、碳酸乙烯酯、碳酸丙烯酯、二甲基亞碸(DMSO)、乙二醇、聚丙二醇、及其組合。若溶劑內之電鍍添加物的揮發性及溶解度能維持在上述指導方針內,則此些例示性溶劑亦可與其他溶劑組合。在許多情況中,溶劑為有機及非水性的,但在某些情況中可使用水。可用以修改基礎溶劑之黏度、介電常數及其他特性以產生具有目標效能之墨水的例示性共溶劑包含碳酸二甲酯、碳酸二乙酯、DMSO、及水。可共同使用之其他例示性共溶劑包含但不限於碳酸二乙酯/碳酸丙烯酯、碳酸二甲酯/碳酸丙烯酯、碳酸二乙酯/碳酸乙烯酯、及碳酸二甲酯/碳酸乙烯酯。
關於墨水的更進一步考量為其黏度。太黏的墨水可能難以處理及/或輸送至列印頭、或難以適合的方式自噴嘴尖端牽引,但不夠黏的墨水可能在基板表面上乾燥之前便快速/輕易呈現塗抹狀。在某些實施例中,墨水可具有介於約0.7-20 cP 之間、更通常具有介於約0.8-3 cP 之間的環境溫度黏度(如在20°C下)。
可在墨水內以特定濃度提供電鍍添加物。在某些實施例中,電鍍添加物的提供濃度可介於約0.01-10 g/L(10-10,000 ppm)之間、或介於約 0.1-10 g/L之間、在某些情況中係介於約0.1-1 g/L(約100-1000 ppm)之間。在某些此類實施例中,電鍍添加物的提供濃度可至少約為0.1 g/L(100 ppm)、或至少約為0.15 g/L(150 ppm)、或至少約為0.2 g/L(200 ppm)。特定應用之電鍍添加物的理想濃度可取決於一些因素例如電鍍添加物的種類及特性、溶劑的種類及特性、後續用以電鍍金屬特徵部之電鍍溶液的組成等。在各種實施例中,目標為使墨水能供給足夠的電鍍添加物完全覆蓋其潤濕的表面(如期望列印墨水位置處之晶種層)及與其潤濕的表面反應而形成吸附材料的至少一單層。應瞭解,單層大致上被限制至已列印有墨水之區域。
除了電鍍添加物及溶劑之外,墨水可包含一或多種額外物種。例如,在某些情況中墨水可包含潤濕劑(如介面活性劑)。當潤濕劑存在時,潤濕劑 可改變溶劑的表面張力,藉此影響墨水液滴的尺寸及所產生之列印圖案及電鍍金屬特徵部的尺寸與形狀。潤濕劑可減少墨水與其上列印墨水之金屬表面(如晶種層)之間的接觸角,藉此改善墨水的潤濕能力。潤濕劑可為不具電化學活性的化合物。在許多情況中,潤濕劑不會接合至金屬表面(如晶種層),因此在沖洗及/或與電鍍溶液接觸時會被溶解掉。可用以作為潤濕劑之例示性介面活性劑包含例如月桂酸硫酸鈉、聚丙烯-或乙二醇、或氧化物。在此些或其他情況中,墨水可包含鹽類。當鹽類存在時,鹽類可改變墨水之蒸氣壓、黏度、及其他特性,藉此影響墨水液滴的尺寸及所產生之列印圖案及電鍍金屬特徵部。例示性之鹽類可例如包含碳酸四甲酯、碳酸四乙酯、檸檬酸四甲酯、檸檬酸四乙酯、四甲基氫氧化物、或四乙基氫氧化物、及硫酸銅。在墨水包含加速劑的情況中,墨水可不具有任何抑制劑。類似地,在墨水包含抑制劑的情況中,墨水可不具有任何加速劑。在某些情況中,例如潤濕劑與加速劑結合使用的情況中,墨水及潤濕劑剛好具有電鍍抑制劑的作用,因此墨水可包含加速劑及抑制劑(如潤濕劑)兩者。下面將更進一步討論電鍍添加物如加速劑、抑制劑及其在電鍍處理期間的互動。
當墨水被輸送至電流體動力噴射列印設備之噴嘴時,墨水可具有特定最大的氧濃度。在某些情況中,可提供除氣裝置以確保墨水中之氧濃度係低於最大目標濃度。除氣裝置可流體連接至墨水儲槽、或流體連接在墨水儲槽與噴嘴之間。在某些實施例中,被輸送至噴嘴之墨水中的最大氧濃度約為1 ppm。亦可藉著包含會與墨水中之氧本身反應且消耗墨水中之氧的物種如有機或無機硫酸,控制墨水中的氧位準。一特定實例為亞硫酸鈉。可在墨水中提供會與氧反應且消耗氧的物種,其濃度應足以將墨水中的氧濃度維持在約 1 ppm或更低。
可影響電流體動力噴射列印處理之結果的另一因素為列印進行的溫度。例如,墨水的溫度可影響墨水的黏度,黏度可影響液滴尺寸及所產生之列印圖案/電鍍特徵部。類似地,基板的溫度可影響墨水多快乾燥。在各種情況中,可在列印期間控制墨水的溫度、噴嘴的溫度、及/或基板的溫度(或其上放置了基板的支撐件的濕度)。例如,在列印期間可將墨水及噴嘴維持在介於約100-200°C之間的溫度下。在此些或其他情況中,在列印期間可控制基板或基板支撐件的溫度。例如,取決於特定的溶劑及墨水特性,可將基板或基板支撐件維持在經冷卻或經加熱的溫度下。例如,在列印期間可將基板或基板支撐件維持在介於約100-200°C的溫度下。
在某些情況中,墨水可為化學穩定的俾以被長久儲存。在其他情況中,墨水可為較不化學穩定的。在某些此類實施例中,可在使用前的短時間內(如使用前之約一個禮拜或更短的時間內、例如使用前之約3天或更短時間內、或使用前之約24小時或更短時間內)藉著在相關溶劑內以期望濃度混合相關成分而製備墨水。
基板亦可具有特定特性。例如,在許多情況中基板為矽半導體晶圓。基板上通常具有一層氧化矽。又,基板通常包含導電晶種層,如圖3A及4A中所示,當基板被提供至電流體動力噴射列印設備時導電晶種層係受到暴露。導電晶種層通常為金屬且通常包含銅、鉭、鎳、或其混合物。在某些情況中亦可使用其他金屬。晶種層可具有介於約50-2000Å之間的厚度。在電流體動力噴射列印處理中列印之後,乾燥的墨水可具有介於約0.01-0.25 μm之間的厚度。在電鍍之後及蝕刻之前,先取電鍍的特徵部可具有介於約0.25-25 μm之間的厚度(如以高度方式量測)。先取電鍍特徵部之間之電鍍金屬(如以相對較慢之速率成長的金屬)的厚度(如以高度方式量測)可介於約0.05-2 μm 之間。如參考圖3D及4D所解釋的,在電鍍之後可使用化學蝕刻蝕刻去除(i)先取電鍍特徵部之間的非所欲金屬;(ii)先取電鍍特徵部之間的非所欲晶種層;(iii)非所欲墨水(若存在任何墨水);及(iv)先取電鍍特徵部上之金屬的上部。在蝕刻之後,先取電鍍之金屬特徵部係彼此空間及電性隔離。經隔離的特徵部可具有介於約0.20-20 μm之間的高度。
