201139760 六、發明說明： 【發明所屬之技術領域】 本發明係關於在半導體裝置中用於形成互連 (interconnect)之技術，尤係關於能夠以高速率將用於互連 之鑛覆金屬（譬如銅）填滿於形成於基板（譬如半導體晶 圓）之表面中之互連凹部（譬如溝槽(t_h)和貫穿孔⑽ hole))中之鍍覆方法與鍍覆骏置。 【先前技術】 為了以间速率將用於互連之鑛覆金屬填滿於形成於 基板（譬如半導體晶圓）之表面中之互連凹部（譬如溝槽 ^貫^)中，下列幾點是很重要的：抑制於基板之場區 面巾鍍覆金叙_率；以及，提升於互連凹部之 底。P中鍍覆金屬之沉積率。因此，當 於使:於，真_之_:= “劑屬之沉積之 t藉由使用包含均勻劑（當消耗時 沉積）之㈣施基板之㈣時 m覆金屬 表面附近之擴散層之厚度而衫同 2成在基板之 果。沐^ <鍍覆金屬抑制沉積效 甚頁抑制妙禮、1錄覆，同時槐拌鑛覆溶液時，明 == 快速流動之基板之場區域之表面中 會“金屬：1: ’反之因為不充分供應均勻劑，因此不 金屬之沉積。於疋，藉由實麵覆’同時授拌鍾溶液時， 322697 4 201139760 變成可能從底部以高速率將鍍覆金屬填滿於互連凹部，同 時完全維持於互連凹部中加速劑之鍵覆金屬沉積加速效 果，並且由於鍍覆金屬之沉積於開口附近而防止互連凹部 之開口之阻隔。 當藉由使用存在於鍍覆溶液中上述添加劑之協同效 應（synergistic effect)實施填滿鍍覆金屬於互連凹部中時， 重複的鑛覆操作可能引致添加劑的改變，導致不穩定的製 程。尤其是當對於一個晶圓需要長鍍覆時間，為鍍覆填滿 锻覆金屬於矽貫穿孔時，於一個晶圓之鍍覆期間將消耗大 量的添加劑。此情況於處理數個晶圓後可能導致鍍覆溶液 之品質改變，造成該鍍覆金屬之填滿不良。 因此，可以想像一種方法，其中，可以允許加速劑（其 中一種上述共同添加劑）僅事先吸附於互連凹部之表面 上’其後藉由使用僅包含抑制劑作為添加劑之鍍覆溶液（嬖 如硫酸銅鍍覆溶液）而實施鍍覆。此種方法期望當藉由: 附之加速劑之效果從互連凹部之底部加速鍍覆金屬之沉° 時，藉由抑制劑之效果抑制鍍覆金屬之沉積於基板之場區 域之表面中。通常是不可能允許加速劑藉由一種處理操二 僅吸附至互連凹部之表面上。本申請人已提出一種方法， 包括下列步驟：於包含鍍覆加速劑之鍍覆溶液中實施基板 表面之第—次鍍覆；藉由引進加速劑去除劑（其能夠^除 或減少加速劑）與基板表面接觸而實施鍍覆加速劑去除^ 理；以及，然後實施基板表面之第二次鍍覆（凹部次: 復；k翏看日本專利公開公報第2007-262486號（專利文獻 201139760 υ，和第20〇6-l31961號（專利文獻2))。 本申請人亦已提出一種方法，該方法包含在鍍覆之前 先施加鑛覆抑制材料（鍍覆抑制劑）至除了互連凹部之表 面外之基板表面（參看日本專利公開公報第2006-274369 號（專利文獻3)，第2006-307279號（專利文獻4)，和第 2007-9247號（專利文獻5))。再者，已經提出一種方法， s玄方法包括於填滿鍍覆金屬於形成在基板表面中互連凹部 中後’去除互連凹部於他們的開口附近之表面中之加速 劑’以及然後形成鍍覆金屬膜於基板之場區域之表面中（參 看曰本專利公開公報第2003-268590號(專利文獻6))。 【發明内容】 加速劑為添加劑本質上用於以由下而上之方式沉積 鍍覆金屬於互連凹部之表面上。於具有高縱橫比（aspect ratio)之互連凹部之情況中，當加速劑吸附至包含互連凹部 之表面之基板之整個表面上時，鍍覆金屬之沉積亦將加速 於互連凹部於他們的開口附近之表面中，而在互連凹部以 由下而上之方式生長之錄覆金屬完全填滿之前，該等開口 將被鑛覆金屬所阻隔，那是可能的。欲解決此問題，揭示 於專利文獻1和2中之方法使用加速劑去除劑（例如，勺 含氯化物離子）實施加速料除處理，以藉由使用氣化= 離子於加速劑上之鮮^㈣從基板表面減少或去除 劑。當執行反向f解時較佳實施此處理。於加速劑去= 理後’實她凹部填滿鍍覆。然而，發現到縱使加 —mu ’因為加速劑之去除不^ (去^ 322697 6 201139760 (desorption))，因此於埋置於互連凹部中之鍍覆金屬中形 成空隙（void) °需要相當長的鍍覆時間以防止形成此種空 隙。此外，使用反向電解使得鍍覆裝置之饋電系統複雜化。 鑑於上述情況而達成本發明。因此，本發明之目的係 提供一種能夠以較高速率將鍍覆金屬填滿於互連凹部中而 不會於互連凹部中埋置之鍍覆金屬中形成空隙之鍍覆方法 與鍍覆裝置。 為了達成上述目的’本發明提供一種鍍覆方法，包括 下列步驟.製備於表面上具有互連凹部之基板；藉由將該 基板/文泡於包含加速劑、金屬離子和酸之第一預先處理溶 液中’而實施該基板之第一預先處理；藉由將該基板浸泡 於包含添加劑而不包含加速劑之第二預先處理溶液中，其 中’該添加劑抑制包含於第一預先處理溶液中之加速劑之 效果’而實施該基板之第二預先處理；以及，然後藉由使 用包含至少一金屬離子、酸和抑制劑而不包含加速劑之鍍 覆溶液而實施該基板之表面之電鍍，藉此填滿鍍覆金屬於 互連凹部中。 因此 藉由實施第二預先處理，將該基板浸泡於包含 添加劑而不包含加速劑之第二預先處理溶液中，其中，今 添加劑抑制包含於該第一預先處理溶液中之加速劑之效 果，存在於該基板之場區域之表面中之加迷劑能夠更安穩 地停止作用（deactivate)。因此變成可能以較高速率將贫覆 金屬填滿於互連凹部中而不會在埋置之鍍覆金屬中步成# 322697 7 201139760 - 於本發明之較佳態樣中，第一預先處理為藉由電解處 理基板之表面同時浸泡該基板於第一預先處理溶液中而實 施之初步電解處理。 於該第一預先處理中，將該基板浸泡於包含加速劑、 金屬離子和酸之第一預先處理溶液中 ，允許該加速劑吸附 至包含互連凹部之表面之基板之整個表面上。此加速劑吸 附製程可以藉由電解處理該基板之表面而穩定地進行。 可以於50至250A/M2電流密度實施初步電解處理。 譬如 SPS (聚二硫二丙烧續酸（bis (3-sulf〇propyl) disulfide))之硫化物（suifur comp〇un(j)可以較佳地使用為 包含於該第一預先處理溶液中之加速劑。 包含於該第一預先處理溶液中之加速劑之濃度通常 可以是5至500" M/L，較佳為50至500# M/L。 包含於該第二預先處理溶液中並且其抑制包含於第 一預先處理溶液中之加速劑之效果之添加劑可以是均勻 劑。 伸乙亞胺聚合物（ethyleneimine polymer )或者其衍生 物（譬如聚乙稀亞胺（polyethyleneimine，PEI))可以較佳 地使用為均勻劑。 PEI作為均勻劑具有高的加速劑停止作用效果。因 此，藉由將加速劑已經吸附於其上之基板浸泡於例如包含 PEI之水硫酸溶液中’則存在於基板之場區域之表面中之 吸附的加速劑可以被選擇性地停止作用。 較佳地，當攪拌該處理溶液時，實施該第一預先處 322697 8 201139760 理、第二預先處理和電鍍之至少其中之一。 於本發明之較佳態樣中，當攪拌該第二預先處理溶液 時，實施該第二預先處理，且當用等於或大於攪拌該第二 預先處理之攪拌強度攪拌該鍍覆溶液時，實施該電鍍。 於本發明之較佳態樣中，於該第一預先處理後基板之 表面用稀硫酸清洗，且於該第二預先處理後基板之表面用 稀硫酸清洗。 相較於基板表面用純水清洗之情況’於第一預先處理 考第一預先處理後基板之表面用稀硫酸清洗可以提升製程 穩定性和均勻性。 本發明亦提供一種鍍覆裝置，用於實施鍍覆於表面中 具有互連凹部之基板之表面，該鍍覆裝置包括：第一預先 處理單元’用於藉由將該基板浸泡於包含加速劑、金屬離 子和酸之第一預先處理溶液中，而實施該基板之第一預先 ’第二預先處理單元，用於藉由將該基板浸泡於包含 ^、、加劑而不包含加速劑之第二預先處理溶液中，其中，該 加劑抑制包含於該第一預先處理溶液中之該加速劑之效 而實施該基板之第二預先處理；以及，鍍覆單元，用 1在該第二預先處理後，藉由使用包含至少一金屬離子、 欠和抑制劑而不包含加速劑之鍍覆溶液而實施該基板之表 面之電鑛’藉此填滿該鍍覆金屬於互連凹部中。 、於本發明之較佳態樣中，該第一預先處理單元被組構 成备浸泡該基板於第一預先處理溶液中時，實施該基板之 表面之電解處理。 9 322697 201139760 於本發明之較佳態樣中，該鍍覆裝置進一步包括第一 清洗單元與第二清洗單元，其中，該第一清洗單元係用稀 硫酸清洗該基板之表面，該基板於該第一預先處理單元中 經歷了第一預先處理，和該第二清洗單元係用稀硫酸清洗 該基板之表面，該基板於該第二預先處理單元中經歷了第 二預先處理。 於本發明之較佳態樣中，該第一預先處理單元、該第 二預先處理單元和該鍍覆單元之至少其中之一設置有攪拌 裝置，用於攪拌該處理溶液；以及，該鍍覆裝置包含控制 部，用於控制該攪拌裝置之攪拌速度、於該第一預先處理 單元中之該第一預先處理時間、於該第二預先處理單元中 之該第二預先處理時間、和於該鍍覆單元中之電鍍時間。 於本發明之較佳態樣中，該第二預先處理單元設置有 攪拌裝置，用於攪拌該第二預先處理溶液；以及，該控制 部，根據該互連凹部之寬度或直徑和深度，決定於該第二 預先處理中該基板之浸泡時間和該第二預先處理溶液之攪 拌強度。 依照本發明，基板之表面之鍍覆可以於存在之加速劑 中實施，該加速劑已被吸附於該基板之表面上，而該加速 劑為互連凹部之主動表面，但是於該基板之場區域之表面 中已經完全被停止作用。此情況使其可能以較高速率將鍍 覆金屬填滿於互連凹部中而不會在埋置之鍍覆金屬中形成 空隙。 【實施方式】 10 322697 201139760 -r 現在將參照圖式詳細說明本發明之較佳實施例。下列 之說明顯示示範情況’其中，製備了具有互連凹部12 (譬 如溝槽和貫穿孔）形成在表面中並且覆蓋了晶種層10之基 板W ’如第5A圖中所示；以及，銅之金屬鍍覆膜14填滿 於互連凹部12中以形成銅之互連，如第5C圖中所示。 第1圖顯示依照本發明之實施例之鍍覆裝置之總體平 面圖。如第1圖中所示，鍍覆裝置20包含三個載入/卸載 部22’各載入/卸載部22,用於在其中安裝基板匣（substrate cassette)，其中，容裝了複數個基板w ;第一預先處理單 疋24 ’用於藉由將該基板w浸泡於包含加速劑、金屬離 子和酸之第一預先處理溶液中，而實施該基板W之第一預 先處理；第二預先處理單元26 ’用於藉由將該基板w浸 泡於包含添加劑而不包含加速劑之第二預先處理溶液中， 其中該添加劑抑制包含於第一預先處理溶液中之加速劑 之=果，而實施該基板w之第二預先處理；以及，二個鍍 覆單元28,用來藉由使用包含至少一金屬離子、酸和抑制 劑而不匕3加速劑之鍍覆溶液來實施該基板w之表面之 電鍍。 鍵覆裝置20亦包含三個清洗單元術、働、術，各 极用稀硫k凊洗（水洗(nnse))基板w之表面；清洗/ 元32’用於於電鍵後清洗和乾燥該基板w;以及， 架广用於將基板W在處理之前和之後暫時放置 ^ Μ基板輸送裝i 36可移動地配置於載入/卸載 ㈣與基板台架34之間，以及第二基板輸送裝置％可移 322697 11 201139760 ^ 動地配置於基板台架34與單元之間。藉由設置在鍍覆裝置 20之外部面板中之控制部4〇控制包含第一預先處理單元 24、第二預先處理單元26和鍍覆單元28之所有單元。 於此實施例中，用於實施基板w之表面之電解處理 (鍍覆）之電解處理單元被使用為第一預先處理單元24。 於是，如第2圖中所示，第一預先處理單元24包含處理槽 44，用於將包含加速劑，例如，譬如sps (聚二硫二丙烷 磺酸）之含硫化合物、金屬離子（銅離子）和酸之第—預 先處理溶液42保持於其中。於第一預先處理溶液42中加 速劑（SPS)之濃度一般為5至500以M/L，較佳為5〇至 500 a M/L。 該第一預先處理單元24亦包含垂直可移動基板保持 器46,用於可拆卸地保持基板w並且將該基板w浸泡於 第一預先處理溶液42中於處理槽44中之預定的位置；例 如由含填銅製成之陽極50，係由陽極保持器48保持並且 被浸泡於第一預先處理溶液42中於處理槽44中之預定的 位置；以及，攪拌槳54作為攪拌裝置，該攪拌紫54^攪 拌機構52之致動往復運動以攪拌陽極.5〇與基板w之間之 第一預先處理溶液42。 於操作中，由基板保持器46所保持之基板貿浸泡於 第一預先處理溶液42中於處理槽44中面對該陽極％之預 定的位置。電源58之負極經由導線56a連接至基板w， 而電源58之正極經由導線56b連接至陽極5〇，以實施某 板W之表面之初步電解處理（鍍覆）作為第一預先處理= 322697 12 201139760 ， 於此處理期間，當需要時，該攪拌機構52之攪拌槳54往 復運動以攪拌該第一預先處理溶液42。於此初步電解處理 中電流密度例如為50至250A/m2。於此處理期間，控制部 40控制用於在第一預先處理溶液42中浸泡基板W之時 間、攪拌槳54之攪拌速度、電流密度等。 如第3圖中所示，第二預先處理單元26包含處理槽 62 ’用於保持包含添加劑（例如，PEI (聚乙烯亞胺））作 為均勻劑之第二預先處理溶液60於其中，其中，該添加劑 抑制加速劑（例如，譬如SPS (聚二硫二丙烷磺酸之 效果’而不包含加速劑。第二預先處理單元26亦包含垂直 可移動基板保持器64，用於可拆卸地保持基板W並且將 該基板W浸泡於第二預先處理溶液60中於處理槽62中之 預定的位置；以及，攪拌槳68作為攪拌裝置，該攪拌槳 68被攪拌機構66之致動往復運動以攪拌該基板w前面之 第二預先處理溶液6〇。 於操作中’由基板保持器64所保持之基板w浸泡於 第一預先處理溶液6〇中於處理槽62中之預定的位置，以 實施該基板W之表面之第二預先處理。於此處理期間，當 玲要時，該攪拌機構66之攪拌槳68往復運動以攪拌該第 —預先處理溶液6〇。於此處理期間，控制部4〇控制用於 在第二預先處理溶液6〇中浸泡基板W之時間、擾拌槳68 之攪拌速度等。 如第4圖中所示，鍍覆單元28包含鍍覆槽72，用於 將包含抑制劑’例如，PEG (聚乙二醇（polyethylene 322697 13 201139760 - gWc01))、金屬離子（銅離子）和酸之鍍覆溶液70保持於 其中。於鑛覆溶液70中抑制劑（PEg)之濃度例如為lm M/L。 鑛覆單元28亦包含垂直可移動基板保持器74，用於 可拆卸地保持基板W並且將該基板w浸泡於鍍覆溶液7〇 中於鐘覆# 72中之預定的位置；例如由含翻製成之陽極 78，係由陽極保持器76保持並且被浸泡於鍍覆溶液7〇中 於鐘覆槽72中之預定的位置；以及，㈣槳82作為授掉 裝置4擾拌紫82被擾拌機構go之致動往復運動以授拌 陽極78與基板W之間之鍍覆溶液7〇。 於操作中，由基板保持器74所保持之基板w浸泡於 鍵覆公液70中於錢覆槽72中面對該陽極78之預定的位 置。鍍覆電源86之負極經由導線叫連接至基板w，而 =覆電源86之正極經由導線_連接至陽極78，以實施 之電鑛。於此鍍覆期間，當需要時，該攪拌 f覆期Η 82往復運動以祕該鍍覆溶液7〇。於此 =!部4〇控_82之擾拌速度等。 裝置之操作，照第5Α至5C圖說明第1圖中所示之鍍覆 裝於載入/卸栽: = 由第-基板輸送農置36從安 W被輸送至基板^ 者之基板_出，且該基板 由第二基板輪送;置38輸送===之基板W然後 …用稀，清洗(水洗)。於;：，=: 322697 201139760 後被轉送至第一預先處理單元24之基板保持器46。 於該第一預先處理單元24中，如第2圖中所示，基 板w浸泡於第一預先處理溶液42中於處理槽44中之預定 的位置，而電壓施加於彼此相對配置之基板w與陽極5〇 之間，以實施基板W之表面之初步電解處理（鍍覆）作為 第一預先處理。藉由該第一預先處理，譬如SPS之加速劑 90被吸附至基板W之包含互連凹部12之表面之整個表面 上’如第5A圖中所示。於此處理期間，當需要時，於處 理槽44中之第一預先處理溶液42用攪拌槳54攪拌。控制 部40控制該第一預先處理狀況，攪拌槳54之攪拌速度等。 於第一預先處理後之基板W然後由該第二基板輸送 裝置38輸送至清洗單元30b，於此處基板w之表面用稀 硫酸清洗（水洗）。於清洗後’基板W然後被轉送至第二 預先處理單元26之基板保持器64。 於該第二預先處理單元26中，如第3圖中所示，藉 由浸泡基板W於處理槽62中之第二預先處理溶液6〇中， 而實施基板W之表面之第二預先處理。藉由該第二預先處 理’譬如PEI之添加劑（均勻劑）92被吸附至互連凹部12 在他們的開口附近之表面上，並且至該基板之場區域之表 面上，如第5B圖中所示。於此處理期間，當需要時，於 處理槽62中之第二預先處理溶液6〇用攪拌槳68攪拌。控 制部40控制該第二預先處理狀況，授拌槳68之授拌速度 等。 ' 藉由此種允許譬如PEI之添加劑（均勻劑）92被吸附 322697 15 201139760 -至互連凹部12在他們的開口附近之表面上，並且至該基板 之場區域之表面上，則已經吸附至互連凹部12在他們的開 口附近之表面上，並且至該基板之場區域之表面上之嬖如 SPS之加速劑90能夠藉由添加劑92而被停止作用，同時 維持存在於互連凹部12中之加速劑90之效果。尤其是， 已經證實PEI作為均勻劑具有高SPS停止作用效果，而存 在於基板之場區域之表面中之SPS可以藉由浸泡該基板於 包含PEI之水硫酸溶液中而被選擇性地停止作用，其中， SPS已被吸附於整個表面區域中。 於第二預先處理後’基板W藉由第二基板輸送裝置 38輸送至清洗單元3〇c，於此處基板w之表面用稀硫酸清 洗（水洗）°於清洗後，基板W然後被轉送至鍍覆單元 28之基板保持器74。 於該錄覆單元28中，如第4圖中所示，基板W浸泡 於鑛覆/谷液70中於鍍覆槽72中之預定的位置，而電壓施 加於彼此相對配置之基板w與陽極78之間，以實施基板 W之表面之電錢。於此鍍覆期間，當需要時，於鍍覆槽72 中之鍍覆溶液70用攪拌槳82攪拌。控制部4〇控制該鍍覆 狀況和授拌紫82之搜掉速度。 ^由此種實施基板W之電鑛，於用添加劑（均勻劑） 、T止已"呈吸附至互連凹部12於他們的開口附近之表面 了基τ之場區域之表面上之譬如sps之加速劑 ^ < ’同時維持存在於互連凹部 12中加速劑90之 效果，能夠藉由力π $ 返劑90之作用而加速於互連凹部π之 16 322697 201139760 ， 底部上鍍覆金屬（銅）14 (由下而上）之沉積，同時藉由 包含於鍵覆溶液中之抑制劑之作用而抑制鍵覆金屬14 沉積於基板W之場區域之表面上，如第5c圖中所示。之 主於鍍覆後之基板W由該第二基板輸送裂置38輸适至 =乾燥單元32 ’於此處基板W之表面用例如純水清： 洗）和乾燥。於乾燥後，基板W由第二基板輸送装置 架μ送至基板台架34。該第一基板輸送裝置36從基板台 22 34取得基板W ,並且將該基板W送回至載入/卸栽: 之基被匠。 、s如SPS之加速劑為添加劑，其不可或缺用來從孽如 j槽和貫穿孔之互連凹部之底部（亦即’以由下而上方式） 積錢覆金屬。於具有高縱橫比之互連凹部之情況中，卷 加逮劑°及附至包含互連凹部之表面之基板之整個表面上， x及加迷劑之效果產生時’鍍覆金屬之沉積將被加速亦於 連凹部12於他們的開口附近之表面，而在互連凹部被由 下而上方式生長之鍍覆金屬完全填滿之前，該等開口將被 鍍覆金屬所阻隔 ，那是可能的。 欲解決此問題，依照本發明，基板首先將承受第一預 先處理’其中，該基板被浸泡於包含加速劑、金屬離子和 & (例如’包含譬如SPS之加速劑之水硫酸銅溶液和氣化 物離子）之第一預先處理溶液中，同時當需要時，電解處 理基板之表面，藉此允許加速劑吸附至基板之包含互連凹 4之表面之整個表面上。然後該基板將承受第二預先處 其中’該基板被浸泡於包含譬如PEI之添加劑（均句 322697 17 201139760 - 劑）之第二預先處理溶液中，其中，該添加劑抑制該加速 劑之效果，使存在於該基板之場區域之表面中與該互連凹 部於他們的開口附近之表面中之加速劑停止作用。添加劑 (均勻劑）可以僅以小數量擴散至互連凹部之表面，而因 此，加速劑保持主動於互連凹部之表面中。然後基板於以 使用包含金屬離子、酸和抑制劑之鍍覆溶液之狀態存在的 加速劑中承受電鍍。於是，鍍覆金屬之由下而上之沉積從 可以保持加速劑之效果之互連凹部之底部進行，反之藉由 於加速劑已經停止作用之基板的場區域之表面中抑制劑之 效果而抑制鍍覆金屬之沉積。即使當使用高鍍覆電流以達 成高鍍覆率時，也不可能在以由下而上方式生長鍍覆金屬 填滿互連凹部之前，將由鍍覆金屬阻隔互連凹部之開口。 因此，變成可能以較高的速率填滿鍍覆金屬於互連凹部中。 為了判定對於第一預先處理、第二預先處理、和電鍍 之最佳處理狀況，藉由晶片測試而檢驗填滿鍍覆金屬於互 連凹部中之各種處理狀況之效果。該等結果係說明於下。 使用具有貫穿孔（互連凹部）圖案之圖案化之晶片作為測 試晶片，該等貫穿孔具有20、30、40與50# m之變化的 直徑和60/zm之深度。於預先處理後，使用遮罩帶將該測 試晶片之電鍍實施於集中在圖案上之6-mm直徑區。使用 該測試晶片製造三電極型之電池(cell)，參考電極（汞/硫 酸汞電極）、鉑陽極、和200-mL斷路器，以及，於該電 池中藉由恆電位器（potentiostat)電位之控制下實施第一 次預先處理和電鍍。 18 322697 201139760 使用水硫酸/硫酸銅溶液（〇 9MCuS〇4 · 5H2〇/〇.56M H2S〇4)作為基本鍍覆錢液(basic piating bath)，以及使用 水lMHJO4溶液，用於在處理步驟之間之清洗（水洗）。 為了在處理步驟之間之清洗（水洗），從確保製程穩定性 和均勻性之觀點，使用稀硫酸較使用純水為佳。 藉由添加基本鍍液PEG (聚乙二醇）作為抑制劑於 O.lmM濃度、氣化物離子於imM濃度和(聚二硫一 丙烷磺酸）作為加速劑於預定的濃度所獲得的溶液被使用 為第一預先處理溶液。於該第一預先處理中，該測試晶片 被浸泡於第一預先處理溶液中，以及施加電 : 劑⑽)吸附至該晶片之包含貫穿孔之表面== 上。於該第二預先處理中，測試晶片被浸泡於藉由添加阳 (聚乙稀亞胺）以預定的濃度至水碰溶液中而獲得之第 二預先處理溶液中。於親中，使用藉由僅添加聚 乙二醇）作為抑制劑於〇. 