TW516120B - Seed layer - Google Patents

Seed layer Download PDF

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Publication number
TW516120B
TW516120B TW090126460A TW90126460A TW516120B TW 516120 B TW516120 B TW 516120B TW 090126460 A TW090126460 A TW 090126460A TW 90126460 A TW90126460 A TW 90126460A TW 516120 B TW516120 B TW 516120B
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TW
Taiwan
Prior art keywords
copper
seed layer
steel
metal
scope
Prior art date
Application number
TW090126460A
Other languages
Chinese (zh)
Inventor
David Merricks
Denis Morrissey
Martin W Bayes
Mark Lefebvre
James G Shelnut
Original Assignee
Shipley Co Llc
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Publication of TW516120B publication Critical patent/TW516120B/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76868—Forming or treating discontinuous thin films, e.g. repair, enhancement or reinforcement of discontinuous thin films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating

Abstract

Disclosed are methods for repairing or enhancing discontinuous metal seed layers prior to subsequent metallization during the manufacture of electronic devices. Such repair methods do not require the use of a second electroplating bath.

Description

516120 A7 B7 經濟部智慧財產局員工消費合作社印製 1 五、發明說明（1 [發明背景] 本發明主要是有關於針對後期金屬化處理的晶種層之 技術湏域更特別的是，本發明是有關於金屬化處理之前 的晶種層修補之方法。 目鈾的小型微電子裝置，諸如次微米幾何形狀，都已 趨向含多重金屬化處理層以做更高密度之處理。一般用以 形成金屬線於半導體晶圓上的金屬，也是一般稱之為配線 (wiring)’疋鋁。鋁的優點在於價格相當便宜，電阻係數低， 非常容易作蝕刻處理。鋁也用來作導通孔（via)的互連線以 便連接不同的金屬層。然而，雖然導通孔/接觸孔之大小縮 至次微米的範圍，但也造成階段覆蓋（step c〇verage)之問 題，轉而當使用鋁來做不同金屬層之間的互連時，則產生 穩定性之問題。這樣的不良階段覆蓋造成高電流密度並且 也促使電子遷移（electromigration)的提高。 有種方法可&供導通孔的改良互連路徑，它可於使 用銘來作為金屬層時而利用諸如鎢這類的金屬來形成完整 的填充塞（filled plug)。然而，鎢製程不合乎成本且較複 雜，鎢的電阻係數高，而且鎢塞孔（tungstenplug)易造成空 隙與接線層的不良介面。 銅可作為積體電路製造的互連金屬化處理之取代材 料。銅的優點是電性特性比鎢還要更好，較佳的電子遷移 特性以及比鋁還要低的電阻係數。其缺點是比鋁與鶴還要 難做餘刻處理並且易遷移至諸如二氧化碎等介電層。為了 避免此種遷移之情形發生，必須於銅層沉積處理之前使用 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 91944 --------^---------M (請先閱讀背面之注意事項再填寫本頁) 516120 A7 __ Β7 五、發明說明（2 諸如氮化鈦、氮化鈕等阻障（barrier丨叮以）層。 般金屬層施加技術，諸如電化學沉積 (electrochemical depositi〇n) ’僅適合將銅金屬施加於導電 層。因此需要在銅的電化學沉積之前，將諸如銅的金屬晶 種層之底層導電晶種層，施加於基板上。施加該晶種層之 方法有許多種，諸如物理蒸氣沉積（physical vap0I· deposition，，，PVD，，）與化學蒸氣沉積（chemicai ^邛的⑴⑽’^乂^’^一般而言’在與其他金屬相較之下， 晶種層比較薄’諸如5G至i埃的厚度。該金屬晶種層 尤其是銅晶種層，可能產生諸如在晶種層與層面之大部分 範圍的表面金屬氧化物（絕緣臈）與層面上出現不連續現象 空洞之區域。這是因為表面層沉積不足而造成，諸如將金 屬沉積於-條可見的線上。若要使完整的金屬層以電化方 式沉積於該晶種層，則在最終的金屬層沉積之前或期間必 須將不連續部分填充，否則最終的金屬層可能會發生空洞 現象。 PCT專利申請㈣w〇99/4773! (Chen)揭露一種藉以 第-蒸氣而提供晶種層之方法，其中該第一蒸氣沉積一種 超薄晶種層’而隨後將該層藉以電化方式強化超薄晶種層 而產生形成最終的晶種層。依據本專利申請，該兩階段製 程提供降低斷續現象之晶種層，也就是降低晶種層覆蓋不 完整或缺少之區域的晶種層。1>知的翻底或超填式電鑛銅 本纸張尺度刺巾關家標準（⑶似伐格（2】〇 x 297公髮「 2 線 91944516120 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 V. Description of the invention (1 [Background of the invention] The present invention is mainly related to the technical field of the seed layer for later metallization. More specifically, the present invention There is a method for repairing the seed layer before metallization. Small microelectronic devices such as sub-micron geometries have tended to contain multiple metallization layers for higher density processing. Generally used to form The