如上所述,墨水通常包含電鍍添加物以促進經列印之區域與未經列印之區域之間的不同的電鍍速率。在許多情況中,添加物為加速劑或抑制劑。在墨水包含加速劑的情況中,電鍍溶液通常包含抑制劑(及選擇性的整平劑)。在墨水包含抑制劑的情況中,電鍍溶液通常包含加速劑(及選擇性的整平劑)。然而在某些情況中,電鍍溶液可不具有(或實質不具有)加速劑、抑制劑、及/或整平劑。在此類情況中,電解液可包含溶劑(如水)、欲電鍍之金屬離子(如電鍍銅特徵部用之銅離子)、及酸。
雖然不欲受限於任何理論或作用機制,但一般相信,電鍍抑制劑如聚乙二醇、聚環氧乙烷、聚丙二醇、及聚環氧丙烷(單獨或與其他電鍍浴添加劑的組合)為表面動力限制(或極化)化合物,其可造成基板-電解液界面各處的壓降大幅增加,尤其是當與表面化學吸附鹵化物(如氯化物或溴化物)一起作用時尤其如此。鹵化物可具有介於抑制劑分子與晶圓表面之間之化學吸附橋樑的功能。抑制劑具有下面兩種作用:(1)增加基板表面存在有抑制劑之區域相對於無抑制劑之區域的局部極化;及(2)增加基板表面的大致極化。增加的極化(局部及/或大致)係對應至增加的電阻率/阻抗,因此使特定施加電位下的電鍍較慢。
一般相信,傳統的電鍍抑制劑雖然不會強吸附或化學吸附至基板表面上且電鍍抑制劑不會被大量地摻入沉積薄膜中,但電鍍抑制劑可能會因電鍍浴中的電解或化學分解而隨著時間緩慢退化。由於傳統的電鍍抑制劑不會強吸附至基板表面上,因此此些分子被提供於墨水中時通常不會造成文中所述之不同的電鍍速率。而是墨水中所提供的電鍍抑制劑可能會在沖洗或與電鍍溶液接觸時被洗掉。傳統電鍍抑制劑通常為相對大的分子,且在許多情況中具有聚合物的本質(如聚環氧乙烷、聚環氧丙烷、聚乙二醇、聚丙二醇、各種共聚合物及其組合物等)。抑制劑的其他實例包含:具有S-功能基團及/或N-功能基團的聚乙烯與聚環氧丙烷、聚環氧乙烷與聚環氧丙烷的嵌段聚合物等。抑制劑可具有線性鏈結構或分支結構。在市售的抑制劑溶液中常同時存在著具有各種分子量的抑制劑分子。不若文中所述之抑制劑(如可在抑制劑墨水中用來作為極化劑者),抑制劑分子通常不會強接合至表面且可藉由沖洗自表面移除、或在與電鍍溶液接觸時可自表面擴散離開而進入電鍍溶液中。因此文中所用的抑制劑分子為極化劑,其可相對鬆散地接合至表面且無法被用於抑制劑墨水中作為主要抑制劑。意即,可針對非造成不同電鍍速率的目的將抑制劑添加至電流體動力噴射列印墨水中。例如,某些抑制劑亦具有潤濕劑/介面活性劑的作用。為了改善墨水在相關晶種層上之潤濕能力的目的,可將此類抑制劑提供至電流體動力噴射列印墨水(如加速劑墨水或抑制劑墨水)中。抑制劑亦可存在於電鍍溶液中,在列印之後基板係於電鍍溶液中受到電鍍。此類抑制劑在墨水為加速劑墨水的情況中尤其有利。
雖然不欲受限於任何理論或作用機制,但一般相信,加速劑(單獨或與其他電鍍浴添加劑的組合)傾向局部地降低和抑制劑存在相關的極化效應,藉此局部地增加電沉積速率。在加速劑吸附最濃的區域中極化效應的降低最顯著(即極化的降低為加速劑吸附之局部表面濃度的函數)。例示性的加速劑包含但不限於二巰基丙磺酸、二巰基乙磺酸、巰基丙磺酸、巰基乙磺酸、二-(3-磺丙基)二硫(SPS)、及其衍生物。在文中之各種實施例中,加速劑包含具有至少一巰基團及一磺酸基的烷鏈或鹽。雖然加速劑可變得強吸附至基板表面且通常因為列印處理及/或電鍍反應而變得橫向表面停滯,但加速劑通常不會被大量包含於薄膜中。是以,當沉積金屬一段足以沉積實質金屬薄膜的時間時,加速劑會留在表面上。
對於本文之目的而言,抑制劑(例如可存在於墨水中)為電化學活性化合物,其(i)與基板表面(如晶種層)反應或變得強吸附至基板表面(如晶種層),俾以在表面受到沖洗或與電鍍溶液時仍留在表面上;及(ii)增加表面之極性(或等同地增加在電鍍期間之電荷轉移電阻、或增加驅動流經表面相同量之電流所需的電壓)。
在某些實施例中,整平劑可存在於墨水及/或電鍍溶液中。雖然不欲受限於任何理論或作用機制,但一般相信,整平劑(單獨或與其他電鍍浴添加劑的組合)具有極化劑的作用。在某些情況中,整平劑可置換加速劑、移除加速劑、或驅動加速劑被包含至成長金屬薄膜層,藉此抵消與加速劑相關的去極化效應。
整平劑可局部增加基板的極化/表面阻抗,藉此在整平劑存在的區域中減緩局部電沉積反應。整平劑的主要特徵在於,整平劑的局部表面濃度在某個程度上係由質量傳輸所決定且整平劑通常會因與表面接觸及/或電還原而被持續消耗至成長電鍍薄膜中或被轉變為非抑制性的副產物。由於此消耗/轉變,因此整平劑被持續供給至表面以維持整平劑在表面處的期望濃度。因此,整平劑主要作用在具有幾何特徵自表面突離且較暴露至溶液環境的表面結構上。此作用「平滑」電沉積層的表面。一般相信,在許多情況中整平劑在基板表面處以等於或接近於擴散限制速率的一速率反應或被消耗,因此連續地供給整平劑通常有利於維持各個時間處的均勻電鍍條件。在某些實施例中,墨水及電鍍溶液兩者皆可不具有整平劑(或類似地,整平劑可存在但僅有微量)。