1 mM之濃度以及氣化物離 'BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for forming an interconnect in a semiconductor device, and more particularly to a metal coated metal that can be used for interconnection at a high rate (for example) Copper) is filled with plating methods and plating in interconnecting recesses (such as trenches (t_h) and through holes (10)) formed in the surface of a substrate such as a semiconductor wafer. [Prior Art] In order to fill the metallized metal for interconnection at an intervening rate in an interconnected recess (such as a trench) formed in a surface of a substrate (such as a semiconductor wafer), the following points are It is very important to suppress the gold plating rate of the surface area of the substrate; and to raise the bottom of the interconnecting recess. The deposition rate of plated metal in P. Therefore, when: _: true _: = "the deposition of the agent is by using a uniform agent (deposited when consumed) (4) substrate (4) when the thickness of the diffusion layer near the metal surface And the shirt is the same as the 20% in the substrate. Mu ^ < plated metal inhibits the deposition effect, the page inhibits the ceremony, 1 recording, and when the mixture is mixed with the solution, the surface of the field of the rapidly flowing substrate In the middle of the "metal: 1:" on the contrary because the uniform agent is not fully supplied, so no metal deposition. Yu Yu, by the solid surface overlay 'while mixing the bell solution, 322697 4 201139760 becomes possible to fill the interconnected metal at the high rate from the bottom of the interconnected recess, while maintaining the bond of the accelerator in the interconnect recess completely The metal deposition accelerates the effect and prevents the opening of the interconnect recess from being blocked due to deposition of the plated metal near the opening. When the plated metal is filled in the interconnect recess by using a synergistic effect of the above-described additives present in the plating solution, repeated ore-covering operations may cause changes in the additive, resulting in an unstable process. In particular, when a long plating time is required for one wafer, and the plating is filled with the forged metal in the through hole, a large amount of additive is consumed during the plating of one wafer. This situation may result in a change in the quality of the plating solution after processing a plurality of wafers, resulting in poor filling of the plating metal. Therefore, a method can be conceived in which an accelerator (one of the above-mentioned co-additives) can be allowed to be adsorbed only on the surface of the interconnecting recess in advance, and then a plating solution containing only an inhibitor as an additive (for example, sulfuric acid) can be used. The copper plating solution) is plated. Such a method desirably suppresses deposition of the plated metal in the surface of the field region of the substrate by the effect of the inhibitor when the effect of the accelerator is accelerated from the bottom of the interconnecting recess. It is generally not possible to allow the accelerator to be adsorbed only onto the surface of the interconnecting recess by a process. The Applicant has proposed a method comprising the steps of: performing a first plating of a substrate surface in a plating solution comprising a plating accelerator; by introducing an accelerator remover (which is capable of removing or reducing an accelerator) Plating accelerator removal is performed in contact with the surface of the substrate; and then, a second plating of the surface of the substrate is carried out (concave portion: ret.; see Japanese Patent Laid-Open Publication No. 2007-262486 (Patent Document 201139760 υ, And No. 20 6-l1961 (Patent Document 2)). The present applicant has also proposed a method comprising applying a mineral-suppressing inhibiting material (plating inhibitor) to the surface other than the interconnecting recesses before plating. The outer surface of the substrate (see Japanese Patent Laid-Open Publication No. 2006-274369 (Patent Document 3), No. 2006-307279 (Patent Document 4), and No. 2007-9247 (Patent Document 5)). In one method, the smectic method includes filling the plating metal with an accelerator in the surface of the interconnecting recess formed in the surface of the substrate, removing the interconnecting recess in the surface near the opening thereof, and then forming a plated metal. In the surface of the field region of the substrate (see Japanese Patent Laid-Open Publication No. 2003-268590 (Patent Document 6)). [Invention] The accelerator is essentially an additive for depositing gold plating in a bottom-up manner. On the surface of the interconnect recess. In the case of an interconnect recess having a high aspect ratio, when the accelerator is adsorbed onto the entire surface of the substrate including the surface of the interconnect recess, the deposition of the plated metal is also Will be accelerated in the surface of the interconnect recess near their opening, and the openings will be blocked by the cladding metal before the interconnect recess is completely filled with the bottom-up growth of the recording metal, that is It is possible to solve this problem, and the method disclosed in Patent Documents 1 and 2 performs an accelerated material removal treatment using an accelerator remover (for example, a spoon containing chloride ions) to use a gasification = ion on an accelerator. The fresh ^ (4) reduce or remove the agent from the surface of the substrate. This process is preferably carried out when performing the reverse f solution. After the accelerator is removed, the recess is filled with the plating. However, it is found that even the addition of -mu ' because The removal of the accelerator does not go to 322697 6 201139760 (desorption), so voids are formed in the plated metal buried in the interconnect recesses. ° A relatively long plating time is required to prevent such voids from being formed. Furthermore, the use of reverse electrolysis complicates the feeding system of the plating apparatus. The present invention has been achieved in view of the above circumstances. Accordingly, it is an object of the present invention to provide a method of filling a plating metal at an interconnecting recess at a relatively high rate. A plating method and a plating apparatus for forming voids in a plating metal embedded in an interconnecting recess. In order to achieve the above object, the present invention provides a plating method comprising the following steps: preparing on the surface with mutual a substrate having a recess; performing a first pre-treatment of the substrate by dipping the substrate into a first pre-treatment solution comprising an accelerator, a metal ion, and an acid; by immersing the substrate in an additive comprising a second pre-treatment solution that does not contain an accelerator, wherein 'the additive suppresses the effect of the accelerator contained in the first pre-treatment solution' and implements the second pre-preparation of the substrate The treatment is performed first; and then, the plating of the surface of the substrate is performed by using a plating solution containing at least one metal ion, an acid, and an inhibitor without including an accelerator, thereby filling the plating metal in the interconnect recess. Therefore, by performing the second pre-treatment, the substrate is immersed in the second pre-treatment solution containing the additive and not including the accelerator, wherein the additive suppresses the effect of the accelerator contained in the first pre-treatment solution, and the present The humectant in the surface of the field region of the substrate can be more stably deactivated. It is thus possible to fill the barrier metal at a higher rate in the interconnect recess without stepping into the embedded plating metal. #322697 7 201139760 - In a preferred aspect of the invention, the first pre-treatment A preliminary electrolytic treatment performed by electrolytically treating the surface of the substrate while immersing the substrate in the first pre-treatment solution. In the first pre-treatment, the substrate is immersed in a first pre-treatment solution comprising an accelerator, metal ions and an acid, allowing the accelerator to adsorb onto the entire surface of the substrate comprising the surface of the interconnect recess. This accelerator adsorption process can be stably performed by electrolytically treating the surface of the substrate. The preliminary electrolysis treatment can be carried out at a current density of 50 to 250 A/M2. For example, SPS (bis (3-sulf〇propyl) disulfide) sulfide (suifur comp〇un (j) can be preferably used to be included in the first pretreatment solution. Accelerator. The concentration of the accelerator contained in the first pretreatment solution may be generally 5 to 500 " M / L, preferably 50 to 500 # M / L. Included in the second pretreatment solution and The additive which suppresses the effect of the accelerator contained in the first pretreatment solution may be a homogenizer. The ethyleneimine polymer or a derivative thereof (such as polyethyleneimine (PEI)) may be compared. It is preferably used as a homogenizer. PEI as a homogenizer has a high accelerator stopping effect. Therefore, it is present in the substrate by immersing the substrate on which the accelerator has been adsorbed in, for example, a water sulfuric acid solution containing PEI. The adsorbed adsorbent in the surface of the field region can be selectively stopped. Preferably, when the processing solution is stirred, the first pre-treatment 322697 8 201139760, second pre-treatment and electroplating are carried out. At least one of the preferred aspects of the present invention, when the second pre-treatment solution is stirred, the second pre-treatment is performed, and the plating is stirred when the second pre-treatment agitation intensity is equal to or greater than the agitation. In the preferred embodiment of the present invention, the surface of the first pre-treated substrate is washed with dilute sulfuric acid, and the surface of the second pre-treated substrate is washed with dilute sulfuric acid. Compared with the surface of the substrate, which is cleaned with pure water, the surface of the first pre-treated substrate is cleaned with dilute sulfuric acid to improve process stability and uniformity. The present invention also provides a plating apparatus for implementation. Plating on the surface of the substrate having interconnecting recesses in the surface, the plating apparatus comprising: a first pre-processing unit 'for immersing the substrate in a first pre-treatment solution containing an accelerator, a metal ion and an acid And performing a first pre-second pre-processing unit of the substrate for immersing the substrate in a second pre-existing portion containing an additive and not containing an accelerator In the solution, wherein the additive inhibits the effect of the accelerator contained in the first pre-treatment solution to perform a second pre-treatment of the substrate; and, the plating unit, after the second pre-treatment, The electroplating of the surface of the substrate is performed by using a plating solution comprising at least one metal ion, under- and inhibitor, and no accelerator, thereby filling the plated metal in the interconnect recess. In a preferred embodiment, the first pre-processing unit is configured to perform electrolytic treatment on the surface of the substrate when the substrate is immersed in the first pre-treatment solution. 