1298750 九、發明說明： 【發明所屬之技術領域】 本發日⑽《於-種雜液與钱方法’且特财關於—種在積體電 :路製造過程中用來沉積金屬層(特別是鋼)的電鍍液與電鍍方法。 • 【先前技術】 隨料導體元件尺寸的不嶋似及碰電路_度錢提升，電路 中各元件電連接的赫性磁之增加，因―要—絲將金屬導線電連接 #圖案的尺寸及位置作出精確控制的製程。而隨著黃光與 刻製程，例如反應性離子酬RI戦其他電漿爛製程的進步;產品^導 線Μ的寬度與間距亦已經進人次微米的範圍。在碰電路及平面顯示器 •製造過程中’利用電沉積或電鍍來形成金屬層是各種沉積方法中最呈潛力 滑、平整且均句的上表面，因此，目前業界多半係針對電鐘硬體及化學組 成的設計來進行努力，以企形成一個能均勻覆蓋整個基底表面，並能填入 微小間隙的高品質薄膜，其中又以利用銅作為電鑛金屬具有特別的優勢。 φ W知驗技術大乡侧歸_料雜財駐要電㈣，而電鐘 浴溶液則夕半會另包含有一些其他的添力口劑，例如氯離子及平整劑 (leveler) ’並可藉由加人促進劑⑽derat〇r)或抑制劑(s卿res 加或減《雜歡速率。而健射這些錢添加細濃賴對基底上 銅沉積之速率與,口口質，以及所產生的金屬化電性表現與物理特性有關鍵性 的&曰；、:而省知的抑制劑卻具有一些缺點，例如會降低電鍍浴溶液對基 .•底表面種晶層之濕潤性，而當電鍍浴溶液對種晶層之濕潤性不均句時，將 會使鐘在種晶層上的金屬層產生—些結構性的缺陷。 為了解决上述問題，本案發明人於中華期5專游請案寶侧彻啊 請日··民國94年3月8日）中曾於提出一種改良的電鐵化學組成與方法，以 0503-A30958TWF;esmond 5 1298750 改=底上麵金屬的溝槽填充能力並減少金屬表面的缺陷。在此篇專利 =本中係使用環氧乙烷_環氧丙齡&細〜獅调pylene 〇xide; E〇_p〇) ’、作為抑制添力口劑，來增加電錢液對基底表面之晶種層的濕潤度，因 而加強其溝槽填絲力並減少電絲面的凹坑(pits)。 EO-PO共聚物在電鍍液中的溶解度跟其所含的兩種單體的組成比例有 ^一般而言，溶解度會隨著E〇的比例提高而上升(因為E0的親水性較 冋）’因此’為了保持足夠的溶解度，E〇的組成比例通常不會低於俱。 然而、，本案發明人發現，雖然提高EO的比例有助於提高溶解度，但如此一 來Ά致抑f]效果交差’特別是溝槽頂端的抑制能力明顯不足，因此會出 斤月底口F工/同(bottom void)、側壁空洞(sidewall v〇id)、或是化學機械研 磨(CMP)後出現凹坑㈣s)等瑕疫，這些問題在衫奈米以下的銅製程中將更 形嚴重。 本么月便疋針對上述問題而提出一種新穎的電鐘液與電鍍方 =，以=在提高抑制劑溶解度的同時仍然保有優異的抑制效果。然而，應 特別注意岐，社㈣現前EapQ抑·關題猶此麟倾之公^ 技，而是本案發明人在研究過程中之發現。 【發明内容】 根據上述’本發明之目的在於提供—種電麟與賴綠，以提高 制劑✓谷解度並同時保有優異的抑制效果。 。 在一較佳實施例中，本發明之電鐘液包括：一電解質溶液；以及一胺 基環氧淡魏硫絲物(amine_bas_撕-ly·)，添加於該電解 負/奋液中，且該絲共聚物至少含有重量比例惠之環氧丙燒。 ^在另-較佳實施例中，本發明之電鍍液包括：一電解質溶液；一胺基 環氧乙烷-環氧丙烷共聚物㈣ne_based Ε〇·卿〇切贈）其至少含有‘ 比例70%之環氧丙烧，添加於該電解質溶液中作為第一抑制劑「以及一= 0503-A30958TWF;esmond 6 1298750 氧乙燒-環氧丙院共聚帅〇_PO鄉。Iymer)，其至少含有重量比例·。之環 乳乙烷，添加於該電解質溶液中作為第二抑制劑。 在i佳實施例中’本發明之麵方法包括下列步驟：提供—電鐘浴， 其包含前述任-實施例之_液；將—基底浸人該電鑛料，·以及由該電 鍍液電鐵一金屬於該基板上。 為縣發明之上述和其他目的、特徵、和優點能更明顯紐，下文特 舉出較佳實麵’並配合所關式，作詳減明如下·· 【實施方式】 本發明之触實施儀於半·造過財，在半導體基底表面 銅晶，層的上方電鑛一銅金屬層，然而本發明並可進一步應用於基底上並 2金屬的電化學電鍍，而非限於銅。此外，本發明之應用範圍亦不限料 導體製造，而可為其他之工業上之應用。 ' 以下將就本㈣之f鍍液與驗方法作進_步描述，射 減量百分比。在本剌之較佳實施财，可萌決習知電鑛 佩生的不對稱沉積或空洞等問題，在45奈米下的間隙仍維持良好的填 充能力。本發日_是使祕有高ρο含量的胺基環氧说環氧丙烧共聚 物(amine-based EO-PO copolymer)作為抑制劑。—方面高ρ〇含接古 其抑制能力’避免溝_部提早封口而將空洞包覆其中，另—方面: 的存在可以提高抑制劑在電鍍液中的溶解度。 土 相較於-般财〇共聚物，絲EO_p〇共聚物具有明顯優異的 (或濁點）。-般的咖〇共聚物，㈣含量大於㈣時，其在G ς 下的濁點(cl〇UdP〇int)it常不超過聰;她之下，胺基Ε〇_ρ〇 伟 Ρ〇含量高達慨’其在αι%酸浴τ_域可高於耽。== 明所使用的胺基卿α絲物至少可含有7_ 浴解度。在本發明之較佳實施例中，胺基Ε〇·ρ〇共聚物約含有⑽魏的 0503-A30958TWF;esmond 7 1298750 PO與5_2〇°/0的EO。雖然在先前技藝中，美國專利us 6531〇46號、us 0773568 號、US 6444110 號曾使用 amine)_ 抑制劑’但是本發明所使用之胺基Εαρ〇共聚物與其高p〇含量之特徵則 是此技術領域中前所未見。 : 適用於本發明之胺基Εαρ〇共聚物包括核心結構具有烯烴二胺 -(al1 冰ene dlamme)之 Ε〇-ρ0 共聚物，例如乙二胺(ethylene diamine)之 ΕΟ-ΡΟ ^ 承物另方面，亦可使用末端結構具有烧基胺(alkyl amine)之EO-PO共 水物例如末‘為12烧基fe：(lauryl amine)或動物脂胺(tallow amine)之EO-PO ® ，、♦物本發明之共聚物可為區段式共聚物(block copolymer)、無規共聚物 (random copol卿er)、或父替式共聚物㈤抬瓜如把c叩〇1仰沈）。在各種胺基 EO-PO共聚物中，又以乙二胺之E〇_p〇區段式共聚物(又稱為ρ〇ι〇删㈣ 效果#寸別好此類型的商業化產品包括Sino-Japan Chemical公司的SNOPOL TE 系列、BASF 公司的 Tetronic 系列、Asahi Denka Kogyo 公司的 ADEKANOL TR系列。胺基Εαρ〇共聚物的重量平均分子量較佳在 2，_】，_之間，更佳在3,000-5,000之間。 在本發明較佳實施例中，上述的胺基E〇_p〇共聚物最好搭配第二個抑 φ制劑一併使用。第二抑制劑最好是EO含量60%以上的EO-PO共聚物。