metal wire on the semiconductor wafer is also commonly called wiring 'aluminum. The advantage of aluminum is that it is relatively cheap, has a low resistivity, and is very easy to be etched. Aluminum is also used as a via. ) Interconnects to connect different metal layers. However, although the size of the vias / contact holes has been reduced to the sub-micron range, it also caused the problem of step coverage. Instead, aluminum was used instead. When interconnecting different metal layers, stability issues arise. Such poor stage coverage causes high current density and also promotes electron migration There is a way to & an improved interconnect path for vias, which can use a metal such as tungsten to form a complete filled plug when using an inscription as a metal layer. However, tungsten The manufacturing process is not cost-effective and complicated. Tungsten has a high electrical resistivity, and tungsten plugs (tungstenplugs) can easily lead to poor interfaces between the void and the wiring layer. Copper can be used as a replacement material for interconnect metallization of integrated circuit manufacturing. Copper The advantages are better electrical properties than tungsten, better electron migration characteristics and lower resistivity than aluminum. Its disadvantages are that it is more difficult to do post processing than aluminum and crane, and it is easy to migrate to such as In order to avoid this kind of migration, it is necessary to use this paper before the copper layer deposition process. This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 91944 -------- ^ --------- M (Please read the precautions on the back before filling out this page) 516120 A7 __ Β7 V. Description of the invention (2 Barriers such as titanium nitride, nitride buttons, etc.) ) Layer. General metal layer application technology, various Electrochemical deposition is only suitable for applying copper metal to the conductive layer. Therefore, before the electrochemical deposition of copper, it is necessary to apply the bottom conductive seed layer of a metal seed layer such as copper to the substrate. There are many methods for applying the seed layer, such as physical vapor deposition (physical vapor deposition, PVD,,) and chemical vapor deposition (chemicai ^ 邛 邛 '^ 乂 ^' ^ Generally speaking, By contrast, the seed layer is relatively thin, such as a thickness of 5G to i Angstroms. The metal seed layer, especially the copper seed layer, may generate areas such as surface metal oxides (insulating plutonium) on the seed layer and the surface layer and discontinuities in the surface layer. This is due to insufficient deposition of the surface layer, such as metal deposits on visible lines. If a complete metal layer is to be electrochemically deposited on the seed layer, the discontinuity must be filled before or during the final metal layer deposition, or voids may occur in the final metal layer. PCT Patent Application No. WO99 / 4773! (Chen) discloses a method of providing a seed layer by a first vapor, wherein the first vapor deposits an ultra-thin seed layer, and then electrochemically strengthens the ultra-thin layer The seed layer is formed to form the final seed layer. According to this patent application, the two-stage process provides a seed layer that reduces discontinuities, that is, a seed layer that reduces areas where the seed layer covers incomplete or missing areas. 1 > Known bottom-over or over-filled electric ore copper Standard for paper towels Standard for household papers (CD-like cutting (2) 0 x 297 Public hair 2 lines 91944