9 322697 201139760 In a preferred aspect of the invention The plating apparatus further includes a first cleaning unit and a second cleaning unit, wherein the first cleaning unit cleans the surface of the substrate with dilute sulfuric acid, and the substrate undergoes a first pre-processing in the first pre-processing unit And the second cleaning unit cleans the surface of the substrate with dilute sulfuric acid, and the substrate undergoes a second pre-treatment in the second pre-processing unit. In a preferred aspect of the present invention, at least one of the first pre-processing unit, the second pre-processing unit, and the plating unit is provided with a stirring device for stirring the processing solution; and the plating The device includes a control unit for controlling a stirring speed of the stirring device, the first pre-processing time in the first pre-processing unit, the second pre-processing time in the second pre-processing unit, and Plating time in the plating unit. In a preferred aspect of the present invention, the second pre-processing unit is provided with a stirring device for stirring the second pre-treatment solution; and the control portion is determined according to the width or diameter and depth of the interconnecting recess The soaking time of the substrate and the stirring strength of the second pre-treatment solution in the second pre-treatment. According to the present invention, the plating of the surface of the substrate can be carried out in the presence of an accelerator which has been adsorbed on the surface of the substrate, and the accelerator is the active surface of the interconnecting recess, but in the field of the substrate The surface of the area has been completely stopped. This condition makes it possible to fill the plated metal in the interconnect recess at a higher rate without forming voids in the buried plated metal. [Embodiment] 10 322697 201139760 - r A preferred embodiment of the present invention will now be described in detail with reference to the drawings. The following description shows an exemplary case in which a substrate W' having an interconnect recess 12 (such as a trench and a through hole) formed in a surface and covering the seed layer 10 is prepared as shown in FIG. 5A; and, copper A metal plating film 14 is filled in the interconnect recess 12 to form an interconnection of copper, as shown in FIG. 5C. Fig. 1 shows a general plan view of a plating apparatus in accordance with an embodiment of the present invention. As shown in FIG. 1, the plating apparatus 20 includes three loading/unloading portions 22' each loading/unloading portion 22 for mounting a substrate cassette therein, in which a plurality of substrates are accommodated. a first pre-processed unit 24' for performing a first pre-treatment of the substrate W by immersing the substrate w in a first pre-treatment solution containing an accelerator, a metal ion and an acid; The processing unit 26' is configured to immerse the substrate w in a second pre-treatment solution containing an additive and not containing an accelerator, wherein the additive inhibits the accelerator contained in the first pre-treatment solution, and is implemented a second pre-treatment of the substrate w; and two plating units 28 for performing the surface of the substrate w by using a plating solution containing at least one metal ion, an acid, and an inhibitor instead of a 匕3 accelerator Plating. The keying device 20 also includes three cleaning units, sputum, and surgery, each of which is washed with a thin sulfur k (washing (nnse)) surface of the substrate w; cleaning / element 32' is used for cleaning and drying the substrate after the electric key w; and, the rack is widely used for temporarily placing the substrate W before and after the processing, the substrate transporting device i 36 is movably disposed between the loading/unloading (four) and the substrate stage 34, and the second substrate conveying device is % The movable 322697 11 201139760 is movably disposed between the substrate stage 34 and the unit. All of the units including the first pre-processing unit 24, the second pre-processing unit 26, and the plating unit 28 are controlled by the control unit 4 provided in the outer panel of the plating apparatus 20. In this embodiment, an electrolytic treatment unit for performing electrolytic treatment (plating) of the surface of the substrate w is used as the first pre-processing unit 24. Thus, as shown in FIG. 2, the first pre-processing unit 24 includes a processing tank 44 for containing a sulfur-containing compound, metal ion (copper) containing an accelerator such as, for example, sps (polydithiodipropanesulfonic acid). The ionic) and acid-pre-treatment solution 42 are retained therein. The concentration of the accelerating agent (SPS) in the first pretreatment solution 42 is generally from 5 to 500 in M/L, preferably from 5 to 500 a M/L. The first pre-processing unit 24 also includes a vertically movable substrate holder 46 for detachably holding the substrate w and immersing the substrate w in a predetermined position in the first pre-treatment solution 42 in the processing tank 44; An anode 50 made of copper-containing filler is held by the anode holder 48 and immersed in a predetermined position in the first pre-treatment solution 42 in the treatment tank 44; and the stirring paddle 54 serves as a stirring device, the stirring violet 54 The actuation of the agitation mechanism 52 is reciprocated to agitate the first pre-treatment solution 42 between the anode and the substrate w. In operation, the substrate trade held by the substrate holder 46 is immersed in the first pre-treatment solution 42 in the processing tank 44 to face a predetermined position of the anode %. The negative electrode of the power source 58 is connected to the substrate w via the wire 56a, and the positive electrode of the power source 58 is connected to the anode 5A via the wire 56b to perform preliminary electrolytic treatment (plating) of the surface of a certain plate W as the first pre-treatment = 322697 12 201139760 During this process, the agitating paddle 54 of the agitation mechanism 52 reciprocates to agitate the first pre-treatment solution 42 as needed. The current density in this preliminary electrolytic treatment is, for example, 50 to 250 A/m2. During this processing, the control unit 40 controls the timing for immersing the substrate W in the first pre-treatment solution 42, the stirring speed of the stirring blade 54, the current density, and the like. As shown in FIG. 3, the second pre-processing unit 26 includes a treatment tank 62' for holding a second pretreatment solution 60 containing an additive (for example, PEI (polyethyleneimine)) as a homogenizing agent, wherein The additive inhibits an accelerator (for example, such as SPS (the effect of polydithiodipropane sulfonic acid) without an accelerator. The second pre-processing unit 26 also includes a vertically movable substrate holder 64 for detachably holding the substrate W and immersing the substrate W in a predetermined position in the second pretreatment solution 60 in the treatment tank 62; and the agitating paddle 68 as a stirring device, the agitating paddle 68 being reciprocated by the agitating mechanism 66 to agitate the a second pre-treatment solution 6 前面 in front of the substrate w. In operation, the substrate w held by the substrate holder 64 is immersed in a predetermined position in the first pre-treatment solution 6 处理 in the processing tank 62 to implement the substrate. The second pre-treatment of the surface of W. During this process, when the requisite, the agitating paddle 68 of the agitation mechanism 66 reciprocates to agitate the first pre-treatment solution 6〇. During this process, The part 4〇 controls the time for immersing the substrate W in the second pre-treatment solution 6〇, the stirring speed of the spoiler 68, etc. As shown in Fig. 4, the plating unit 28 includes a plating tank 72 for The plating solution 70 containing the inhibitor 'for example, PEG (polyethylene 322697 13 201139760 - gWc01), metal ion (copper ion) and acid is retained therein. The inhibitor in the ore coating solution 70 ( The concentration of PEg) is, for example, lm M/L. The ore cover unit 28 also includes a vertically movable substrate holder 74 for detachably holding the substrate W and immersing the substrate w in the plating solution 7〇 in the bell cover# a predetermined position in 72; for example, an anode 78 containing a turn-over, held by an anode holder 76 and immersed in a predetermined position in the plating solution 7 in the bellows 72; and, (iv) paddle 82 As the transfer device 4, the reciprocating motion of the scintillation mechanism go is disturbed by the scrambler mechanism to feed the plating solution 7 between the anode 78 and the substrate W. In operation, the substrate held by the substrate holder 74 is w Soaking in the keying solution 70 in the money cover 72 facing the predetermined position of the anode 78 The negative electrode of the plating power source 86 is connected to the substrate w via a wire, and the positive electrode of the overlying power source 86 is connected to the anode 78 via a wire _ to implement the electric ore. During the plating, the stirring f is applied during the plating. Η 82 reciprocating motion to secrete the plating solution 7 〇. This =! 