整平劑化合物大致上基於其電化學功能與影響而加以分類為整平劑,且不需要特定的化學結構或配方。然而,整平劑通常包含一或多個氮、胺、醯亞胺或咪唑,且亦可包含硫官能基團。某些整平劑包含一或更多的五元與六元環及/或共軛有機化合物衍生物。氮基團可形成環結構的一部分。在含胺的整平劑中,胺類可為一級、二級、或三級烷基胺或芳基胺。又,胺可為芳基胺或雜環胺。胺的實例包含但不限於二烷基胺、三烷基胺、芳烷基胺、三唑、咪唑、三唑、四唑、苯并咪唑、苯并三唑、哌啶、嗎啉、哌嗪、吡啶、噁唑、苯并噁唑、嘧啶、喹啉、及異喹啉。尤其可使用咪唑與吡啶。整平劑的另一實例為健那綠B。整平劑化合物亦可包含乙醇基團。例如,整平劑可包含一通用骨幹(類似於如在聚乙二醇或聚環氧乙烷中所見的骨幹)及安插至鏈上的胺官能基片段(如健那綠B)。環氧化物的實例包含但不限於環氧鹵丙烷如環氧氯丙烷與環氧溴丙烷、及聚環氧化物化合物。尤其可使用具有兩或更多環氧化物部分的聚環氧化物化合物,該兩或更多環氧化物部分係藉由含醚鍵聯結合在一起。某些整平劑化合物為聚合性的,但某些為非聚合性的。聚合性整平劑化合物的實例包含但不限於聚乙烯亞胺、聚醯胺胺、及一胺與各種氧環氧化物或硫化物的反應產物。非聚合性整平劑及電鍍抑制化合物的一實例為6-巰基-己醇。類似地,許多其他的有機硫醇及非含硫醇-磺團化合物的化合物在吸附至表面時可作為整平劑/電鍍抑制劑。適合的整平劑的另一實例為聚乙烯吡咯烷酮(PVP)。
大體而言,加速劑增加電鍍速率而抑制劑及整平劑減少電鍍速率。由於整平劑亦具有減少電鍍速率的功能,因此在某些整平劑符合抑制劑條件的情況下可將此些整平劑視為是本申請案之目的下的抑制劑。如上所述,抑制劑為會變得接合至基板表面(如晶種層)且具有優先遲緩抑制劑存在處(相對於抑制劑不存在處)之電鍍反應之作用的物種。當使用抑制劑墨水時,由於抑制劑墨水中之抑制劑的局部電鍍抑制作用應持續夠久的時間以在電鍍期間產生電鍍對比 (如不存在抑制劑的區域具有較多電鍍而在存在抑制劑的區域具有較少電鍍)。
電鍍處理中所用的電解液可具有特別的特性。在一實例中,電流體動力噴射列印處理中所用之墨水包含電鍍加速劑(如加速劑墨水)。是以,電鍍處理中所用之電解液可不具有加速劑(或僅具有微量的加速劑)。這能確保加速劑僅吸附在基板表面上的期望位置處如列印有加速劑墨水且期望金屬特徵部之位置。在此些情況中,電解液包含一或多種其他電鍍添加物如抑制劑及選擇性的整平劑。例示性的抑制劑濃度可介於10至1000 ppm之間且例示性的整平劑濃度(當整平劑存在時)可介於約0.1至2 ppm之間。又,電解液通常包含之銅離子(如來自於硫酸銅或其他來源)的濃度係介於約10-60 g/L之間、酸(如硫酸)的濃度約為5-180 g/L、鹵素離子(如氯、溴、氟等)的濃度約為30-80 ppm。鹵素離子可具有促進抑制劑分子吸附至基板表面的作用。在此實例中,在電鍍期間施加電流至基板,使銅沉積在受到列印及未受到列印之區域上,但優先沉積(如沉積較多)在列印有加速劑墨水的區域上。
在另一實例中,電流體動力噴射列印處理中所用之墨水包含電鍍抑制劑(如抑制劑墨水)。是以,電鍍處理中所用之電解液可不具有抑制劑(或可僅具有微量的抑制劑)。這能確保抑制劑僅吸附在基板表面上的期望位置處如列印有抑制劑墨水且不期望金屬特徵部之位置。在某些實施例中,用以電鍍特徵部之電鍍溶液可僅包含一酸(如介於約5-180 g/L之間的硫酸)及銅離子(如介於約10-60 g/L之間)。然而,取決於抑制劑墨水中之抑制劑與電鍍浴中所用之加速劑之間的相對表面吸附強度,一或多種額外成分如加速劑、氯離子、及抑制劑可存在於電鍍浴中以促進電鍍速率對比。尤其,若抑制劑較強地吸附且在表面處不會被加速劑所置換,則加速劑可存在於電鍍溶液中且吸附至無抑制劑的表面區域。在此些情況中,電解液可包含一或多種其他電鍍添加物如加速劑及選擇性的整平劑。例示性的加速劑濃度可介於約10-1000 ppm之間,例示性的整平劑濃度(當整平劑存在時) 可介於約0.1-2 ppm之間。又,電解液通常包含之銅離子(如來自於硫酸銅或其他來源)的濃度係介於約10-60 g/L之間、酸(如硫酸)的濃度約為5-180 g/L、且在各種情況中鹵素離子(如氯、溴、氟等)的濃度約為30-80 ppm。在此實例中,在電鍍期間施加電流至基板,使銅沉積在受到列印及未受到列印之區域上,但優先沉積(如沉積較多)在無抑制劑墨水的區域上。
在加速劑弱吸附至基板表面上而抑制劑強吸附至基板表面上的替代性實施例中,在將抑制劑列印至表面上之後,在電鍍之前可將加速劑如巰基丙磺酸暴露至整個表面。在此實施例中例如在以抑制劑墨水選擇性地列印表面之後,在基板表面旋轉時將包含1 g/L 巰基丙磺酸(或其他加速劑)的溶液噴灑或以其他方式提供至基板表面,以將整個表面暴露至加速劑。雖然不欲受限於任何特定的模型或理論,但加速劑會吸附至無抑制劑之金屬表面區域而不會與列印的抑制劑反應或置換抑制劑。接著以水噴灑表面以沖洗表面,接著選擇性地旋乾表面。這留下表面上有兩種區域:吸附有來自列印處理之制劑的區域、及吸附有來自噴灑處理之加速劑的區域。吸附有抑制劑的區域係對應至列印有抑制劑墨水的區域,而吸附有加速劑的區域係對應至此些區域的相反部分。接續在電鍍溶液(其可不具有任何加速劑)中的表面電鍍導致兩種區域之間的電鍍速率高對比。
在電鍍基板之後,使基板受到化學蝕刻操作以移除多餘的電鍍金屬、墨水、及晶種層,藉此使獨立的金屬特徵部依期望在空間及電性上隔離。蝕刻處理可涉及使基板與化學蝕刻劑接觸。蝕刻處理進行一段足以移除非所欲材料的時間,但此時間不足以完全移除期望的金屬特徵部。