雖 然南PO含量的抑制劑可以提高溝槽填充能力，但是卻會將電解質溶液的界 面張力降低到3(M〇 dyne/cm2。界面張力太低會產生泡床，導致晶圓表面沿 著曰曰圓旋轉方向形成一系列排成弧線的凹坑(pits)。因此，在本發明中可視’ 需要加入E〇含量大於60%的第二抑制劑，以將界面張力提高到5〇_6〇 ’ dyne/em2。兩種_細組合可以提高電鍍的填雜力，又同時轉高的界 -面張力以濕潤晶種層表面，避免產生凹坑。 本發明之電鍍液與方法可適用於各種金屬之電鍍，例如銅、鋁、鎳、 鉻鋅錫金、報、錯以及鏡，本發明亦可適用於含有數種金屬的電鑛， 但以銅合金電链較佳，尤其是銅電鍍。銅電鍍液之化學組成應已為熟習相 0503-A30958TWF；esm〇nd 8 1298750 關技藝者所熟知，通常包含有一電解質以及一個或多個銅離子來源，但不 以此為限，而適合的電解質則包含有硫酸(sulfUricacid)、醋酸(aceticadd)、 氟硼酸(fluoroboric acid)、曱磺酸(methane sulfonic acid)、乙磺酸(她咖 sulfonic acid)、三氟甲磺酸(砸u〇rmethane sulf〇nic add)、苯磺酸⑽㈣ sulfomc aC1d)、甲硫酸(methyl sulf〇nic add)、對甲苯績酸她聊犯腕 acid)、氫氯酸(hydrocWoncacid)、磷酸(ph〇sph〇ricacid]等，但並不以此為限， 而可包含有其他類型之電解質’而電鐘液中酸的濃度約為每公升i至· 克，此外，這些酸可另包含有一鹵素離子來源，例如氯離子。適當的銅離 子來源可為；5贏銅、氯化銅、酸銅、石肖酸銅、氣蝴酸銅、甲確酸銅、苯 猶_及射料_ ’缝砂此雜，而w其他麵的銅離子 來源’且電鑛液中銅的濃度通常約為每公升1〇至3〇〇克。 胺土 EOPO，、永物（作為第一抑制劑）在電鑛液争的濃度較佳約 100 300ppm冋EO含夏的E〇_p〇共聚物(作為第二抑制劑)在電鑛液中的 濃度較佳約测0ppm。此外，電鍍液中亦可加入濃度2_5〇鹏的 此促進劑可為各種朗之促補，以加速金屬的電鍍沉積過程。 本發明中細編程猶餅包含有：電鐘 至灣；麵流約騎平方公分Μ至 ^ in z, qc - 毛文J口，以及電鍍>合溶液溫 二全屬進 又’料，若需要彻鱗機械研磨(CMP)製程來對受 狀電麟絲㈣加人濃躺為5咖规至5 mol/L之平整劑。 立' 0 請參照第1圖，第！圖中 系統H)，系統H)可為-習知㈣m用末贿本發明的電化學電錄 標準電鍍室、，浴容;14钱—=含有Γ具有—可_流源12之 係為-欲進行銅_之半導體V 116以及陰極18，其中陰極18 等體日日片基底。％極16與陰極18公別細山 的導線38連接到可調式綠源12，電齡容器 由適當 浴溶液2〇。電化學電鍍㈣ 、J虞有—電解質電錄 系統10更可進一步包含有一旋轉裝置，以在電錢過 0503-A30958TWF;esmond 1298750 程中使基底18在電解質電鑛浴溶液2〇内旋轉，此部分應已為熟習該項技 術者所熟知，故在此不予贅述。 化學電鐘系統K)可另包含有-對繞流過濾導管24、一繞流幫浦/過渡 '器30以及一電解液儲存槽34,以在需要的時候將額外的電解質導入電鍍浴 :容器14内。繞流過濾導管Μ通常會延伸過陽極16，且於朝陽極16上方氧 ^ 化表面22的兩端設有開口，繞流過濾導管24係連接至位於電解液儲存槽 —W卜的繞流幫浦/過渡器30，而繞流幫浦/過渡器3〇則係藉由一儲存槽輸入 f路32來連接到電解液儲存槽34，而電解液儲存槽34則藉由儲存槽輸出 •鴻36連接到電鍍浴容器14。在此，所要再次強調的是，前述之電化學電 鍍系統10僅係為各種適用於本發日月的系統中之一例，本發明仍可利用其他 ，- 設計之系統來達成。 〃 請繼續參閱第1-3圖、如第3圖中步驟S1所示，根據本發明之方法， 一金屬晶種層19，例如銅，已預先沉積於晶片基底18上，其中金屬晶種層 19可根據習知技術中的方法來沉積於基底i8上，例如可採用一化學氣相沉 積製耘或一物理氣相沉積製程來進行，且金屬晶種層19之厚度約為^至 1500 埃(angstrom) 〇 接著，如第3圖中步驟S2所示，將電解質電鍍液2〇置於電鍍浴容器 14内，通常電解質電鐘液20内會含有濃度約為每公升5毫 莫耳(mol)之促進劑，並可能含有濃度約為每公升5毫莫耳至'5莫耳之平整 劑或其他添加劑。接著如第3圖中步驟S3所示，將高p〇含量之胺 基EO-PO共聚物汸一抑制劑)與高E〇含量㈣％)的E〇_p〇共聚物(第二抑 麵/選擇性添加)添加至電觀2〇巾，並與電鑛液2〇戈全混合。隨後再將 陽極16與基底18浸入賴浴溶液2〇内，並經由導線3δ連^到=電 流源12〇 口工 如第3圖之步驟S4所示，當將陰極/基底18浸入電鍍浴溶液2〇内後， 基底18上之晶種層19會與電鑛浴溶液.2〇，接觸，此時，電鑛洛溶液會 0503-A30958TWF;esmond 10 1298750 將晶種層19的整個表面完全 ^ 21 ；9 0Til ^ ^ 加熱到約摄PMn z；。— 叙而έ，會將電鍍浴溶液20 12將在常m 5又而在物雜學槪魏1G的操辦，電流源 位imr壓之電位差至陽極16與陰極/基底18上，這電 衣％陽極16與陰極/基底Μ之磁場，並進一步费塑 谷液20中銅離子的分佈狀況。在 ，^，叉〜 2伏特，時門約9八# 又電鍍躺應用上，所加加之電位約為 安立、、”、里而所使用之電艘電流約為每平方公分0.2至2〇毫 女士口 ’基底18的轉速約為备八於 面22處_將會縣奸 口此’在祕16的氧化表 陰極/晶片社界面處形成==原，亚於硫酸銅電鑛浴編與 溝2〇能完全濕化晶種層19的整個表面而且具有較佳之 續二·：=:本= 雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本 明，任何«此技藝者，林麟本㈣之精神和範肋，當可作任X 更動與潤飾’耻本發明之倾麵#視後附之巾料補騎界定:為 【圖式簡單說明】 第1圖為本發明實施辦—電化學麵搞之示意圖。 第2圖係顯示本發明實施例帽—金屬層電鍍至基底之剖面示意圖 第3圖係顯示本發明實施例东之電鍍友法之流穩亂。 