4 4 control _82 disturbing speed, etc. The operation of the device, according to the fifth to 5C diagram shown in Figure 1 Loading/unloading: = The substrate is transported from the first substrate to the substrate, and the substrate is transported by the second substrate; the substrate is transported by the substrate === Then... use thin, clean (washed). After::, =: 322697 201139760 is then transferred to the substrate holder 46 of the first pre-processing unit 24. In the first pre-processing unit 24, as shown in FIG. 2, the substrate w is immersed in a predetermined position in the first pre-treatment solution 42 in the processing tank 44, and a voltage is applied to the substrate w and the substrate w disposed opposite to each other. A preliminary electrolytic treatment (plating) of the surface of the substrate W is performed between the anodes 5〇 as the first pretreatment. By this first pre-treatment, an accelerator 90 such as SPS is adsorbed onto the entire surface of the substrate W including the surface of the interconnect recess 12 as shown in Fig. 5A. During this treatment, the first pre-treatment solution 42 in the treatment tank 44 is agitated with a stirring paddle 54 as needed. The control unit 40 controls the first pre-processing state, the stirring speed of the agitating paddle 54, and the like. The substrate W after the first pre-treatment is then transported by the second substrate transfer device 38 to the cleaning unit 30b where the surface of the substrate w is washed (washed) with dilute sulfuric acid. After cleaning, the substrate W is then transferred to the substrate holder 64 of the second pre-processing unit 26. In the second pre-processing unit 26, as shown in Fig. 3, a second pre-treatment of the surface of the substrate W is carried out by immersing the substrate W in the second pre-treatment solution 6 of the processing tank 62. The second pre-processed 'such as PEI additive (homogeneous agent) 92 is adsorbed onto the surface of the interconnect recess 12 near their opening and onto the surface of the field region of the substrate, as shown in FIG. 5B Show. During this treatment, the second pretreatment solution 6 in the treatment tank 62 is agitated with a stirring paddle 68 as needed. The control unit 40 controls the second pre-processing condition, the mixing speed of the mixing paddle 68, and the like. By allowing the additive (homogeneous agent) 92 such as PEI to be adsorbed 322697 15 201139760 - to the surface of the interconnect recess 12 near their opening, and to the surface of the field region of the substrate, it has been adsorbed to The interconnecting recesses 12 are on the surface near their openings, and the accelerator 90, such as SPS, on the surface of the field region of the substrate can be stopped by the additive 92 while remaining in the interconnect recess 12 The effect of the accelerator 90. In particular, it has been confirmed that PEI as a homogenizing agent has a high SPS stopping effect, and SPS present in the surface of the field region of the substrate can be selectively stopped by immersing the substrate in a water sulfuric acid solution containing PEI. Among them, SPS has been adsorbed in the entire surface area. After the second pre-treatment, the substrate W is transported to the cleaning unit 3〇c by the second substrate transfer device 38, where the surface of the substrate w is cleaned (washed) with dilute sulfuric acid (after washing), and then the substrate W is transferred to the substrate W. The substrate holder 74 of the plating unit 28. In the recording unit 28, as shown in FIG. 4, the substrate W is immersed in a predetermined position in the plating/sink 70 in the plating tank 72, and a voltage is applied to the substrates w and anodes disposed opposite each other. Between 78, to implement the electricity of the surface of the substrate W. During this plating, the plating solution 70 in the plating tank 72 is stirred by the stirring paddle 82 as needed. The control unit 4 controls the plating condition and the search speed of the mixing violet 82. ^The electric ore of the substrate W is used, and the additive (homogeneous agent) is used to adsorb to the surface of the region of the surface of the interconnecting recess 12 near the opening of the base τ such as sps The accelerator ^ < ' while maintaining the effect of the accelerator 90 present in the interconnecting recess 12 can be accelerated by the force π $ repelling agent 90 in the interconnection recess π 16 322697 201139760, the metal plating on the bottom Deposition of (copper) 14 (bottom-up) while inhibiting the deposition of the bonding metal 14 on the surface of the field of the substrate W by the action of an inhibitor contained in the bonding solution, as shown in Figure 5c Show. The substrate W after the plating is transferred from the second substrate transporting slit 38 to the drying unit 32' where the surface of the substrate W is cleaned with, for example, pure water: and dried. After drying, the substrate W is sent to the substrate stage 34 by the second substrate transfer device μ. The first substrate transfer device 36 takes the substrate W from the substrate stage 22 34 and returns the substrate W to the loading/unloading. The accelerator of s, such as SPS, is an additive which is indispensable for accumulating metal from the bottom of the interconnecting recess such as the j-groove and the through-hole (i.e., in a bottom-up manner). In the case of interconnecting recesses having a high aspect ratio, the deposition of the plating metal will occur when the effect of x and the humectant is generated on the entire surface of the substrate and the substrate attached to the surface including the interconnecting recesses. Accelerated also on the surface of the recess 12 near their opening, and before the interconnect recess is completely filled by the bottom-up grown plating metal, the openings will be blocked by the plated metal, which is possible of. To solve this problem, in accordance with the present invention, the substrate will first be subjected to a first pre-treatment, wherein the substrate is immersed in a solution comprising an accelerator, a metal ion, and a copper sulphate solution and a vapor containing an accelerator such as SPS. The first pre-treatment solution of the ions, while simultaneously treating the surface of the substrate, as needed, thereby allowing the accelerator to adsorb onto the entire surface of the substrate comprising the surface of the interconnect recess 4. The substrate will then be subjected to a second pre-treatment in which the substrate is immersed in an additive (such as 326697 17 201139760-agent) containing, for example, PEI, wherein the additive inhibits the effect of the accelerator, The accelerator present in the surface of the field region of the substrate and the surface of the interconnecting recess in the vicinity of their opening cease to function. The additive (homogeneous agent) may diffuse to the surface of the interconnect recess only in a small amount, and thus the accelerator remains active in the surface of the interconnect recess. The substrate is then subjected to electroplating in an accelerator present in a state of using a plating solution containing metal ions, an acid and an inhibitor. Thus, the bottom-up deposition of the plated metal proceeds from the bottom of the interconnecting recess that can maintain the effect of the accelerator, and vice versa by the effect of the inhibitor in the surface of the field region of the substrate on which the accelerator has ceased to function. Metal-coated deposits. Even when a high plating current is used to achieve a high plating rate, it is impossible to block the opening of the interconnect recess by the plating metal before the plating metal is filled in the bottom-up manner to fill the interconnect recess. Therefore, it becomes possible to fill the plating metal in the interconnect recess at a higher rate. In order to determine the optimum processing conditions for the first pre-treatment, the second pre-treatment, and the electroplating, the effects of filling various processing conditions of the plated metal in the interconnected recesses were examined by wafer testing. These results are illustrated below. A patterned wafer having a pattern of through holes (interconnect recesses) having a diameter varying by 20, 30, 40 and 50 #m and a depth of 60/zm was used as the test wafer. After pre-treatment, the test wafer was plated using a mask tape to a 6-mm diameter zone centered on the pattern. A three-electrode type cell, a reference electrode (mercury/mercuric sulfate electrode), a platinum anode, and a 200-mL circuit breaker were fabricated using the test wafer, and a potentiostat potential was used in the battery. The first pre-treatment and electroplating were carried out under control. 18 322697 201139760 Use water sulfuric acid/copper sulfate solution (〇9MCuS〇4 · 5H2〇/〇.56M H2S〇4) as the basic piating bath, and use water lMHJO4 solution for the treatment step Cleaning (washing). For the cleaning (washing) between the processing steps, it is preferred to use dilute sulfuric acid rather than pure water from the viewpoint of ensuring process stability and uniformity. A solution obtained by adding a basic plating solution PEG (polyethylene glycol) as an inhibitor at a concentration of O.lmM, a vapor ion at an imM concentration, and (polydithiopropanesulfonic acid) as an accelerator at a predetermined concentration is Used as the first pre-treatment solution. In the first pre-treatment, the test wafer is immersed in the first pre-treatment solution, and the application of electricity: (10) is adsorbed onto the surface of the wafer including the through hole ==. In the second pretreatment, the test wafer is immersed in a second pretreatment solution obtained by adding cation (polyethyleneimine) to a predetermined concentration to the water solution. In the parent, use only by adding polyethylene glycol as an inhibitor to the concentration of 〇. 1 mM and vaporization away from '