圖6顯示用以進行電鍍的一例示性電鍍池。通常電鍍設備包含一或多個電鍍池,複數基板(如複數晶圓)可在電鍍池中受到處理。圖6中僅顯示單一電鍍池以維持畫面清晰。為了最佳化電鍍及確保電鍍添加物可在長期間內作用,應避免電鍍添加物和陽極反應。因此,有時電鍍池之陽極與陰極區域會藉由薄膜分離,俾使具有不同組成的電鍍溶液可在每一區域中受到使用。陰極區域中的電鍍溶液被稱為陰極電解液;陽極區域中的電鍍溶液被稱為陽極電解液。電鍍添加物可被限制於陰極電解液以避免其與陽極的非所欲反應。可使用多種工程設計將陽極電解液與陰極電解液導入電鍍設備中。
參考圖6,其顯示根據一實施例之電鍍設備601的橫剖面圖。電鍍浴603包含電鍍溶液(具有文中所提供的組成),電鍍溶液在圖中被顯示為位準605。此容器的陰極電解液係適合將基板容納於陰極電解液中。晶圓607被浸沒於電鍍溶液中且受到安裝於可旋轉轉子611上的「殼式」基板支撐件609所支撐,可旋轉轉子611使得殼式基板支撐件609能與晶圓607一起旋轉。在發証予Patton等人之美國專利US 6,156,167及發証予Reid等人之美國專利US 6,800,187中詳細揭露了具有適合與本發明一起使用之態樣之殼式電鍍設備的一般說明,將其所有內容包含於此作為參考。
陽極613係設置於電鍍浴603內的晶圓下方並藉由薄膜615如離子選擇薄膜和晶圓區域分離。例如,可使用Nafion™陽離子交換薄膜(CEM)。陽極薄膜下方的區域通常被稱為「陽極室」。離子選擇陽極薄膜615允許電鍍池之陽極區域與陰極區域之間的離子交流,但避免在陽極處所產生的粒子進入晶圓附近污染晶圓。陽極薄膜亦可用以在電鍍處理期間分散電流,藉此改善電鍍均勻度。發証予Reid 等人的美國專利US 6,126,798與US 6,569,299中提供了適合之陽極薄膜的詳細說明。離子交換薄膜如陽離子交換薄膜尤其適合此些應用。此些薄膜係通常由離子聚合物材料如包含磺酸基團之全氟化共聚物(如Nafion™)、磺化的聚醯亞胺、及此領域中人已知適合陽離子交換之其他材料所製成。適合之Nafion™薄膜的選擇性實例包含來自Dupont de Nemours Co 的N324與N424薄膜。
在某些情況中,可控制通過電鍍浴的對流及/或擴散。協助擴散的一典型方法為藉由泵浦617提供電鍍溶液的對流。此外,可使用振動攪動或音波攪動構件以及晶圓旋轉。例如,可將振動傳感器608附接至殼式晶圓支撐件609。泵浦617持續地將電鍍溶液提供予電鍍浴603。電鍍溶液大致上向上流經陽極薄膜615與擴散板619而流至晶圓607中央,接著徑向地向外流過晶圓607。亦可自電鍍浴603的側邊將電鍍溶液提供至電鍍浴的陽極區域中。接著電鍍溶液自電鍍浴603溢流至溢流儲槽621。接著電鍍溶液受到過濾(未顯示)並返回泵浦617,完成電鍍溶液的再循環。在電鍍池的某些組態中,不同的電解液循環經過電鍍池包含陽極的部分,但利用具有適度滲透性的薄膜或離子選擇薄膜可避免此不同的電解液與主電鍍溶液混合。
參考電極631係位於電鍍浴603外的分離室633上,分離室633受到來自主電鍍浴603的溢流補充。或者在某些實施例中,參考電極係儘可能地靠近基板表面,且參考電極室係藉由毛細管或其他方法連接至晶圓基板的一側或晶圓基板的正下方。在某些較佳實施例中,設備更包含連接至晶圓外緣的接觸感測接腳,接觸感測接腳係用以感測在晶圓外緣處的金屬晶種層的電位但不會將任何電流帶至晶圓。
參考電極631通常可用於期望受控制之電位下的電鍍。參考電極631可為各種常用類型中的一者如汞/硫酸汞、氯化銀、飽和甘汞、或銅金屬。在某些實施例中,除了參考電極外可使用與晶圓607直接接觸的接觸感測接腳以更精確地量測電位(未顯示)。
DC電源635可用以控制流至晶圓607之電流。電源635具有負輸出接腳639,負輸出接腳639係經由一或多個滑環、刷與接觸件(未顯示)而電連接至晶圓607。電源635的正輸出接腳641係電連接至位於電鍍浴603中的陽極613。電源635、參考電極631、及接觸感應接腳(未顯示)可連接至系統控制器647,系統控制器647除了其他功能外尤其能對電鍍池的元件提供電流與電位的調制。例如,控制器可使電鍍發生在電位控制及電流控制範圍中。控制器可包含程式指令,此些程式指令明確定義需被施加至電鍍池之各種元件的電流與電壓位準以及需改變此些位準的時序。當施加順向電流時,電源635使晶圓607偏壓以相對於陽極613具有負電位。這使得電流自陽極613流向晶圓607且晶圓表面(陰極)上發生電化學還原反應(如Cu2+
+ 2 e-
= Cu0
),這造成導電層(如銅)沉積至晶圓表面上。可將惰性陽極614安裝於電鍍浴603內之晶圓607的下方並藉由薄膜615而與晶圓區域分隔。
設備亦可包含用以將電鍍溶液之溫度維持在特定位準的加熱器645。電鍍溶液可用以將熱傳輸至電鍍浴中的其他元件。例如,當晶圓607被載入至電鍍浴中時,可開啟加熱器645與泵浦617以經由電鍍設備601循環電鍍溶液直到整個設備的溫度變得實質上均勻。在一實施例中,加熱器係連接至系統控制器647。系統控制器647可連接至熱耦以接收電鍍設備內之電鍍溶液的溫度反饋並決定是加需要額外加熱。
控制器通常包含一或多個記憶體裝置及一或多個處理器。處理器可包含CPU或電腦、類比及/或數位輸入/輸出連接件、步進馬達控制板等。在某些實施例中,控制器控制電鍍設備的所有活動。包含用以根據本發明實施例控制製程操作之指令的非瞬變機器可讀媒體可耦合至系統控制器。