012U 五、發明說明（3 ) 溶液為酸性溶液。因此， 曰播^ ^ 要利用I知的鍍銅溶液來修補 :性: 分，則需要兩種電解電鐘溶液，即-種 化電解電鍍溶液與-種酸性電解鍍銅溶液。在使用 %知的電解電鍍溶液 使用 合之岸理。“… 層做完全之洗淨與中 处 ，右廠商要將該鹼性強化方法配合酸性電 將錢⑤具（P1扣ng tGGi)之⑽ 加倍，否則產能將降低。 里 使用無電解鍍覆，尤1 4 > ，、疋採"、、電鍍鋼時，多使用膠鋼 ( 如C〇PPe〇作為一種催化劑。例如，美國專利 ，2,560與4,68l,630(Brasch)揭露含少量電離把的膠銅， 該電離纪可作為-種無電解鑛銅溶液的催化劑，尤其是速 度緩慢的無電解鑛鋼溶液。但該催化劑並不是用來製造積 體電路。 、 線 有鑑於上情’一直有需要不使用第二種電解電鍍溶液 之不連續晶種層之修補方法。該方法特制在元件電鐘 上，且該元件的外型非常小，如〇 5微米（含）以下。 [發明概述] 經濟部智慧財產局員工消費合作社印製 依據本發明乃提供一種驚人的發明，此發明可不用鹼 性電解電鏡溶液也可修補或強化不連續的金屬晶種層，而 提供一種實質上不含不連續部分之金屬晶種層。 在一方面，本發明提供一種方法，該方法是強化基板 上所"L積的不連續金屬晶種層，包含下列之處理步驟：將 基板上所沉積的金屬晶種層與含少量可離子化鈀化合物 (icnizable palladium) 銅膠粒子（copper c〇ll〇1d 本紙張尺度適用中國國家標準（CNS)A4規格(2i〇x 297公爱‘---- 3 91944 516120 經 濟 部 ，智 慧 財 產 局 員 工 消 費 合 作 社 印 製 4 A7 五、發明說明（4 ) partlcies)的銅膠組成物接觸，以形成實質上連續之晶種 層。 、 在第二方面，本發明提供一種方法，該方法是將晶種 層的表面上之金屬層做電沉積處理，處理步驟包含：將基 板上所沉積的金屬晶種層與含有少量可離子化&化合物以 及大量銅膠粒子的銅膠組成物接觸，以形成實質上連續之 晶種層；以及將該基板與含有一種或—種以上的金屬離子 和電解質的電鍍液接觸。 在第三本發明提供一㈣子裝置之製造方法， 該方法包括下列步驟··將電子裝置基板上所沉積的金屬晶 種層與含有少量可離子化絶與大量鋼膠粒子的鋼膠組成物 接觸’以形成貫質上連續之晶種層；以及將該基板與含有 一種或一種以上的金屬離子和電解質的電鍍液接觸。 [發明之詳細說明] 在本說明書之全文中所使用之縮寫符號除非另外特別 明確表示者以外，代表下列之涵義：nm =奈米 (nanometers)，μπ^微米（micr〇n、; ASF =每平 方夬呎之安培；g/L=r克/升（grams per iiter) ; 克分子濃 度（_1訂）；以及ppm=百萬分之_份（pam per milH〇n)。 在本說明書之全文中，，，形態，，”feature，，是表示基板上 的4何外形（geometries)，諸如但不局限為溝漕與導通孔。” 導通孔’’’’Aperture”是表示凹陷之外形，諸如導通孔與溝 β。微小形態’’’’small features，，之一詞是表示一微米或以 之尺寸大小的外形〇 ”極微小形態，，，，very sma〗l features” 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公餐]------------------- 91944 ^--------^---------^ {請先閱讀背面之注意事項再填寫本頁) 516120 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（5 是表示0.5微米或以下之尺寸大小的外形。同樣地，”小 孔’’’’small apertures，，是表示孔徑尺寸大小為一微米或以下 U 1厂m)，而’，極小孔，，”very small apenures，，是表示孔徑尺 寸大小為0.5微米或以下U〇.5#m)。本說明書全文中， 除非另外特別註明，電鍍，，platlng”是表示金屬。”沉積 (deP〇Sitlon)’，與”電鍍（p〗atlng)，，在本說明中可互換使用。” 促進劑（accelerator)’’是指一種增強電鍍率之化合物。，，抑制 劑（suppressor)”是指一種抑制電鍍率之化合物。，，鹵化物 (halide)疋扣氟化物、氣化物、溴化物、與埃化物。 除非另外註明’否則所有百分比與比例皆表示重量 比。所有範圍均包含在内且可結合的。 本發明提供一種可強化基板上所沉積的不連續金屬晶 種層，包含下列之處理步驟：將基板上所沉積的金屬晶種 層與含有少量可離子化鈀化合物和大量銅膠粒子之鋼膠成 分互相接觸’以形成實質上連續之晶種層。依此方法可獲 得實質上不會有不連續或者空洞之晶種層，最佳情況則是 使晶種層完全保持連續。該晶種層最好含有銅或鋼合金。 所辨少置’’是指低於大約5〇0/〇左右。同樣地，，，大量，，則是 指高於50%左右。 基板可為含有供後述之金屬電鏟之用之晶種層，目的 是做後續的金屬電沉積作業，而實際上基板是用來製造電 子元件。舉例而言，基板含有，但不局限於€ 1 μηι、‘ 0·5μπι ’以及$ 〇 18μπι之孔徑大小。實際上，基板實質上 含有用以製造積體電路與半導體之晶圓。 ‘紙張尺度適用中關冢標準（cns)A4規格⑵Qx 297公爱）-" - 5 91944 --------^--------- (請先閱讀背面之注意事項再填寫本頁) 516120 A7 B7 經 濟 部 智 慧 財 •產 局 員 工 消 費 合 社 印 製 6 玉、發明說确（ 適用本發明使用的銅膠均發表於美國專利 4,762,560(Brasch)’為本發明之目的併入本說明書内供參 考。混合一種或一種以上的銅化合物，穩定劑以及還原劑 而調製成銅膠粒子。適當的銅化合物可藉由一種或一種以 上的還原劑還原之任何鋼化合物。該鋼化合物含有但不局 限於硫酸銅、較好是五水合物（CuS〇45H2〇)、亞磷酸鹽銅、 磷酸鹽銅、氨基磺酸鹽鋼（copper sulfamate)、醋酸鹽銅、 氯化銅、硝酸鹽銅、檸檬酸鹽銅、甲酸鹽鋼、葡萄酸銅等。 雖然銅化合物因本身優點而使膠質溶液的鋼金屬（零價銅） 含量為1至8g/L左右，較好是2·5至7·5左右，更好是5g/L 左右，但是銅之相對含量比例卻不是那麼重要。因此，以 CuSO/H^O而論，在還原之前，銅化合物應佔1〇至， 最好是20g/L左右之含量。 