ImM之濃度至基本鍍液而獲得之鍍覆溶 ' ^ 孩錢覆金屬 (銅）以預定的電位沉積於該測試晶片之* 〜衣面上，藉此殖 滿該鍍覆金屬（銅）於該貫穿孔中。 、 於各處理中’藉由攪拌器晶片之機構以 zuQrpm之旋 轉速度攪拌該處理溶液。在第一預先處理之前， 酸溶液實施測試晶片之清洗（水洗）30秒鐘’、先用水硫 $ ’以及處理之 間間隔20秒《於清洗期間，電池保持其 狀 (open circuit state)。於鍍覆後，拋光(p〇iish)測試曰 9 6之剖面以翻 察埋置於該貫穿孔中之銅之狀態。 ^ 322697 19 201139760 評估下列處理狀況之效果：於浸泡基板（晶片）於第 一預先處理溶液中期間之初步電解電流以及於該第一預先 處理中於該第一預先處理溶液中加速劑之濃度；於該第二 預先處理溶液中添加劑（均勻劑）之濃度以及於該第二預 先處理中基板浸泡時間；以及，於電鍵中錢覆之過電壓 (overvoltage)。下列將作詳細說明。 A.於第一預先處理中初步電解狀況 進行實驗以檢驗於第一預先處理中初步電解狀況（電 流狀況）之效果。選擇50A/m2、ΙΟΟΑ/m2和250A/m2作為 使用於浸泡該基板（晶片）於第一預先處理中於第一預先 處理溶液中之電流密度。為了充電’施加加速劑之吸附作 用，對於所有選擇的電流密度固定於全部（SoooQ/mb ， 初步電解時間變化如下：600秒、300秒和120秒。於第一 預先處理溶液中加速劑之濃度為50AM。其他的製程狀況 顯示於下列表1中。實驗的結果顯示於第6圖中，第6圖 為於製程後測試晶片之一系列橫剖面之顯微照片。如能夠 從第6圖中看出，鍍覆生長率於3〇〇秒-l〇〇A/m2之情形為 最高。第6圖亦表示增加電流沒有導致增加鍍覆生長率。 於此方面，想像得到加速劑之擴散也許亦影響加速劑之初 步吸附。 322697 20 201139760 ' [表 i] 製程 基礎 添加劑 時間 電位 電流密 度 PEG/ mM Cl/ mM SPS/ μΜ PEI/ βΜ /s /mV.vs MSE /A/m2 水洗 H2S〇4 - - ~ 30 開 路 第一鍵 液 鍍覆鍍 液 0.1 1 50 - 600,300,120 - -50,-100, -250 水洗 H2S〇4 - - 25 開路 第二鍍 液 H2S〇4 - - - 1 30 開路 水洗 H2S〇4 - - - 25 開 路 第三鍍 液 鍍覆鍍 液 0.1 1 1800 -575 - 雖然加速劑之吸附於基板之表面上可能僅藉由浸泡 該基板於包含加速劑、金屬離子和酸之第一預先處理溶液 中而達成，但是為了穩定該製程，較佳還是使用電解法。 B.於第一預先處理中於第一預先處理溶液中加速劑之濃度 進行實驗以檢驗於第一預先處理中於第一預先處理 溶液中加速劑之濃度之效果。選擇5/zM、50"M和500 //Μ作為加速劑於第一預先處理溶液中之濃度。在300秒 -ΙΟΟΑ/m2狀況下實施初步電解。其他的製程狀況顯示於下 列表2中。實驗的結果顯示於第7圖中，第7圖為於製程 後測試晶片之一系列橫剖面之顯微照片。如能夠從第7圖 中看出，參照20-/z Μ之貫穿孔，當於第一預先處理溶液 21 322697 201139760 中加速劑之濃度為50/zM時，鍍覆生長率為最高。參照具 有為30至50# m直徑之貫穿孔，鍍覆生長率隨著加速劑 濃度之增加而增加。於第一預先處理中加速劑之最佳濃度 因此考慮在50 /z Μ與500 # Μ之間。 [表2] 製程 基礎 添加劑 時間 電位 電流密 度 PEG/ mM Cl/ mM SPS/ "M PEI/ βΜ /s /mV.vs MSE /A/m2 水洗 H2S〇4 - - - 30 開路 第一鍍 液 鍍覆 鍍液 0.1 1 5,50,5 00 - 300 - -100 水洗 H2S〇4 - - - 25 開路 第二鍍 液 h2so4 - - - 1 30 開路 水洗 H2S〇4 - - _ - 25 開路 第三鍍 液 鍍覆 鍍液 0.1 1 • 1800 -575 - C.於第二預先處理中於第二預先處理溶液中添加劑（均勻 劑）之濃度 進行實驗以檢驗於第二預先處理中於第二預先處理 溶液中添加劑（均勻劑）之濃度之效果。選擇0.1 、1 # Μ和10/ζ Μ作為添加劑於第二預先處理溶液中之濃 度。浸泡晶片於第二預先處理溶液中之時間為30秒。其他 的製程狀況顯示於下列表3中。實驗的結果顯示於第8圖 中，第8圖為於製程後測試晶片之一系列橫剖面之顯微照 片。如能夠從第8圖中看出，當藉由將晶片浸泡於具有濃 22 322697 201139760 度0.1//Μ之第二預先處理溶液中經過3〇秒鐘實施二 預先處理時，貫穿孔之開口被電_鍾之鋼阻隔了以: 空隙形成在埋置於貫穿孔中的鋼中。此情況表示添加劑停 止作用存在於晶片之場區域之表面中和於貫穿孔於他們的 開口附近表面中之加速劑的效果不足。從貫穿孔中鑛覆金 屬之生長，於第二預先處理溶液中1//Μ作為添加：之濃 度係考慮為適當。第8圖亦證明加速劑於晶片之整個表面 中完全停止作用，並且當藉由將該晶片浸泡於具有Μ 之添加劑濃度之第二預先處理溶液中經過3〇秒實施該第 一預先處理時均勻地進行鑛覆。 [表3] 製程 基礎 添加劑 間 ---^ 電位 電流密 度 PEG/ mM Cl/ mM SPS/ im PEI/ βΜ /s /mV.v sMSE /A/m2 水洗 h2so4 - - - - 30 第一鍍 液 鑛覆链 液 0.1 1 50 - 300 -50,-10 0-250 水洗 h2so4 - - - 25 1政 第二鍍 液 h2so4 - - o.u, 10 30 開路 水洗 h2so4 - - - 25 ?4 第三鍍 液 鍍 液 0.1 1 - 釋 180 0 -575 D.於第二預先處理中基板浸泡時間 進行實驗以檢驗於第二預先處理中基板（晶片）浸泡於 第二預先處理溶液中時間之效果。選擇Μ作為添加劑 322697 23 201139760 於第二預先處理溶液中之濃度。晶片浸泡時間變化如下：5 秒、30秒和60秒。其他的狀況顯示於下列表4中。實驗 的結果顯示於第9圖中，第9圖為於製程後測試晶片之一 系列橫剖面之顯微照片。如能夠從第9圖中看出，當藉由 將晶片浸泡於第二預先處理溶液中經過5秒鐘實施該第二 預先處理時，鍍覆金屬能夠以最高速率填滿入該等貫穿 孔。此情況被考慮到係由於事實上相較於晶片浸泡於第二 預先處理溶液中經過30秒之情況，更限制停止作用之加速 劑存在於該等貫穿孔之頂部區域中。從第二預先處理溶液 之添加劑濃度之效果和晶片浸泡時間之效果，將可了解 到，添加劑（均勻劑）之消耗和擴散於第二預先處理中是 重要的因素。 [表4] 製程 基礎 添加劑 時 間 電位 電流密 度 PEG/ mM Cl/ mM SPS/ βΜ PEI/ βΜ /s /mV.v sMSE /A/m2 水洗 H2S〇4 - - - 30 f4 路 第一 鍍液 鍍覆鍍 液 0.1 1 50 - 300 - -100 水洗 H2S〇4 _ 25 開路 第二 鍍液 H2S〇4 - - - 1 5,3 0,6 0 開路 水洗 h2so4 - - - 25 ?4 路 第三 鍍液 鍍覆鍍 液 0.1 1 180 0 -575 - 24 322697 201139760 E.於電鍍中鍍覆過電壓 進行實驗以檢驗於電鍍期間電位之效果。因為存在於 晶片之場區域之表面中以及於貫穿孔在他們的開口附近之 表面中之加速劑藉由第二預先處理而被停止作用，因此考 慮到可能使用高鍍覆電流。為了證明此點，於下列變化的 電位施行電鍍：-550mV、-575mV和-600mV。其他的製程 狀況顯示於下列表5中。實驗的結果顯示於第10圖中，第 10圖為於製程後測試晶片之一系列橫剖面之顯微照片。如 能夠從第10圖中看出，當電鍍於高負電位-600mV實施 時，鍍覆金屬（銅）於30分鐘完全填滿入20-//Μ之貫穿孔 而沒有在埋置之鍍覆金屬中形成空隙。再者，未觀察到鍍 覆金屬之沉積於晶片之場區域之表面中於填滿該鍍覆金屬 於該等貫穿孔（該等貫穿孔係關聯到電位之改變）中之不 利的影響。 [表5] 製程 基礎 添加劑 時間 電位 電流 密度 PEG/ mM Cl/ mM SPS/ μΜ PEI/ βΜ /s /mV.vs MSE /A/m2 水洗 H2S〇4 - 30 開路 第一 鍍液 鍍覆鍍 液 0.1 1 50 - 300 - -100 水洗 H2S〇4 - - - 25 開路 第二 鍍液 h2so4 - - - 1 30 開路 水洗 H2S〇4 - - - 25 開路 第三 鍍液 鍍覆鍍 液 0.1 1 - 1800 -550,-575,-600 - 25 322697 201139760 藉由在高濃度含氯化物離子溶液中反向電解進行參 考實驗以檢驗加速劑之吸附。 F.藉由在高濃度含氯化物離子溶液中反向電解該加速劑 之吸附（參考實驗） 如使用於上述實驗中之相同的基本鍍液係使用於此 參考實驗中。當浸泡上述之測試晶片於如上述包含l〇〇y Μ濃度之加速劑之第一預先處理溶液中時，首先實施初步 電解處理（第一預先處理）於ΙΟΟΑ/m2之電流密度經過300 秒。其次，為了從該晶片之場區域之表面去吸附加速劑， 該晶片被浸泡於包含高濃度之氯化物離子之處理溶液中， 而該系統承受反向電解。於此種處理後，實施晶片表面之 銅電鍍。詳細的製程狀況顯示於下列表6中。實驗的結果 顯示於第11圖中，第11圖為於製程後測試晶片之一系列 橫剖面之顯微照片。 [表6] 製程 基礎 添加劑 時間 電位 電流密 度 PEG/ mM Cl/m Μ SPS/ βΜ /s /mV /A/m2 第一鍍 液 標準 0.1 1 100 300 - -100 第二鍍 液 標準 0.1 1 - 20 100 第三鍍 液 標準 0.1 1 -- 3000 -575 26 322697 201139760 如能夠從第11圖看到，當實施電鍍3000秒將鍍覆金 屬（銅）填滿於貫穿孔中時，空隙集中形成在埋置於2〇_ 之貫穿孔帽覆金屬（銅）巾。如果晶片藉由加速劑 去吸附方法而被預先處理，其中，該晶片被浸泡於包含高 濃度之氯化物離子之處理溶液中，同時為了從該晶片的場 區域之表面去除加速劑而實施反向電解，此情況表示主要 銅鍍覆必須實施至少3000秒❶關於此種預先處理方法，反 向電解提升加速劑之去吸附。於是，如果實施了加速劑去 吸附預先處理而沒有作反向電解，亦即，僅僅藉由將晶片 浸泡於處理溶液巾，則加速劑去吸附效果料足，藉此鐘 覆金屬之沉積將不能夠被充分抑制於晶片之場區域之表面 中和於貫穿孔於他們的開口附近表面中。 上述實驗之結果於是證明鍍覆金屬能夠藉由實施將 基板浸泡於包含譬如SPS之加速劑、金屬離子和酸之第一 預先處理*液巾之該基板之第—預先處理，實施藉由將該 基板浸泡於包含譬如PEI之添加劑（均勻劑）之第二預先 處理溶液中之該基板之第二預先處理，其中，該添加劑抑 制包含於該第-預先處理溶液巾之加㈣之效果，然後藉 由使用包含至少—金屬離子、酸和抑制劑而不包含加速劑 之鍍覆溶液來實施該基板之電鍍，而以高速率填滿於基板 之互連凹。p中。尤其是，PEi為添加劑（均勻劑）具有高 sps停止作用效果。已經吸附於基板表面上之sps能夠藉 由將該基板浸泡於包含PEI之水硫酸溶液中而停止作用。 322697 27 201139760 依照本發明’藉由實施將該基板浸泡於包含譬如PEI 之添加劑（均勻劑）之第二預先處理溶液中之該基板之第 二預先處理’則已經吸附於基板表面上之譬如SPS之添加 劑能夠被選擇性地停止作用於基板之場區域之表面中，亦 即’表面區域而非互連凹部之表面。此情況使得能夠從互 連凹部之底部選擇性的生長鍍覆金屬。因此，例如對於具 有直控20//M和深度6〇βΜ之貫穿孔，能夠於3〇分鐘完 成無空隙填滿鍍覆貫穿孔(v〇id_free via_舰ng plating)，並 且包含預先處理時間之總處理時間不超過4〇分鐘。 上述實驗結果亦表示控制於互連凹部深度之能力，可 =藉由於第一預先處理中控制譬如sps之加速劑吸附之 置，使加速劑停止作用效果有效地運用於該互連凹部，以 及於第—預先處理中加速劑停止作用效果。此情況轉而表 不透過調整預先㈣處理狀況以高速率無間隙地填滿鍵覆 金屬，各種深度之互連凹部（譬如溝槽和貫穿孔）之能力。 尤其疋，可以藉由依於互連凹部之縱橫比改變於第二預先 處理中於第二預先處理溶液中添加劑（均句劑）之濃度、 基板浸泡時間等，而可達成意欲的填滿凹職覆^溶液擾 拌狀況亦影響互連凹部之深度，而加速.止作用 於該互 連凹部。 虽於基板表面上，例如藉由攪拌，而產生處理溶液流 動時，形成在基板表面附近之贿層之厚度通常與流體之 速度形成反比。-種㈣處理溶液流過基板表面之流體速 度之方法為使用旋轉的圓盤。於此方法中，旋轉圓盤之旋 322697 28 201139760 轉速度正比於處理溶液流過旋轉圓盤表面之流體速度。參 考形成在旋轉圓盤的表面上之擴散層之厚度，圓盤之旋轉 速度ω與擴散層之厚度6之間的關係可以由下列公式 (V.G. Levich等人，“物理化學流體力學，，，新澤西州恩格 爾伍德懸崖（Englewood Cliffs，N.J.)，普軟提斯_哈爾 (Prentice-Hall) ( 1962))分析地決定：占二以⑴口、 1/66Γ1/2 (其中，D表示擴散係數，而p表示動力黏度）。 第12圖為顯不依照上述公式計算旋轉圓盤之旋轉速 度與形成在作為銅鍍覆溶液之水硫酸銅/硫酸溶液（硫酸銅 鍍覆溶液）中基板表面之上的擴散層厚度之間的關係之圖 式。 於此情況，因為互連凹部（譬如溝槽和貫穿孔）之小 ，度或直徑，因此沒有處理溶液之流體被引起於互連凹 部，依於流過基板表面之處理溶液之流體速度而形成在基 板表面上之擴散層上之厚度，決定對於物質從溶液中之點 移動至基板表面所花費的時間。於擴散層中，物質主要藉 ，由擴散移動。為了簡化之㈣，採用—維模式作為範例， 從擴散層之上表面擴散之化學物種濃度隨時間改變能夠藉 :解擴散方程式而決定’如第13圖中所示。於硫酸:鍍覆 /奋液中鋼離子之擴散係數係使用為擴散方程式中之散係 ° ' 如可以從第13圖中看到，從擴散層之上表面之點之 距離愈長’則化學物種到達該點要花愈多的時間。再者， 從第12圖中顯然看出，擴散層之厚度依於處理溶液之流體 322697 29 201139760 速度。這些資料建議 攪拌強度將㈣ θ &理巾第—縣處理溶液之 應和吸附至基板之得大㈣化學物種（加速劑）將供 上，反之於第二預先Γ部（譬如貫穿孔和溝槽）之底部 和實施，而使得化、理中第—贱處理溶液之㈣將溫 板之場區域之表面+種（添加劑（均勻劑））將僅到達基 面。 ，和於互連凹部於他們的開口附近之表 大寬ΐ或盐於因為互連凹部（譬如溝槽和貫穿孔）之 互連:部之:C拌溶液而使處理溶液之流體亦產生於 深度方向之物理溶液之流體影響移動於互連凹部之 貝孓移動距離。 ί/Μ夕」而σ現在考慮到分別具有1〇μΜ、30/ζΜ* 50 ，處理3類型之貫穿孔’希望㈣拌該處理溶液時係允 =理，巧穿孔。假定所有的貫穿孔具有％ ^、之冰度’和處理溶液藉由擾拌紫之方式卩0.3米/秒或 首3米/秒之槳移動速錢拌，以數值分析判定處理溶液於 穿孔中以及於他們的開口之附近之貫穿孔之表面之流動 、態。根據分析結果’可以評估預先處理雜之流體相關 ^攪拌強度和貫穿狀聽侵人貫穿狀情況如下。第14 ‘”’員示貝穿孔之直徑與處理溶液之流體侵入貫穿孔中深度 之間的關係。於第14圖中’侵入深度㈣⑽⑻定義 W處理4液於1毫米/秒（_/see)之流體速度流動到達 之深度。 如月b夠從第14圖看出，當處理溶液以相同的槳移動 30 322697 201139760 速度擾拌時，侵入深度隨著增加貫穿孔直徑而增加。當溶 液以1.3毫米/秒之紫移動速度授拌時，為了獲得第二預先 處理溶液之流體於50-yM之貫穿孔之侵入深度與於 // Μ之貫穿孔獲得相同的侵入深度，則必須以〇 3米/秒之 紫移動速度擾掉該溶液。於疋’於較大直徑貫穿孔於貫穿 孔之冰度方向流體速度分佈可以造成與於較小直徑貫穿孔 藉由使用較低的攪拌強度而有相似的流體速度分佈。因 此，藉由於第二預先處理期間，控制擾拌槳之擾拌強度（移 動速度）’則可以均等於各種直彳空或寬度之互連凹部於互 連凹部之深度方向中添加劑（均勻劑）之效果。 如上述說明，於第二預先處理中，可以藉由控制第二 預先處理溶液之攪拌強度係是否互連凹部為窄的一種於該 凹部中沒有溶液之流動基於該溶液之攪拌而產生，或者該 互連接凹部為寬的一種於該凹部中溶液之流動係依據該溶 液之授拌而產生，而控制於該互連凹部中受到添加劑（均 勻劑）效果之於該互連凹部中的深度範圍。因此，對於具 有任何大小之互連凹部之基板，能夠於該基板之場區域之 表面中和於他們的開口附近之互連凹部之表面中抑制加速 劑之效果，反之可以維持於互連凹部中加速劑之效果，尤 其於他們的底部。此情況使得可以完成鍍覆之由下而上之 生長。 對於能夠抑制加速劑之效果之於互連凹部之他們的 開口附近之表面深度較佳是在大約從基板之場區域之表面 至互連凹部之底部之深度之一半至三分之一。藉由從形成 322697 31 201139760 在基板表面之上之擴散層之上表面擴散至互連凹部之底 部，而輸送用於抑制加速劑效果之添加劑（均勻劑）。因 此，抑制加速劑之效果反比於從擴散層之最近上表面之距 離。 於電鑛中，必須快速供應金屬離子至互連凹部之底 部，且因此需要強力擾拌鑛覆溶液。因此，鑛覆溶液於電 鍍中較佳將以等於或高於在第二預先處理中攪拌強度之攪 拌強度來攪拌。 雖然已經說明了 SPS作為加速劑，但是可能使用其他 的硫化物作為加速劑。其他可以使用之硫化物之範例包含 SPS之同分異構物’二3_磺酸_2_羥丙基（bis (3-sulfo-2-hydroxypr〇pyl))二硫化物及其鈉鹽、3_苯並 0塞吐 _2_ 硫代丙績酸（3- ( benzothiazolyl-2-thio ) propylsulfonicacid)及其鈉鹽、3-磺酸N，N-二曱基二硫代 氨基曱酸（3-sulfopropylN，N-dimethylditliiocarbamate)及 其鈉鹽、Ο-乙基-S- (3-磺酸）-碳酸二乙酯（〇_6比丫1-8-(3-sulfopropyl) -diethylcarbonate)及其鉀鹽、硫脲及其 衍生物等。 雖然已經說明了 PEI作為添加劑（均勻劑），但是可 能使用用於抑制加速劑之效果之其他的化合物。此種化合 物之範例包含含氮聚合物，例如，譬如聚乙稀四氫P各酮 (polyvinyl pyrrolidone)或其衍生物、和習用上已經用為均 勻劑之健那綠B (Janus Green B)之陽離子聚合物；醞胺 化合物；硫代醯胺化合物；具有苯胺或破咬環之化合物； 32 322697 201139760 雜環化合物；簡明雜環化合物；和胺基羧酸 (aminocarboxylic acid) 〇 雖然已經說明了聚乙婦作為用於鍛覆之抑制劑’但是 可能使用其他的抑制劑。其他可以使用之抑制劑之範例包 含聚丙二醇、乙一醇與丙二醇之共聚物（C〇P〇lymer)和其衍 生物、聚乙嫦醇、叛甲基纖維素等。 例如具有直徑20//m和深度6〇/ζιη之貫穿孔使用於上 述實驗中。對於相同直徑但是具有較大深度之貫穿孔，可 以藉由於第二預先處理中於第二預先處理溶液中增加添加 劑（均勻劑）之濃度或延長基板浸泡時間而實施無間隙填 滿穿孔鍍覆。於實驗的範例中，用於浸泡第二預先處理溶 液基板之時間例如為5秒鐘。就於實際裝置中之低再生性 之觀點而言’此種短基板浸泡時間也許為不適當。於是， 較佳是設定較長的基板浸泡時間。對於具有相同的直徑和 相同的深度之貫穿孔可以藉由減少於第二預先處理溶液中 添加劑（均勻劑）之濃度而適當地延長基板浸泡時間。 對於具有含有各種直徑和深度之貫穿孔，或者具有含 有各種直徑和深度之溝槽之基板，可以藉由事先實施相同 基板之鏟覆測試而決定於第二預先處理溶液中之適當添加 劑（均勻劑）濃度和於第二預先處理中適當的基板浸泡時 間。亦可以根據比較此種測試之結果與擴散分析之結果而 決定具有各種寬度或直徑以及各種深度之貫穿孔或溝槽之 基板’於第二預先處理溶液中之適當添加劑（均勻劑）濃 度和第二預先處理中適當的基板浸泡時間。藉由使用儲存 33 322697 201139760 此種測S式結果和分析結果之資料之資料庫而可能提供可以 自動控制基板浸泡時間和於第二預先處理中於第二預先處 理溶液中之添加劑（均勻劑）濃度之鍍覆裝置。 雖然已參照較佳實施例而詳細說明了本發明，但是應 該了解到本發明不限於上述之實施例，而是在本文中所表 現之本發明概念之範圍内可以作各種之改變和修釋。 【圖式簡單說明】 第1圖為依照本發明之實施例之鍍覆裝置之總體平面 rm · 圓， 第2圖為設置在顯示於第i圖中之鍍覆裝置中之第一 預先處理單元之示意圖； 第3圖為設置在顯示於第j圖中之錢覆裝置中之第二 預先處理單元之示意圖； 。第4圖為設置在顯示於第！圖中之鑛覆裝置中之鍵覆 單元之示意圖； 第5Α圖至第5C圖為說明藉由於第！圖中所顯示之鍵覆 裝置’將鍍覆金屬填滿於互連凹部之製程步驟之順序之圖式； 第6圖為於電鑛後測試晶片之一系列橫剖面之顯微昭 片’顯示於該第-預先處理中於初步電解狀況之驗證實驗 之結果； 系列橫剖面之顯微照 預先處理溶液中於加 第7圖為於電鍍後測試晶片之一 片，顯示於該第一預先處理中於第— 速劑之濃度之驗證實驗之結果； 第8圖為於電鍍制試晶片之-系珊剖面之顯微照 322697 34 201139760 -片，顯示於該第二預先處理中於第二預先處理溶液中於添 加劑（均勻劑）之濃度之驗證實驗之結果； 第9圖為於電鍍後測試晶片之一系列橫剖面之顯微照 片，顯示於該第二預先處理中於晶片浸泡時間之驗證實驗 之結果； 第10圖為於電鍍後測試晶片之一系列橫剖面之顯微 照片，顯示於電鍍中於過電壓鍍覆之驗證實驗之結果； 第11圖為於電鍍後測試晶片之一系列橫剖面顯之微 照片，顯示藉由在含有高濃度氯離子溶液中反向電解，加 速劑之去吸附之驗證實驗之結果，進行作為參考實驗； 第12圖為顯示旋轉圓盤之旋轉速度與形成在硫酸銅 鍍覆溶液中基板表面之上之擴散層厚度之間的關係之圖 式； 第13圖為顯示從擴散層之上表面之深度與化學物種 之標準化濃度之間的關係之圖式；以及 第14圖為顯示貫穿孔之直徑與處理溶液之流體侵入 貫穿孔中深度之間的關係之圖式。 