0503-A30958TWF,*esmond 11 1298750 【主要元件符號說明】 ίο〜電化學電鍍系統； 14〜電鍍浴容器； 18〜陰極； 20〜電鍍浴溶液； 22〜氧化表面； 30〜繞流幫浦/過濾器； 34〜電解液儲存槽； 38〜導線； 12〜電流源； 16〜陽極； 19〜晶種層； 21〜金屬層； 24〜繞流過濾導管； 32〜儲存槽輸入管路； 36〜儲存槽輸出管路； S1-S5〜電鍍之流程步驟1298750 IX. Description of the invention: [Technical field to which the invention belongs] This issue (10) "In the case of a kind of miscellaneous liquid and money" and special wealth related to - in the integrated body: road manufacturing process used to deposit metal layers (especially Steel) plating solution and plating method. • [Prior Art] The size of the incoming conductor components is different and the circuit is increased. The increase in the magnetic properties of the components in the circuit is increased by the size of the wire. The process of making precise control of the position. With the progress of yellow light and engraving process, such as reactive ion RI, other plasma smashing process; the width and spacing of the product wire Μ have also entered the sub-micron range. In the process of manufacturing touch screens and flat-panel displays, the use of electrodeposition or electroplating to form metal layers is the most potential smooth, flat and uniform upper surface of various deposition methods. Therefore, most of the current industry is aimed at electric clock hardware and The chemical composition is designed to work hard to form a high-quality film that uniformly covers the entire substrate surface and can be filled with minute gaps, which in turn has particular advantages in utilizing copper as an electro-mineral metal. φ W knowledge technology Daxiang side return _ material miscellaneous money resident electricity (four), while the electric clock bath solution will include some other additional force agent, such as chloride ion and leveler. By adding a promoter (10) derat〇r) or an inhibitor (sqing res plus or minus the rate of miscellaneous joy. And the shot of the money to add a fine concentration on the rate of copper deposition on the substrate, oral taste, and produced The metallization electrical properties and physical properties are critical &:;, and the known inhibitors have some disadvantages, such as reducing the wettability of the plating bath solution on the base layer. When the electroplating bath solution is uneven on the wettability of the seed layer, it will cause some structural defects in the metal layer on the seed layer. In order to solve the above problems, the inventor of the present invention has visited the Chinese period 5 In the case of the case, please go to the Republic of China on March 8th, 1994.) I have proposed an improved composition and method of electric iron, which is modified by 0503-A30958TWF; esmond 5 1298750 Ability and reduce defects on metal surfaces. In this patent = the use of ethylene oxide _epoxy propylene age & fine ~ lion tone pylene 〇 xide; E 〇 _p 〇) ', as a suppressive force agent to increase the liquid money to the substrate The wetness of the seed layer of the surface thus strengthens its groove filling force and reduces the pits of the wire surface. The solubility of the EO-PO copolymer in the plating solution is different from the composition ratio of the two monomers