有很多種穩定劑可用來形成銅膠體（c〇pper cc>llc)id)。 明膠是一種最有利的穩定劑。而其他合適的穩定劑包含， 但不局限於，聚乙烯醇、聚丙烯醯胺、褐藻酸鈉、單油酸 鹽聚梨酸酯（polysorbate mono-oleate)、糊精（膠與殺粉）、 聚芳基磺酸，諸如聚苯磺酸與聚烷基萘磺酸，及其鹽。尤 其是聚芳基績酸之驗金屬鹽（例如聚苯績酸之鹽及聚烧基 萘之鹽）膠質調製時所用之穩定劑或成品膠質本身中之穩 定劑是作為穩定膠質之用途。不用穩定劑也可調製膠質， 而且雖然有用，但卻在競爭性之商業用途上十分穩定。穩 定劑在膠質溶液中之含量，以大約1至3 g/L左右為較佳， 而最佳是大約2g/L。 本紙張尺度適用中國國家標準（CNS)A4規格（2】0>< 297公釐） 91944 -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 516120 經濟部智慧財產局員工消費合作社印製 7 A7 五、發明說明（ .許多種還原劑之任一種於 々可用以形成銅膠。適當的還 原劑包含，但不局限於，水合 Q硏、领氫化卸、連二亞硫酸 鋼、硼氫化經 '哪氫化納' 7 . 飞 乙硼烷鉀、二甲基胺甲硼烷 (dimethylamine borane ? ΐ>ΜAU \ ^ ΜΑβ)等。ϋΜΛβ為最佳溶劑。 其他的還原劑也可以使用，β 仁疋在酸性條件下，每一種的 還原能力應與DMAB —樣或相梦 + a 等。在使用删氮化物還原劑 時，較好是溶液的酸驗值降5 Mu 抑 馱蜓值降至DMAB的酸鹼值之近似範 圍。還原劑可以有利的以组八 、D形態使用。雖然膠質溶液中012U 5. Description of the invention (3) The solution is an acidic solution. Therefore, if you want to use the known copper plating solution to repair: properties: points, you need two types of electrolytic clock solution, that is, a seeded electrolytic plating solution and an acidic electrolytic copper plating solution. In the use of the known electrolytic plating solution, use Anode. "... The layer is completely cleaned and the middle part, the right manufacturer must double the amount of money (P1 ng tGGi) with the alkaline strengthening method combined with acid electricity, otherwise the production capacity will be reduced. The use of electroless plating, In particular, in the case of electroplating steel, rubber steel (such as CoppeO is used as a catalyst. For example, US patents 2,560 and 4,68l, 630 (Brasch) disclose a small amount of ionization. The ionized copper can be used as a catalyst for electroless copper ore solution, especially the slow electroless ore steel solution. But the catalyst is not used to make integrated circuits. There is always a need to repair the discontinuous seed layer without using a second electrolytic plating solution. This method is specially made on a component electric clock, and the appearance of the component is very small, such as below 0. 5 microns (inclusive). [Invention Overview] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs according to the present invention is to provide an amazing invention. This invention can repair or strengthen the discontinuous metal seed layer without alkaline electrolytic electron microscopy solution, and provides a substantial The metal seed layer does not include a discontinuous part. In one aspect, the present invention provides a method for strengthening a discontinuous metal seed layer formed on a substrate by "L product", including the following processing steps: The deposited metal seed layer and a small amount of icnizable palladium copper colloid particles (copper c〇ll〇1d) This paper size applies to China National Standard (CNS) A4 specifications (2i〇x 297 public love '- -3 91944 516120 Printed by the Ministry of Economic Affairs and the Intellectual Property Bureau's Consumer Cooperatives 4 A7 5. The copper glue composition of the invention description (4) partlcies) is contacted to form a substantially continuous seed layer. In the second aspect, The invention provides a method. The method is to perform an electrodeposition treatment on a metal