【主要元件符號說明】 10 晶種層 12 互連凹部 14 鍍覆金屬 20 鍍覆裝置 22 載入/卸載部 24 第一預先處理單元 35 322697 201139760 26 28 30a、30b、30c 第二預先處理單元 鍍覆單元 清洗單元 32 清洗/乾燥單元 34 基板台架 36 第一基板輸送裝置 38 第二基板輸送裝置 40 控制部 42 第一預先處理溶液 44、62 處理槽 46 、 64 、 74 垂直可移動基板保持器 48 ' 76 陽極保持器 50、78 陽極 52 攪拌機構 54、68、82 攪拌槳 56a、56b、84a、84b 導線 58 電源 60 第二預先處理溶液 66、80 攪拌機構 70 鍍覆溶液 72 鍍覆槽 86 鍍覆電源 90 加速劑 92 添加劑（均勻劑） W 基板 36 322697The plating solution obtained by the concentration of ImM to the basic plating solution is deposited on the surface of the test wafer at a predetermined potential, thereby filling the plated metal (copper) In the through hole. The treatment solution was stirred at a rotation speed of zuQ rpm by a mechanism of a stirrer wafer in each treatment. Prior to the first pretreatment, the acid solution was subjected to test wafer cleaning (water washing) for 30 seconds', first with water sulfur $' and between treatments for 20 seconds. During the cleaning, the battery was in an open circuit state. After the plating, the cross section of the 曰 96 was polished to examine the state of the copper buried in the through hole. ^ 322697 19 201139760 evaluates the effect of the following processing conditions: the initial electrolysis current during soaking the substrate (wafer) in the first pre-treatment solution and the concentration of the accelerator in the first pre-treatment solution in the first pre-treatment; The concentration of the additive (homogeneous agent) in the second pre-treatment solution and the substrate soaking time in the second pre-treatment; and the overvoltage of the over-voltage in the key. The following will be described in detail. A. Initial Electrolytic Condition in the First Pre-Process An experiment was conducted to examine the effect of the preliminary electrolysis condition (current condition) in the first pre-treatment. 50 A/m2, ΙΟΟΑ/m2, and 250 A/m2 were selected as current densities for immersing the substrate (wafer) in the first pretreatment in the first pretreatment solution. In order to charge 'adsorption of the accelerator', the current density is fixed at all for all (SoooQ/mb, the initial electrolysis time changes are as follows: 600 sec, 300 sec and 120 sec. Accelerator concentration in the first pretreatment solution It is 50 AM. Other process conditions are shown in Table 1. The results of the experiment are shown in Figure 6, and Figure 6 is a photomicrograph of a series of cross-sections of the test wafer after the process. It can be seen that the plating growth rate is the highest in the case of 3 〇〇 -1 〇〇 A / m 2 . Figure 6 also shows that increasing the current does not lead to an increase in the plating growth rate. In this respect, it is possible to imagine the diffusion of the accelerator. It also affects the initial adsorption of accelerators. 322697 20 201139760 ' [Table i] Process Base Additives Time Potential Current Density PEG/ mM Cl/ mM SPS/ μΜ PEI/ βΜ /s /mV.vs MSE /A/m2 Washed H2S〇4 - - ~ 30 open circuit first button liquid plating bath 0.1 1 50 - 600,300,120 - -50,-100, -250 Washed H2S〇4 - - 25 Open second plating solution H2S〇4 - - - 1 30 Open flush H2S 〇4 - - - 25 open third plating solution Plating bath 0.1 1 1800 -575 - although the adsorption of the accelerator on the surface of the substrate may be achieved only by immersing the substrate in the first pre-treatment solution containing the accelerator, metal ions and acid, in order to stabilize the The process, preferably using electrolysis. B. performing an experiment on the concentration of the accelerator in the first pretreatment solution in the first pretreatment to verify the concentration of the accelerator in the first pretreatment solution in the first pretreatment Effect: Select 5/zM, 50 "M and 500 // Μ as the accelerator in the first pre-treatment solution. Perform preliminary electrolysis in the case of 300 sec-ΙΟΟΑ/m2. Other process conditions are shown in the following table 2 The results of the experiment are shown in Fig. 7. Fig. 7 is a photomicrograph of a series of cross sections of the test wafer after the process. As can be seen from Fig. 7, the through hole of 20-/z Μ is referred to. When the concentration of the accelerator in the first pretreatment solution 21 322697 201139760 is 50/zM, the plating growth rate is the highest. Referring to the through hole having a diameter of 30 to 50 # m, the plating growth rate is accompanied by the accelerator Increase in concentration The increase in the optimum concentration of the accelerator in the first pretreatment is therefore considered between 50 / z Μ and 500 # 。. [Table 2] Process Base Additive Time Potential Current Density PEG / mM Cl / mM SPS / " M PEI/ βΜ /s /mV.vs MSE /A/m2 Washed H2S〇4 - - - 30 Open first plating bath plating solution 0.1 1 5,50,5 00 - 300 - -100 Washed H2S〇4 - - - 25 Open second plating bath h2so4 - - - 1 30 Open circuit wash H2S〇4 - - _ - 25 Open third plating bath plating solution 0.1 1 • 1800 -575 - C. In the second pre-treatment The concentration of the additive (homogeneous agent) in the pretreatment solution was tested to examine the effect of the concentration of the additive (homogeneous agent) in the second pretreatment solution in the second pretreatment. The concentrations of 0.1, 1 #Μ and 10/ζ Μ were added as additives in the second pretreatment solution. The time for immersing the wafer in the second pretreatment solution was 30 seconds. Other process conditions are shown in Table 3 below. The results of the experiment are shown in Figure 8, which is a photomicrograph of a series of cross-sections of the test wafer after the process. As can be seen from Fig. 8, when the wafer is immersed in a second pretreatment solution having a concentration of 22 322 697 201139760 degrees 0.1 / / 经过 for 2 sec seconds, the opening of the through hole is The electric_bell steel is blocked to: The void is formed in the steel buried in the through hole. This case indicates that the additive stopping action is present in the surface of the field region of the wafer and the effect of the accelerator in the surface near the opening in their opening is insufficient. From the growth of the ore-coated metal in the through-hole, the concentration of 1//Μ in the second pretreatment solution is considered to be appropriate. Figure 8 also demonstrates that the accelerator completely ceases to function in the entire surface of the wafer and is uniform when the first pre-treatment is performed by immersing the wafer in a second pre-treatment solution having an additive concentration of ruthenium for 3 seconds. Ground cover. [Table 3] Process base additive---^ Potential current density PEG/ mM Cl/ mM SPS/ im PEI/ βΜ /s /mV.v sMSE /A/m2 Washed h2so4 - - - - 30 First plating liquid ore Chaining solution 0.1 1 50 - 300 -50, -10 0-250 Washed h2so4 - - - 25 1st second plating bath h2so4 - - ou, 10 30 open water washing h2so4 - - - 25 ?4 third plating bath 0.1 1 - Release 180 0 - 575 D. An experiment was conducted in the second pre-treatment substrate soak time to examine the effect of the time during which the substrate (wafer) was immersed in the second pre-treatment solution in the second pre-treatment. The concentration of cesium as the additive 322697 23 201139760 in the second pretreatment solution is selected. The wafer immersion time changes as follows: 5 seconds, 30 seconds, and 60 seconds. Other conditions are shown in Table 4 below. The results of the experiment are shown in Figure 9, which is a photomicrograph of a series of cross-sections of the test wafer after the process. As can be seen from Fig. 9, when the second pretreatment is carried out by immersing the wafer in the second pretreatment solution for 5 seconds, the plated metal can be filled into the through holes at the highest rate. This case is considered to be due to the fact that the cessation of the stopping agent is present in the top region of the through-holes due to the fact that the wafer is immersed in the second pre-treatment solution for 30 seconds. From the effect of the additive concentration of the second pretreatment solution and the effect of the wafer immersion time, it will be appreciated that the consumption and diffusion of the additive (homogeneous agent) is an important factor in the second pretreatment. [Table 4] Process Base Additive Time Potential Current Density PEG/ mM Cl/ mM SPS/ βΜ PEI/ βΜ /s /mV.v sMSE /A/m2 Washed H2S〇4 - - - 30 f4 Road First Plating Plating Plating solution 0.1 1 50 - 300 - -100 Washed H2S〇4 _ 25 Open second plating solution H2S〇4 - - - 1 5,3 0,6 0 Open circuit wash h2so4 - - - 25 ?4 way third plating plating Coating solution 0.1 1 180 0 -575 - 24 322697 201139760 E. Electroplating overvoltage in electroplating was carried out to test the effect of potential during electroplating. Since the accelerator present in the surface of the field region of the wafer and the accelerator in the surface of the through hole near their opening are stopped by the second pre-treatment, it is considered that a high plating current may be used. To prove this, electroplating was performed at the following varying potentials: -550 mV, -575 mV, and -600 mV. Other process conditions are shown in Table 5 below. The results of the experiment are shown in Figure 10, which is a photomicrograph of a series of cross-sections of the test wafer after the process. As can be seen from Figure 10, when electroplating is performed at a high negative potential of -600 mV, the plated metal (copper) is completely filled into the 20-//Μ through-holes for 30 minutes without being embedded in the plating. A void is formed in the metal. Furthermore, the adverse effects of the deposition of the plated metal on the surface of the field region of the wafer in filling the plated metal in the through-holes (the changes in the through-holes associated with the potential) are not observed. [Table 5] Process Base Additive Time Potential Current Density PEG/ mM Cl/ mM SPS/ μΜ PEI/ βΜ /s /mV.vs MSE /A/m2 Washed H2S〇4 - 30 Open First Plating Plating Solution 0.1 1 50 - 300 - -100 Washed H2S〇4 - - - 25 Open second bath h2so4 - - - 1 30 Open flush H2S〇4 - - - 25 Open third plating bath 0.1 1 - 1800 -550 , -575, -600 - 25 322697 201139760 The adsorption of the accelerator was examined by conducting a reference experiment in reverse electrolysis in a high concentration chloride