通常存在著和控制器647相關的使用者界面。使用者界面可包含顯示螢幕、設備及/或製程條件的圖形化軟體顯示、及使用者輸入裝置如指向裝置、鍵盤、觸控螢幕、麥克風等。可以任何傳統的電腦可讀程式語言撰寫控制電鍍製程用的電腦程式碼,電腦可讀程式語言例如是組合語言、C、C++、Pascal、Fortran或其他語言。可藉由處理器執行編譯過的物件碼或腳本以進行程式中所認定的任務。根據文中實施例可使用之電鍍設備的一實例為科林研發之Sabre設備。電沉積可在形成一更大電沉積設備的複數元件中進行。
圖7顯示一例示性電沉積設備的上視概圖。電沉積設備700可包含三個分離的電鍍模組702、704與706。電沉積設備700亦可包含針對各種處理操作加以配置的三個分離模組712、714與716可。例如,在某些實施例中,模組712、714與716中的一或多者可為旋轉沖洗乾燥(SRD)模組。此類模組可用以在墨水列印於基板上之後沖洗及乾燥基板。在其他實施例中,模組712、714與716中的一或多者可為複數電填充後模組(PEM),每一電填充後模組係用以進行一功能如基板受到電鍍模組702、704與706中之一者處理後之邊緣斜角移除、背側蝕刻、及酸清洗。在某些實施例中,模組712、714、及716中的一或多者可用以在基板上提供晶種層。在此些或其他實施例中,模組712、714、及716中的一或多者可用以如文中所述預處理基板,例如以濕式或乾式處理方法自晶種層之上表面移除氧化物層。在此些或其他實施例中,模組712、714、及716中的一或多者可為用以進行文中所述之電流體動力噴射列印處理的電流體動力噴射列印模組。此類電流體動力噴射列印模組可具有參考圖5所述之特徵部中的一或多者。在此些或其他實施例中,模組712、714、及716中的一或多者可為如文中所述用以在電鍍後化學蝕刻基板的化學蝕刻模組。在某些實施例中,可提供額外的模組(未顯示)以進行文中所述的此些功能及其他功能。
電沉積設備700包含中央電沉積室724。中央電沉積室724為用來作為電鍍模組702、704與706中之電鍍溶液的化學溶液的容納室。電沉積設備700亦包含可儲存並輸送電鍍溶液用之添加物的劑量系統726。化學品稀釋模組722可儲存並混合用來作為蝕刻劑的化學品。過濾與泵抽單元728可過濾中央電沉積室724用的電鍍溶液並將其泵抽至電鍍模組。
系統控制器730提供用以操作電沉積設備700所需的電子與界面控制。系統控制器730(其可包含一或多個實體或邏輯控制器)控制電鍍設備700之部分或全部特性。
藉由系統控制器730的類比及/或數位輸入連接件可自各種處理設備感測器提供用以監控處理的訊號。可在處理設備的類比及數位輸出連接件上輸出用以控制處理的訊號。可被監測之處理設備感測器的非限制性實例包含質量流量控制器、壓力感測器(如壓力計)、熱偶、光學位置感測器等。受到適當程式化的反饋與控制演算法可與來自此些感測器的數據一起使用以維持處理條件。
交付設備740可自基板晶圓盒如晶圓盒742或晶圓盒744選擇一基板。晶圓盒742或744可為前端開口標準艙(FOUP)。FOUP為一外殼,其被設計用以在受控環境中安全穩固地支撐基板並允許基板被設有適當裝載艙口及機器人搬運系統的設備移除以接受製程或量測。交付設備740可利用真空附接或某些其他附接機制抓取基板。
交付設備740可與晶圓搬運站732、晶圓盒742或744、傳送站750、或對準器748交界。交付設備746可自傳送站750取得對基板之接取。傳送站750可為一槽口或一位置,交付設備740與746可毋需行經對準器748而自該槽口或該位置傳送基板或將基板送達至該槽口或該位置。然而在某些實施例中,為了確保基板在交付設備746上適當地對準以被精準地傳送至電鍍模組,交付設備746可利用對準器748對準基板。交付設備746亦可將基板傳送至電鍍模組702、704、或706中的一者、或用於各種處理操作之分離模組712、714、及716中的一者。
根據上述方法之處理操作一實例可以下列方式進行:(1)將銅或另一材料電沉積至電鍍模組704中的基板上;(2)在模組712中的SRD中沖洗及乾燥基板;及(3)在模組714中進行邊緣斜角移除。
為了在製造環境中實施使用,設備可用以使得基板經歷有順序的有效率循環:電鍍、沖洗、乾燥、及PEM處理操作。為達此目的,可將模組712配置為旋轉沖洗乾裝置及邊緣斜角移除室。具有此類模組712時,只需在電鍍模組704與模組712之間傳送基板以進行銅電鍍及EBR操作。在某些實施例中,文中所述的方法將在包含電鍍設備及步進裝置的系統中實施。
圖8中概略例示電沉積裝置800的另一實施例。在此實施例中,電沉積設備800具有一系列之電鍍池807,每一電鍍池807包含一電鍍浴,電鍍浴係以一對或複數對的方式配置。除了電鍍本身,電沉積設備800可進行各種電鍍相關的其他處理與子步驟例如旋轉沖洗、旋轉乾燥、金屬與矽的濕式蝕刻、無電鍍沉積、預濕與預化學處理、還原、退火、光阻剝除、及表面預活化等。在某些實施例中,電沉積設備800可包含用以進行文中所述之各種操作的一或多個模組,此些操作包含晶種層沉積、電流體動力噴射列印、及化學蝕刻。圖8由上往下概略顯示電沉積設備800且在圖示中只顯示單層或「樓板」,但此領域中具有通常技術者當瞭解,此類設備如科林研發公司之SabreTM
3D設備可具有彼此上下「堆疊」之兩或多層且每一層可能具有相同類型或不同類型之複數處理站。