contained therein. Generally, the solubility increases as the ratio of E〇 increases (because the hydrophilicity of E0 is relatively low). Therefore, in order to maintain sufficient solubility, the composition ratio of E〇 is usually not lower than that. However, the inventor of the present invention found that although increasing the proportion of EO contributes to the improvement of solubility, the effect of the effect of the EOf] is particularly poor, especially the inhibition ability of the top of the groove is obviously insufficient, so the bottom of the mouth will be /Bottom void, sidewall v〇id, or pits (4) s) after chemical mechanical polishing (CMP), these problems will be more serious in the copper process below the shirt. In this month's note, a novel electric clock solution and electroplating method are proposed for the above problems to reduce the solubility of the inhibitor while still maintaining excellent suppression. However, special attention should be paid to the fact that the company (4) is currently the EapQ and the title is still the public technology, but the discovery of the inventor in the research process. SUMMARY OF THE INVENTION According to the above-mentioned invention, it is an object of the invention to provide a kind of electric lining and lysine to improve the degree of solution of the preparation ✓ while maintaining an excellent inhibitory effect. . In a preferred embodiment, the electric clock solution of the present invention comprises: an electrolyte solution; and an amine-based epoxy fluorescein (amine_bas_ tear-ly·), which is added to the electrolytic negative/exciting liquid, And the silk copolymer contains at least a weight ratio of propylene oxide. In another preferred embodiment, the electroplating bath of the present invention comprises: an electrolyte solution; an amine-based ethylene oxide-propylene oxide copolymer (IV) ne_based Ε〇·〇〇〇), which contains at least a ratio of 70% The propylene-acrylic acid is added to the electrolyte solution as the first inhibitor "and one = 0503-A30958TWF; esmond 6 1298750 oxy-ethene-epoxy propylene copolymer _PO township. Iymer), which contains at least the weight a ratio of cyclohexane, added to the electrolyte solution as a second inhibitor. In a preferred embodiment, the method of the present invention comprises the steps of: providing an electric clock bath comprising the foregoing any of the examples The liquid is immersed in the substrate, and the electroplating liquid is electroplated with a metal on the substrate. The above and other objects, features, and advantages of the invention are more obvious. The preferred embodiment is the same as that of the closed type, and the details are as follows: [Embodiment] The touch implement of the present invention is made in the middle of the semiconductor substrate, and the copper is crystallized on the surface of the semiconductor substrate. Metal layer, however the invention can be further applied to the base Electrochemical plating of the metal is not limited to copper. In addition, the application range of the present invention is not limited to the manufacture of conductors, but can be applied to other industries. 