ion-containing solution. F. Adsorption of the accelerator by reverse electrolysis in a high concentration chloride ion-containing solution (Reference experiment) The same basic plating solution used in the above experiment was used in this reference experiment. When the test wafer described above was immersed in the first pretreatment solution containing the accelerator of the concentration of l〇〇y 上述 as described above, the preliminary electrolytic treatment (first pretreatment) was first carried out at a current density of ΙΟΟΑ/m2 for 300 seconds. Second, in order to adsorb the accelerator from the surface of the field region of the wafer, the wafer is immersed in a treatment solution containing a high concentration of chloride ions, and the system is subjected to reverse electrolysis. After this treatment, copper plating of the wafer surface is carried out. The detailed process status is shown in Table 6 below. The results of the experiment are shown in Fig. 11, which is a photomicrograph of a series of cross sections of the test wafer after the process. [Table 6] Process Base Additive Time Potential Current Density PEG / mM Cl / m Μ SPS / β Μ / s / mV / A / m2 First plating standard 0.1 1 100 300 - -100 Second plating standard 0.1 1 - 20 100 Third plating standard 0.1 1 -- 3000 -575 26 322697 201139760 As can be seen from Figure 11, when plating is performed for 3000 seconds to fill the through-hole with the plated metal (copper), the voids are concentrated in the buried A metal (copper) towel is placed over the through hole of 2〇. If the wafer is pretreated by an accelerator desorption method, wherein the wafer is immersed in a treatment solution containing a high concentration of chloride ions while performing reverse in order to remove the accelerator from the surface of the field region of the wafer Electrolysis, this means that the main copper plating must be carried out for at least 3000 seconds. Regarding this pretreatment method, the reverse electrolysis enhances the desorption of the accelerator. Therefore, if the accelerator is applied to the adsorption pretreatment without reverse electrolysis, that is, only by immersing the wafer in the treatment solution towel, the accelerator desorption effect is sufficient, whereby the deposition of the metal coating will not It can be sufficiently suppressed in the surface of the field region of the wafer and in the surface of the through hole in the vicinity of their opening. The result of the above experiment then proves that the plated metal can be pre-processed by performing the immersion of the substrate on the substrate containing the first pre-treatment* liquid towel such as SPS accelerator, metal ion and acid, by performing Substrate immersing in a second pre-treatment of the substrate in a second pre-treatment solution comprising an additive (homogeneous agent) such as PEI, wherein the additive inhibits the effect of the addition (4) contained in the first pre-treatment solution towel, and then borrows Electroplating of the substrate is carried out by using a plating solution comprising at least - metal ions, acids and inhibitors without an accelerator, and filling the interconnect recesses of the substrate at a high rate. p. In particular, PEi is an additive (homogeneous agent) with a high sps stop effect. The sps that has been adsorbed on the surface of the substrate can be stopped by immersing the substrate in a water sulfuric acid solution containing PEI. 322697 27 201139760 A second pre-treatment of the substrate by immersing the substrate in a second pre-treatment solution containing an additive (homogeneous agent such as PEI) in accordance with the present invention has been adsorbed onto the surface of the substrate such as SPS The additive can be selectively stopped in the surface of the field region of the substrate, i.e., the surface region rather than the surface of the interconnecting recess. This condition enables selective growth of the plating metal from the bottom of the interconnecting recess. Therefore, for example, for a through hole having a direct control of 20//M and a depth of 6〇βΜ, the void-free filled plating through hole (v〇id_free via_ship ng plating) can be completed in 3 minutes, and the pre-processing time is included. The total processing time does not exceed 4 minutes. The above experimental results also indicate the ability to control the depth of the interconnect recess, which can be effectively applied to the interconnect recess by the acceleration of the accelerator in the first pre-treatment, such as sps, and the effect of the accelerator stop action. First—the effect of stopping the action of the accelerator in the pre-treatment. This condition in turn does not compensate for the ability to fill the metal, the interconnected recesses of various depths, such as trenches and through-holes, at high rates without gaps by adjusting the pre-(4) processing conditions. In particular, it is possible to achieve an intended filling of the job by changing the aspect ratio of the additive (syntax) in the second pre-treatment solution according to the aspect ratio of the interconnecting recess, the substrate soaking time, and the like. The solution disturbing condition also affects the depth of the interconnecting recess, and the acceleration stops acting on the interconnecting recess. Although the flow of the treatment solution occurs on the surface of the substrate, for example, by agitation, the thickness of the brittle layer formed near the surface of the substrate is generally inversely proportional to the velocity of the fluid. - (4) The method of treating the velocity of the fluid flowing through the surface of the substrate by using a rotating disk. In this method, the rotation of the rotating disk 322697 28 201139760 is proportional to the velocity of the fluid flowing through the surface of the rotating disk. Referring to the thickness of the diffusion layer formed on the surface of the rotating disk, the relationship between the rotational speed ω of the disk and the thickness 6 of the diffusion layer can be determined by the following formula (VG Levich et al., "Physical Chemistry and Fluid Dynamics,", New Jersey The Englewood Cliffs (NJ), Prentice-Hall (1962), analytically determined: accounted for (1), 1/66Γ1/2 (where D represents the diffusion coefficient, Wherein p represents the dynamic viscosity). Figure 12 is a graph showing the rotational speed of the rotating disk and the surface of the substrate formed in the copper sulfate/sulfuric acid solution (copper sulfate plating solution) as a copper plating solution. A diagram of the relationship between the thicknesses of the diffusion layers. In this case, because of the small, degree or diameter of the interconnecting recesses (such as trenches and through holes), fluids without processing solutions are caused by interconnecting recesses, depending on The thickness of the fluid flowing through the processing solution flowing over the surface of the substrate to form a thickness on the diffusion layer on the surface of the substrate determines the time it takes for the material to move from the point in the solution to the surface of the substrate. The material is mainly borrowed and moved by diffusion. To simplify (4), using the -dimensional model as an example, the concentration of chemical species diffusing from the surface above the diffusion layer can be determined by the solution of the diffusion equation as shown in Figure 13. In the case of sulfuric acid: the diffusion coefficient of the steel ion in the plating/excitation liquid is used as the dispersion in the diffusion equation ° ' As can be seen from Fig. 13, the longer the distance from the point above the diffusion layer' It takes more time for the chemical species to reach this point. Furthermore, it is apparent from Figure 12 that the thickness of the diffusion layer depends on the fluid of the treatment solution 322697 29 201139760. These data suggest that the stirring intensity will be (4) θ & The towel-counter treatment solution and the large (four) chemical species (accelerator) that are adsorbed to the substrate will be supplied, and vice versa, at the bottom and implementation of the second pre-pits (such as through-holes and grooves), (1) The surface + species (additive (homogeneous agent)) of the field of the warm plate will only reach the base surface, and the wide open or salt of the interconnected recess near their opening to The interconnection of the interconnecting recesses (such as the trenches and the through holes): the C: mixing solution causes the fluid of the processing solution to also be generated by the fluid in the depth direction of the physical solution to affect the moving distance of the bellows moving in the interconnecting recess. ί/Μ夕" and σ now considers that there are 1〇μΜ, 30/ζΜ* 50, respectively, and the type 3 through-holes are expected to be (4) mixed with the treatment solution. Assume that all the through holes have % ^, the degree of ice' and the treatment solution is mixed by the method of scrambled purple 卩 0.3 m / sec or the first 3 m / s paddle moving speed, and the treatment solution is determined by numerical analysis in the perforation. And the flow and state of the surface of the through hole near their opening. According to the analysis result, it can be evaluated that the pre-treatment fluid is related to the stirring intensity and the penetration intrusion is as follows. The 14 ''' member shows the relationship between the diameter of the perforation of the shell and the depth of the fluid in the treatment solution invading the through hole. In Fig. 14, the 'invasion depth (4) (10) (8) defines W treatment 4 liquid at 1 mm/sec (_/see) The velocity at which the fluid velocity flows reaches. As seen in Figure 14, when the treatment solution is scrambled at the same paddle speed of 30 322697 201139760, the depth of invasion increases with increasing the diameter of the through hole. When the solution is 1.3 mm At the