再次參考圖8,經由前端裝載FOUP 801將欲受到電鍍的複數基板806大致上饋送至電沉積設備800,在此實例中,藉由前端機器人802將欲受到電鍍的複數基板806自FOUP 801搬運至電沉積設備800的主基板處理區,前端機器人802可以多維度自複數接取站中的一者收回受到轉子803驅動的基板806並將基板806移動至複數接取站中的另一者—在此實例中複數接取站顯示兩個前端接取站804及兩個前端接取站808。前端接取站804與808可包含例如預處理站、旋轉沖洗乾燥(SRD)站。前端機器人802之側至側的橫向移動係利用機器人軌道802a來完成。每一基板806可被杯狀/錐狀組件(未顯示)所支撐,杯狀/錐狀組件係由連接至馬達(未顯示)的轉子803所驅動,馬達係附接至安裝架809。在此實例中亦顯示四「雙」電鍍池807,因此總共八個電鍍池807。系統控制器(未顯示)可耦合至電沉積設備800以控制電沉積設備800的部分或全部特性。可程式化或以其他方式配置系統控制器以執行根據前文中所述之處理的指令。
可修改基板處理設備如圖7及8中所示者以包含與圖5之電流體動力噴射列印設備相關之特徵部中的一或多者。
在某些實施例中,控制器為系統的一部分,其為上述實例的一部分。此類系統可包含半導體處理設備,半導體處理設備包含一處理工具或複數處理工具、一處理室或處理製程室、一處理平臺或複數處理平臺、及/或複數的特定處理元件(晶圓座臺、氣體流動系統等)。在一特定實例中,系統包含參考圖2B所述的各種設備。設備中的兩或更多者可組合為單一設備、或其可彼此分離。上面已提供特定實例。此些系統係與一些電子裝置整合,此些電子裝置係用以在半導體晶圓或基板處理之前、期間及之後控制系統的操作。此些電子裝置係稱為「控制器」,其可控制一系統或複數系統的各種元件或子部件。取決於處理需求及/或系統類型,控制器可被程式化以控制文中所揭露的任何處理包含輸送處理氣體、溫度設定(如加熱及/或冷卻)、壓力設定、真空設定、功率設定、射頻(RF)產生器設定、RF匹配電路設定、頻率設定、流率設定、流體輸送設定、位置與操作設定、晶圓傳輸進入或離開設備與連接至特定系統或與特定系統具有界面的其他傳輸設備及/或裝載互鎖機構。
概括地說,控制器可被定義為具有各種積體電路、邏輯、記憶體及/或軟體的電子裝置,其可接收指令、發佈指令、控制操作、致能清理操作、致能終點量測等。積體電路可包含儲存了程式指令之具有韌體形式的晶片、數位訊號處理器(DSP)、被定義為特殊應用積體電路(ASIC)的晶片及/或能執行程式指令(如軟體)的一或多個微處理器或微控制器。程式指令可為與控制器通訊之具有各種獨立設定(或程式檔案)形式的指令,其定義為了在半導體晶圓上或針對半導體晶圓、或對一系統進行特定處理所用的操作參數。在某些實施例中,操作參數為製程工程師為了完成一或多膜層、材料、金屬、氧化物、矽、二氧化矽、表面、電路及/或晶圓之晶粒之製造期間的一或多個處理步驟所定義之配方的一部分。
在某些實施例中控制器為整合至系統、耦合至系統、藉由網路連接至系統、或其組合的電腦的一部分或控制器耦合至電腦。例如,控制器係位於雲端中或工廠主機電腦系統的全部或部分中,這允許使用者遠端接取晶圓處理。電腦可致能遠端接取系統以監控製造操作的目前進展、檢視過去製造操作的歷程、自複數製造操作檢視驅勢或效能度量、改變現有處理的參數、設定處理步驟以符合現有處理、或開始一新的處理。在某些實例中,遠端電腦(或伺服器)可經由電腦網路對系統提供處理配方,電腦網路包含區域網路或網際網路。遠端電腦可包含使用者介面,使用者介面讓使用者能進入或程式化參數及/或設定,然後自遠端電腦與系統通訊。在某些實例中,控制器接收數據形式的指令,其明確定義了在一或多個操作期間欲進行之每一處理步驟的參數。應瞭解,參數可特別針對欲施行之處理的類型及控制器用以交界或控制之設備的類型。因此如上所述,可分散控制器如藉著包含一或多個藉由網路互連並朝向共同目的如文中所述之處理與控制工作的離散控制器。為了此類目的的分散控制器的實例為處理室上的一或多個積體電路,其係與一或多個位於遠端(例如位於平臺位準或遠端電腦的一部分)的積體電路通訊而共同控制處理室中的製程。
不受限地,例示性的系統可包含電漿蝕刻室或模組、沉積室或模組、旋轉沖洗室或模組、金屬鍍室或模組、清理室或模組、邊緣蝕刻室或模組、物理氣相沉積(PVD)室或模組、化學氣相沉積(CVD)室或模組、原子層沉積(ALD)室或模組、原子層蝕刻(ALE)室或模組、離子植入室或模組、軌道室或模組、及和半導體晶圓之製造相關或用於製造半導體晶圓的任何其他半導體處理系統。
如上所述,取決於設備所欲進行的處理步驟或複數處理步驟,控制器可與下列的一或多者通訊交流:其他設備的電路或模組、其他設備的元件、叢集設備、其他設備的界面、相鄰設備、鄰近設備、位於工廠內的設備、主電腦、另一控制器、或半導體製造工廠中用以將晶圓容器載入與載出設備位置及/或裝載接口的材料運輸用設備。
結論
文中所述之技術能以高精準度形成極小尺寸(如<0.5 μm)的精細內連線、墊、及其他金屬特徵部。有利地,可在不使用參考圖1A及1B所說明之傳統處理流程中的傳統處理、設備、及材料的情況下實施技術。例如,文中之技術毋須使用光阻、微影設備、光阻烘烤設備、光阻固化設備、光罩、顯影化學品及設備、氧電漿除渣設備、或光阻清理及剝除設備。是以,能實質上減少與形成精細內連線、墊、及其他金屬特徵部相關的所有權及處理費用。電流體動力噴射列印能寫細線而滿足現行及未來之市場技術需求。例如,封裝RDL配線目前涉及形成>5 μm的線及空間,但在接下來的數年內會朝向>2 μm及更小的方向移動。相較於遠遠較昂貴及複雜的傳統處理流程,文中所述之技術提供以低成本形成此類特徵部的一條路。