'The following will be the plating and testing of the (f) f The method is described in step _step, the percentage of shot reduction. In the better implementation of this book, it can be used to determine the asymmetric deposition or void of the electric ore, and maintain a good filling in the gap of 45 nm. Capability. This is the use of amine-based EO-PO copolymer as an inhibitor to improve the content of high-efficiency. Avoid the groove sealing part to cover the cavity early, and the other side: can improve the solubility of the inhibitor in the plating solution. The soil phase is superior to the general-purpose copolymer, the silk EO_p〇 copolymer is obviously excellent. (or cloud point). - The general curry copolymer, (4) When the content is greater than (4), its cloud point (cl〇UdP〇int)it under G 常 often does not exceed Cong; under her, amine Ε〇 _ 〇 〇 Ρ〇 Ρ〇 Ρ〇 高达 慨 慨 慨 慨 慨 慨 慨 慨 慨 慨 其 其 α α α α α α α α α α α The kiwi alpha filament may contain at least 7_bath resolution. In a preferred embodiment of the invention, the amine ruthenium rhodium copolymer contains about (10) Wei's 0503-A30958TWF; esmond 7 1298750 PO and 5_2 〇 °/ EO of 0. Although in the prior art, U.S. Patent Nos. 6,531,430, US Pat. No. 6,773,568, US Pat. No. 6,444,110 have used amine) inhibitors, but the amine Εαρ〇 copolymers used in the present invention and their high p〇 content The characteristics are unprecedented in the art.: The amine-based Εαρ〇 copolymer suitable for use in the present invention comprises a Ε〇-ρ0 copolymer having a core structure having an olefin diamine-(al1 ice ene dlamme), such as ethylene Amine (ethylene diamine) - ΡΟ ^ In other respects, it is also possible to use an EO-PO eutrophic compound having an alkylamine at the terminal structure, for example, a 12-base fe: (lauryl amine) or an animal. EO-PO ® of the tallow amine, the copolymer of the present invention may be a block copolymer, a random copolymer, or a parent copolymer (5) Lifting the melon like sinking c叩〇1). In various amine-based EO-PO copolymers, E〇_p〇 segmental copolymers of ethylenediamine (also known as ρ〇ι〇) (four) effect #寸别别 This type of commercial products include Sino -SNOPOL TE series from Japan Chemical Co., Tetronic series from BASF, and ADEKANOL TR series from Asahi Denka Kogyo Co., Ltd. The weight average molecular weight of the amine Εαρ〇 copolymer is preferably between 2, _, _, more preferably 3,000. In a preferred embodiment of the invention, the above-mentioned amine-based E〇_p〇 copolymer is preferably used in combination with a second φ-reducing agent. The second inhibitor