purple moving speed of the second, the depth of penetration of the fluid for obtaining the second pre-treatment solution into the 50-yM through-hole is the same as the penetration depth of the through-hole of the Μ, and must be 〇3 m/ The purple movement speed of the second disturbs the solution. The fluid velocity distribution in the ice direction of the larger diameter through hole in the through hole can be similar to that of the smaller diameter through hole by using a lower stirring strength. The fluid velocity distribution. Therefore, by the second pre-processing period, the disturbing mixing strength (moving speed) of the control spoiler can be equal to the depth of the interconnecting recesses of various straight hollows or widths. The effect of the additive (homogeneous agent) in the direction. As described above, in the second pre-treatment, the flow of no solution in the recess can be controlled by controlling whether the stirring strength of the second pre-treatment solution is such that the interconnecting recess is narrow. Produced based on the stirring of the solution, or the interconnecting concave portion is wide, and the flow of the solution in the concave portion is generated according to the mixing of the solution, and is controlled by the additive (homogeneous agent) effect in the interconnecting concave portion. a range of depths in the interconnecting recess. Thus, for substrates having interconnect recesses of any size, the accelerator can be inhibited in the surface of the field region of the substrate and in the surface of the interconnecting recess near their opening The effect, on the other hand, can be maintained in the effect of the accelerator in the interconnecting recesses, especially on their bottoms. This situation allows the bottom-up growth of the plating to be completed. For those who can suppress the effect of the accelerator on the interconnecting recesses The surface depth near the opening is preferably about one-half the depth from the surface of the field region of the substrate to the bottom of the interconnect recess One-third. An additive (homogeneous agent) for suppressing the effect of the accelerator is transported by diffusing from the upper surface of the diffusion layer above the surface of the substrate from 322697 31 201139760 to the bottom of the interconnecting recess. The effect of the agent is inversely proportional to the distance from the nearest upper surface of the diffusion layer. In the electric ore, it is necessary to rapidly supply metal ions to the bottom of the interconnecting recess, and thus it is necessary to strongly disturb the ore coating solution. Therefore, the ore coating solution is electroplated. It is preferred to stir at a stirring strength equal to or higher than the stirring strength in the second pretreatment. Although SPS has been described as an accelerator, other sulfides may be used as an accelerator. Other examples of sulfides that may be used Contains the isomer of SPS 'bis 3-sulfo-2-hydroxypr〇pyl) disulfide and its sodium salt, 3_benzoxoxime _ 2_ benzothiazolyl-2-thio propylsulfonic acid and its sodium salt, 3-sulfopropyl N, N-dimethylditliiocarbamate Its sodium salt, Ο-ethyl-S- (3-sulfonic acid)-diethyl carbonate (〇_6 is more than 1-8-(3-sulfopropyl)-diethylcarbonate) and its potassium salt, thiourea and its derivatives. Although PEI has been described as an additive (homogeneous agent), other compounds for suppressing the effect of the accelerator may be used. Examples of such compounds include nitrogen-containing polymers such as, for example, polyvinyl pyrrolidone or derivatives thereof, and Janus Green B, which has been conventionally used as a homogenizing agent. Cationic polymer; guanamine compound; thioguanamine compound; compound with aniline or bite ring; 32 322697 201139760 heterocyclic compound; simple heterocyclic compound; and aminocarboxylic acid 〇 although already illustrated Women as inhibitors of forging' may use other inhibitors. Examples of other inhibitors which may be used include polypropylene glycol, a copolymer of ethyl alcohol and propylene glycol (C〇P〇lymer) and derivatives thereof, polyethylene glycol, methyl cellulose, and the like. For example, a through hole having a diameter of 20/m and a depth of 6 〇/ζι is used in the above experiment. For the through holes of the same diameter but having a large depth, the gap-free filling of the perforated plating can be carried out by increasing the concentration of the additive (homogeneous agent) in the second pretreatment solution or extending the substrate soaking time in the second pretreatment. In the experimental example, the time for soaking the second pre-treated solution substrate was, for example, 5 seconds. Such short substrate soaking times may be inappropriate from the standpoint of low regenerability in actual devices. Thus, it is preferred to set a longer substrate soaking time. For the through holes having the same diameter and the same depth, the substrate soaking time can be appropriately extended by reducing the concentration of the additive (homogeneous agent) in the second pretreatment solution. For a substrate having through holes having various diameters and depths, or having a groove having various diameters and depths, an appropriate additive (homogeneous agent) in the second pretreatment solution can be determined by performing a shovel test of the same substrate in advance. The concentration and the appropriate substrate soak time in the second pre-treatment. It is also possible to determine the concentration of the appropriate additive (homogeneous agent) in the second pretreatment solution of the substrate having various widths or diameters and various depths of the through holes or trenches based on the results of the comparison test and the results of the diffusion analysis. The appropriate substrate soaking time in the two pre-treatments. It is possible to provide an additive (homogeneous agent) which can automatically control the substrate soaking time and the second pretreatment in the second pretreatment solution by using a database storing 33 322697 201139760 such S-type results and analysis results. Concentration plating device. Although the present invention has been described in detail with reference to the preferred embodiments thereof, it is understood that the invention is not limited to the embodiments described above, but various changes and modifications can be made within the scope of the inventive concept presented herein. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a general plan rm · circle of a plating apparatus according to an embodiment of the present invention, and FIG. 2 is a first pre-processing unit provided in a plating apparatus shown in FIG. Figure 3 is a schematic diagram of a second pre-processing unit disposed in the money-carrying device shown in Figure j; Figure 4 shows the settings in the first! A schematic diagram of the keying unit in the ore-covering device in the figure; Figures 5 to 5C are diagrams illustrating the use of the first! The keying device shown in the figure is a diagram of the sequence of the steps of the process of filling the plating metal with the interconnected recess; FIG. 6 is a microscopic slice of the cross-section of the series of test wafers after the electric ore. The result of the verification experiment of the preliminary electrolysis condition in the first pretreatment; the microscopic pretreatment solution of the series cross section is added to the seventh picture to test a piece of the wafer after electroplating, which is displayed in the first pretreatment. The result of the verification experiment of the concentration of the first speed agent; Fig. 8 is the photomicrograph of the electroplating test wafer - 322697 34 201139760 - sheet, shown in the second pre-treatment in the second pre-treatment The result of the verification experiment of the concentration of the additive in the solution (homogeneous agent); Figure 9 is a photomicrograph of a series of cross sections of the test wafer after electroplating, showing the verification experiment of the wafer soaking time in the second pretreatment Figure 10 is a photomicrograph of a series of cross-sections of the test wafer after electroplating, showing the results of the verification test on over-voltage plating in electroplating; Figure 11 is a test wafer after electroplating A series of micrographs showing cross-sections showing the results of a verification experiment of desorption of accelerators by reverse electrolysis in a solution containing a high concentration of chloride ions, as a reference experiment; Figure 12 shows the rotation of a rotating disc A graph of the relationship between the velocity and the thickness of the diffusion layer formed on the surface of the substrate in the copper sulfate plating solution; Figure 13 is a graph showing the relationship between the depth from the upper surface of the diffusion layer and the normalized concentration of the chemical species. Fig. 14 and Fig. 14 are diagrams showing the relationship between the diameter of the through hole and the depth of the fluid of the treatment solution invading the through hole. [Main component symbol description] 10 seed layer 12 interconnection recess 14 plating metal 20 plating device 22 loading/unloading portion 24 first pre-processing unit 35 322697 201139760 26 28 30a, 30b, 30c second pre-processing unit plating Cover unit cleaning unit 32 cleaning/drying unit 34 substrate stage 36 first substrate conveying device 38 second substrate conveying device 40 control portion 42 first pre-treatment solution 44, 62 processing grooves 46, 64, 74 vertical movable substrate holder 48 ' 76 Anode holder 50, 78 Anode 52 Stirring mechanism 54, 68, 82 Stirring paddle 56a, 56b, 84a, 84b Wire 58 Power supply 60 Second pre-treatment solution 66, 80 Stirring mechanism 70 Plating solution 72 Plating groove 86 Plating Power Supply 90 Accelerator 92 Additive (Homogeneous Agent) W Substrate 36 322697