layer on the surface of the seed layer. The processing step includes: depositing the metal seed layer deposited on the substrate with a small amount of ionizable & compounds and a large amount of copper. The copper paste composition of the colloidal particles is contacted to form a substantially continuous seed layer; and the substrate is contacted with a plating solution containing one or more metal ions and an electrolyte. In a third aspect of the present invention, there is provided a method for manufacturing a ladle device, which method includes the following steps: a metal seed layer deposited on a substrate of an electronic device and a steel plastic containing a small amount of ionizable insulation and a large amount of steel plastic particles The composition is contacted 'to form a continuous seed layer; and the substrate is contacted with a plating solution containing one or more metal ions and an electrolyte. [Detailed Description of the Invention] As used throughout this specification, Abbreviations refer to the following meanings, unless specifically stated otherwise: nm = nanometers, μπ ^ micron (micr〇n ,; ASF = amperes per square square foot; g / L = r grams / liter ( grams per iiter); gram concentration (1 order); and ppm = parts per million (pam per mil Hon). Throughout this specification, "morphology" means "geometries" on the substrate, such as but not limited to trenches and vias. "Vias" "Aperture" means Outer shapes of depressions, such as vias and grooves β. "Small features", the word "small features", means a shape that is one micron or larger in size, "very sma", "very sma" l features " This paper size applies to China National Standard (CNS) A4 specification (210 χ 297 meals) ------------------- 91944 ^ -------- ^- -------- ^ {Please read the notes on the back before filling out this page) 516120 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (5 is the size of 0.5 microns or less Shape. Similarly, "small apertures" and "small apertures" indicate aperture sizes of one micrometer or less (U 1 factory m), and ', very small apertures, and "very small apenures" indicate aperture sizes. 0.5 μm or less U.5 # m). Throughout this specification, unless otherwise specified, electrical "Platlng" means metal. "Deposition (dePo Sitlon) '," and "plating (p) atlng), are used interchangeably in this description. "Accelerator '" refers to a compound that enhances the plating rate. "Suppressor" refers to a compound that suppresses the plating rate. ,, halide (halide) button fluoride, gaseous, bromide, and ethene. Unless stated otherwise, all percentages and ratios are by weight. All ranges are inclusive and combinable. The invention provides a discontinuous metal seed layer deposited on a substrate, which includes the following processing steps: a metal seed layer deposited on a substrate and a steel paste containing a small amount of ionizable palladium compound and a large amount of copper paste particles The ingredients are in contact with each other 'to form a substantially continuous seed layer. According to this method, a seed layer having substantially no discontinuities or voids can be obtained, and