preferably has an EO content of 60% or more. EO-PO copolymer. Although the inhibitor of South PO content can improve the groove filling ability, it will reduce the interfacial tension of the electrolyte solution to 3 (M〇dyne/cm2. If the interfacial tension is too low, a bubble bed will be generated, resulting in The surface of the wafer forms a series of arc-shaped pits along the direction of the circle rotation. Therefore, in the present invention, it is possible to add a second inhibitor having an E〇 content of more than 60% to improve the interfacial tension. To 5〇_6〇' dyne/em2. Two _ fine combinations can be improved The plating filling force, at the same time, increases the boundary-surface tension to wet the surface of the seed layer to avoid pits. The plating solution and method of the invention can be applied to the plating of various metals, such as copper, aluminum, nickel, chromium. Zinc tin gold, newspaper, error and mirror, the invention can also be applied to electric ore containing several metals, but copper alloy electric chain is preferred, especially copper electroplating. The chemical composition of copper electroplating solution should be familiar with 0503- A30958TWF; esm〇nd 8 1298750 is well known to those skilled in the art and usually contains an electrolyte and one or more sources of copper ions, but not limited thereto, and suitable electrolytes include sulfuric acid (sulfuric acid), acetic acid (aceticadd), Fluoroboric acid, methane sulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid (10) (tetra) sulfomc aC1d), Methyl sulfonate (methyl sulf〇nic add), p-toluene acid, she talks about wrist acid), hydrochloric acid (hydrocWoncacid), phosphoric acid (ph〇sph〇ricacid), etc., but not limited to this, but may include Other types of electrolytes The concentration is about i to gram per liter. In addition, these acids may additionally contain a source of halogen ions, such as chloride ions. Suitable sources of copper ions may be; 5 win copper, copper chloride, copper acid, copper silicate , gas sulphuric acid copper, copper sulphate, benzene _ and _ _ _ sew sand this miscellaneous, and w other sources of copper ions 'and the concentration of copper in the electric ore is usually about 1 〇 to 3 per liter Mike. The amine EOPO, the permanent substance (as the first inhibitor) is preferably concentrated in an electric ore solution at a concentration of about 100 300 ppm 冋 EO containing summer E〇_p〇 copolymer (as a second inhibitor) in the electric ore solution. The concentration is preferably about 0 ppm. In addition, the promoter can also be added to the plating solution at a concentration of 2_5 〇鹏, which can be used to accelerate the electroplating deposition process of the metal. The fine programming of the present invention includes: an electric clock to the bay; the surface flow is about to ride a square centimeter to ^ in z, qc - the hairy J mouth, and the plating > the solution temperature is all in the same as the material, if A scale mechanical grinding (CMP) process is required to add a leveling agent of 5 gram to 5 mol/L to the acantron.