雖然為了清楚瞭解本發明的目的已詳細說明前述實施例,但當明白,在隨附請求項的範疇內可進行某些變化及修改。應注意,有許多實施本發明之處理、系統、及設備的替代方式。因此本發明之實施例應被認為是例示性而非限制性的,且實施例不限於文中所提供之細節。
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205:操作
207:操作
150:物理汽相沉積設備
152:光阻沉積設備
154:光阻圖案化設備
155:光阻顯影設備
156:電漿蝕刻設備
158:電鍍設備
160:光阻剝除設備
162:化學蝕刻設備
250:晶種層沉積設備
252:電流體動力噴射列印設備
254:電鍍設備
256:化學蝕刻設備
300:基板
301:晶種層
302:加速劑墨水
303:金屬
303d:金屬特徵部
400:基板
401:晶種層
402:抑制劑墨水
403:金屬
403d:金屬特徵部
900:基板
901:晶種層
911:附著阻障層
912:擴散阻障層
913:焊接層
500:基板
501:噴嘴
502:墨水
503:噴嘴尖端
504:電位
505:墨水液滴
506:距離
601:電鍍設備
603:電鍍浴
605:位準
607:晶圓
608:振動傳感器
609:殼式基板支撐件
611:轉子
613:陽極
615:薄膜
614:惰性陽極
615:薄膜
617:泵浦
619:擴散板
621:溢流儲槽
631:參考電極
633:分離室
635:電源
639:負輸出接腳
641:正輸出接腳
645:加熱器
647:系統控制器
700:電沉積設備
702:電鍍模組
704:電鍍模組
706:電鍍模組
712:模組
714:模組
716:模組
722:化學品稀釋模組
724:中央電沉積室
726:劑量系統
728:過濾與泵抽單元
730:系統控制器
732:晶圓搬運站
740:交付設備
742:晶圓盒
744:晶圓盒
746:交付設備
748:對準器
750:傳送站
800:電沉積設備
801:FOUP
802:前端機器人
802a:機器人軌道
803:轉子
804:前端接取站
806:基板
807:鍍池
808:前端接取站
809:安裝架
圖1A之流程圖說明一種利用基於光阻之技術的金屬特徵部形成方法。
圖1B顯示用以進行圖1A之方法之處理設備的各種部件。
圖2A之流程圖說明根據文中之一實施例的一種金屬特徵部的形成方法。
圖2B例示用以進行圖2A之方法之處理設備。
圖3A-3D顯示在電流體動力噴射列印處理中經歷利用加速劑墨水之圖2A方法之部分製造完成之半導體基板。
圖4A-4D顯示在電流體動力噴射列印處理中經歷利用抑制劑墨水之圖2A方法之部分製造完成之半導體基板。
圖5例示根據某些實施例之在電流體動力噴射列印處理期間之噴嘴與基板的放大圖。
圖6顯示根據某些實施例電鍍池。
圖7例示根據某些實施例之具有複數電鍍池及其他特徵之電鍍設備。
圖8顯示根據某些實施例之具有複數電鍍池及其他特徵之電鍍設備。
圖9A-9D例示根據某些實施例經歷多層薄膜堆疊形成之部分製造完成之半導體基板。
200:方法
201:操作
203:操作
205:操作
207:操作
Claims (33)
- 一種在基板上沉積金屬的方法,該方法包含: (a)接收包含一晶種層的一基板,其中該晶種層為導電的且在該基板之一表面上受到暴露; (b)經由電流體動力噴射列印將一墨水以一圖案列印至該晶種層上,其中該墨水包含溶解於一溶劑中之一電鍍添加物,其中該電鍍添加物包含一加速劑或一抑制劑,其中該電鍍添加物吸附至該晶種層上;及 (c)經由一先取沉積(preferential deposition)將一金屬電鍍至該基板上,該先取沉積在來自該墨水之該電鍍添加物存在的位置處提供一第一沉積速率並在來自該墨水之該電鍍添加物不存在的位置處提供一第二沉積速率,其中該第一沉積速率係不同於該第二沉積速率電鍍。
- 如請求項1之在基板上沉積金屬的方法,其中該電鍍添加物包含一加速劑且該第一沉積速率係大於該第二沉積速率俾使該金屬優先沉積在來自該墨水之該加速劑存在的位置處。
- 如請求項2之在基板上沉積金屬的方法,其中該加速劑包含具有至少一巰基及一磺酸基的一烷鏈、或一酸鹽。
- 如請求項3之在基板上沉積金屬的方法,其中該加速劑包含巰基丙烷磺酸或巰基乙烷磺酸。
- 如請求項3之在基板上沉積金屬的方法,其中該墨水中之該溶劑包含選自由下列者所組成之群組的至少一材料:水、松油醇、碳酸乙烯酯(ethylene carbonate)、碳酸丙烯酯、二甲基亞碸 (DMSO)、乙二醇、及丙二醇。
- 如請求項2之在基板上沉積金屬的方法,更包含化學蝕刻該基板以移除在(c)中沉積之該金屬的一部分及該晶種層的一部分,藉此在來自該墨水之該加速劑存在的位置處形成金屬特徵部,該等金屬特徵部係彼此空間隔離。
- 如請求項6之在基板上沉積金屬的方法,其中在(c)中於電解液中電鍍該基板,該電解液包含: 介於約10-1000 ppm之間之電鍍抑制劑添加物; 介於約10-60 g/L之間之銅離子; 介於約5-180 g/L之間之酸;及 介於約30-80 ppm之間之鹵素離子。
- 如請求項7之在基板上沉積金屬的方法,其中該電解液係不具有加速劑或僅具有微量之加速劑。