立' 0 Please refer to Figure 1, the first! In the figure, system H), system H) can be - conventionally known as (four) m with the bribe of the invention, the electrochemical electro-recording standard plating chamber, bath capacity; 14 money - = containing Γ has - can be - source 12 is - The semiconductor V 116 and the cathode 18 are to be subjected to copper, and the cathode 18 is a body substrate. The wire 38 of the % pole 16 and the cathode 18 are connected to the adjustable green source 12, and the electrical age container is 2 适当 from the appropriate bath solution. Electrochemical plating (4), J-electrolyte recording system 10 may further comprise a rotating device for rotating the substrate 18 in the electrolyte electric bath solution 2 在 in the process of electricity exchange 0503-A30958TWF; esmond 1298750, Some of them should be familiar to those skilled in the art and therefore will not be repeated here. The chemical clock system K) may further comprise a pair of bypass filter conduits 24, a bypass pump/transition unit 30 and an electrolyte reservoir 34 for introducing additional electrolyte into the plating bath as needed: container 14 inside. The bypass filter conduit Μ generally extends through the anode 16 and is provided with openings at both ends of the oxidization surface 22 above the anode 16. The bypass filter conduit 24 is connected to a flow bypass located in the electrolyte storage tank. The pump/transition unit 30 and the bypass pump/transition unit 3 are connected to the electrolyte storage tank 34 by a storage tank input f path 32, and the electrolyte storage tank 34 is output through the storage tank. 36 is connected to the plating bath vessel 14. Here, it is to be emphasized again that the electrochemical plating system 10 described above is only one of various systems suitable for use in the present invention, and the present invention can be achieved by other systems of design. Continuing to refer to Figures 1-3, as shown in step S1 of Figure 3, a metal seed layer 19, such as copper, has been previously deposited on the wafer substrate 18 in accordance with the method of the present invention, wherein the metal seed layer 19 can be deposited on the substrate i8 according to a method in the prior art, for example, by a chemical vapor deposition or a physical vapor deposition process, and the thickness of the metal seed layer 19 is about 1.25 to 1500 Å. (angstrom) Next, as shown in step S2 in Fig. 3, the electrolyte plating solution 2 is placed in the plating bath vessel 14, and usually the electrolyte clock solution 20 contains a concentration of about 5 millimoles per liter (mol). Promoter, and may contain a leveling agent or other additive at a concentration of from about 5 millimolar to about 5 moles per liter. Next, as shown in step S3 of Figure 3, the high-p〇 content of the amine-based EO-PO copolymer 汸-inhibitor) and the high E 〇 content (four%)% of the E〇_p〇 copolymer (second suppressor) / Selectively added) Add to the electric 2 wipes and mix thoroughly with the electric ore. Then, the anode 16 and the substrate 18 are immersed in the bath solution 2, and connected to the current source 12 via the wire 3δ, as shown in step S4 of FIG. 3, when the cathode/substrate 18 is immersed in the plating bath solution. After 2 〇, the seed layer 19 on the substrate 18 will be in contact with the electric ore bath solution. 2〇, at this time, the electro-mine solution will be 0503-A30958TWF; esmond 10 1298750 will completely cover the entire surface of the seed layer 19. 21 ; 9 0Til ^ ^ Heated to approximately PMn z; — 叙 έ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The magnetic field of the anode 16 and the cathode/substrate is further reduced by the distribution of copper ions in the valley liquid 20. In, ^, fork ~ 2 volts, time gate about 9 eight # and electroplating application, the applied potential is about Anli, ", and the current used in the electric boat is about 0.2 to 2 每 per square centimeter The opening speed of the woman's mouth 'base 18 is about 20 in the face of the surface _ will be the county rape mouth this 'in the secret 16 oxidation table cathode / wafer interface interface == original, sub-copper sulfate electric mine bath and groove 2 〇 can completely wet the entire surface of the seed layer 19 and has a better continuation of the second:: =: This = although the invention has been disclosed above in several preferred embodiments, but it is not intended to limit the invention, any « This artist, Lin Linben (four) spirit and Fan Ri, can be used as X change and retouching 'shame of the invention' of the face # 视后附巾料补骑 definition: for [schematic simple description] Figure 1 The embodiment of the present invention is a schematic diagram of an electrochemical surface. Fig. 2 is a schematic cross-sectional view showing the plating of a cap-metal layer to a substrate according to an embodiment of the present invention. Fig. 3 is a view showing the flow of the electroplating method of the embodiment of the present invention. 0503-A30958TWF, *esmond 11 1298750 [Main component symbol description] ίο~electrochemical plating system 14~ electroplating bath container; 18~ cathode; 20~ electroplating bath solution; 22~ oxidized surface; 30~ bypass pump/filter; 34~ electrolyte storage tank; 38~ wire; 12~ current source; 19~ seed layer; 21~metal layer; 24~ bypass filter conduit; 32~ storage tank input pipeline; 36~ storage tank output pipeline; S1-S5~ plating process step
0503-A30958TWF;esmond 120503-A30958TWF; esmond 12