- 如請求項1之在基板上沉積金屬的方法,其中該電鍍添加物包含一抑制劑,其中該第一沉積速率係低於該第二沉積速率俾使該金屬優先沉積在來自該墨水之該抑制劑不存在的位置處。
- 如請求項9之在基板上沉積金屬的方法,其中該抑制劑包含選自由下列者所組成之群組的至少一材料:6-巰基己醇及苯并三唑。
- 如請求項9之在基板上沉積金屬的方法,更包含化學蝕刻該基板以移除在(c)中沉積之該金屬的一部分、在(b)中列印的該墨水、及該晶種層的一部分,藉此在來自該墨水之該抑制劑不存在的位置處形成金屬特徵部,該等金屬特徵部係彼此空間隔離。
- 如請求項9之在基板上沉積金屬的方法,其中在(c)中於電解液中電鍍該基板,該電解液包含: 介於約0-1000 ppm之間的加速劑; 介於約10-60 g/L之間的銅離子;及 介於約5-180 g/L之間的酸。
- 如請求項12之在基板上沉積金屬的方法,其中該電解液不具有該抑制劑、或僅具有微量的該抑制劑。
- 如請求項1-13中任一項之在基板上沉積金屬的方法,其中該基板更包含位於該晶種層下方的一附著阻障層,該方法更包含: (d)化學蝕刻該基板以移除在(c)中沉積之該金屬的一部分及該晶種層的一部分,藉此形成金屬特徵部,該等金屬特徵部係彼此空間隔離;及 (e)將一第二金屬電鍍至該基板上,其中該第二金屬係選擇性地沉積至在(d)中所形成的該等金屬特徵部上但實質上不形成在該附著阻障層上。
- 如請求項14之在基板上沉積金屬的方法,其中該第二金屬形成一擴散阻障層,該方法可更包含: (f)將一焊接材料電鍍至該擴散阻障層上,該焊接材料係選擇性地沉積在(e)中所形成的該擴散阻障層上但實質上不形成在該附著阻障層上。
- 如請求項1-13中任一項之在基板上沉積金屬的方法,其中該墨水中的該電鍍添加物與該基板上的該晶種層反應並化學結合至該晶種層。
- 一種基板處理系統,該系統包含: 一電流體動力噴射列印設備,包含: 一噴嘴,具有一直徑介於約50-5000 nm之間之一開口; 一墨水儲槽,係與該噴嘴呈流體連接; 一基板支撐件,係用以在列印期間支撐該基板;及 一電源,係用以在該噴嘴與該基板支撐件之間、或該噴嘴與該基板之間施加一電位; 一電鍍設備,包含: 一腔室,用以容納電解液; 一基板支撐件,係用以在電鍍期間支撐該基板; 一陽極;及 一電源,係用以在電鍍期間於該陽極與該基板之間施加一電位;及 一控制器,係用以: 利用該電流體動力噴射列印設備將一墨水以一圖案列印至該基板上,其中該墨水包含溶解於一溶劑中之一電鍍添加物,其中該電鍍添加物包含一加速劑或一抑制劑;及 在將該墨水列印至該基板上之後,利用該電鍍設備將一金屬電鍍至該基板上,該電鍍操作係經由一先取沉積進行,該先取沉積在來自該墨水之該電鍍添加物存在的位置處提供一第一沉積速率並在來自該墨水之該電鍍添加物不存在的位置處提供一第二沉積速率,其中該第一沉積速率係不同於該第二沉積速率電鍍。
- 如請求項17之基板處理系統,更包含用以在該基板上沉積一晶種層之一設備,其中該控制器係用以在該墨水列印至該基板上之前使該晶種層沉積在該基板上。
- 如請求項18之基板處理系統,更包含用以自該基板移除該金屬之一化學蝕刻設備,其中該控制器係用以移除電鍍至該基板上之該金屬的一部分及移除該基板上之該晶種層的一部分。
- 如請求項17-19中任一項之基板處理系統,其中該電流體動力噴射列印設備及該電鍍設備係共同於一單一設備中提供。
- 一種電流體動力噴射列印用之墨水,該墨水包含: (a)一電鍍添加物,包含一加速劑或一抑制劑,其中該電鍍添加物係以介於約0.1-10 g/L之間的一濃度存在;及 (b)一溶劑,具有: 一蒸氣壓,在25°C時係等於或小於約24托;及 一介電常數,係介於約40-90之間; 其中該墨水具有介於約0.7-20 cP之間的一黏度,且 其中該電鍍添加物係完全溶解於該溶劑中。
- 如請求項21之電流體動力噴射列印用之墨水,其中該墨水中之氧的一濃度約為1 ppm或更低。
- 如請求項21之電流體動力噴射列印用之墨水,更包含可與氧反應且消耗氧的一物種,其中可與氧反應且消耗氧的該物種係以足以將該墨水中之氧的濃度維持在約1 ppm或更低的一濃度存在。
- 如請求項23之電流體動力噴射列印用之墨水,其中可與氧反應且消耗氧的該物種包含一亞硫酸鹽化合物。
- 如請求項21之電流體動力噴射列印用之墨水,其中該電鍍添加物包含該加速劑。
- 如請求項21之電流體動力噴射列印用之墨水,其中該電鍍添加物包含該抑制劑。
- 如請求項26之電流體動力噴射列印用之墨水,更包含鹵素離子,該鹵素離子之一濃度係介於約30-80 ppm之間。
- 如請求項21-27中任一項之電流體動力噴射列印用之墨水,其中該溶劑包含選自由下列者所組成之群組的至少一材料:水、松油醇、碳酸乙烯酯、碳酸丙烯酯、二甲基亞碸(DMSO)、乙二醇、及丙二醇。
- 如請求項28之電流體動力噴射列印用之墨水,其中該溶劑為有機的。
- 如請求項21-27中任一項之電流體動力噴射列印用之墨水,其中該溶劑具有介於約95-275°C之間的一自然沸點。
- 如請求項21-27中任一項之電流體動力噴射列印用之墨水,其中該溶劑包含一第一共溶劑及一第二共溶劑。
- 如請求項21-27中任一項之電流體動力噴射列印用之墨水,其中該墨水包含一潤濕劑。
- 如請求項21-27中任一項之電流體動力噴射列印用之墨水,其中該墨水包含一鹽類。
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