the best case is to keep the seed layer completely continuous. The seed layer preferably contains copper or a steel alloy. Distinguished "'means less than about 50,000 / 0. Similarly, a large amount means higher than about 50%. The substrate may include a seed layer for a metal electric shovel described later for the purpose of performing subsequent metal electrodeposition operations. In fact, the substrate is used to manufacture electronic components. For example, the substrate contains, but is not limited to, a pore size of € 1 μm, ‘0.5 μm’, and a diameter of 18 μm. In fact, the substrate essentially contains wafers used to make integrated circuits and semiconductors. 'The paper size applies the Zhongguanzuo standard (cns) A4 specification⑵Qx 297 public love)-"-5 91944 -------- ^ --------- (Please read the precautions on the back first (Fill in this page again) 516120 A7 B7 Printed by the Ministry of Economic Affairs, Intellectual Property, Industry Bureau, Consumer Cooperatives, 6 Jade, invention confirmed (the copper glue used in the present invention is published in U.S. Patent 4,762,560 (Brasch) 'for the purpose of this invention It is incorporated herein by reference. The copper colloidal particles are prepared by mixing one or more copper compounds, stabilizers and reducing agents. Any suitable copper compound can be reduced by one or more reducing agents. Any steel compound. The steel compound contains, but is not limited to, copper sulfate, preferably pentahydrate (CuSO45H20), copper phosphite, copper phosphate, copper sulfamate, copper acetate, copper chloride, Copper nitrate, copper citrate, formate steel, copper gluconate, etc. Although the copper compound has its own advantages, the content of the steel metal (zero-valent copper) in the colloidal solution is about 1 to 8 g / L, preferably 2 · About 5 to 7 · 5, more preferably about 5g / L, The relative content of copper is not so important. Therefore, in terms of CuSO / H ^ O, before reduction, the copper compound should occupy 10 to, preferably about 20 g / L. There are many stabilizers available To form a copper colloid (copper cc > llc) id). Gelatin is one of the most advantageous stabilizers. And other suitable stabilizers include, but are not limited to, polyvinyl alcohol, polyacrylamide, sodium alginate, polysorbate mono-oleate, dextrin (gel and powder), Polyarylsulfonic acids, such as polybenzenesulfonic and polyalkylnaphthalenesulfonic acids, and their salts. In particular, metal stabilizers of polyarylates (such as polyphenylenes and polynaphthalene salts) are used as stabilizers in the preparation of colloids or stabilizers in the finished colloid itself to stabilize colloids. Gum can be formulated without stabilizers, and although useful, it is very stable for competitive commercial use. The content of the stabilizer in the colloidal solution is preferably about 1 to 3 g / L, and most preferably about 2 g / L. This paper size is applicable to China National Standard (CNS) A4 specifications (2) 0 > < 297 mm) 91944 ------------- Installation -------- Order --- ------ line (Please read the notes on the back before filling this page) 516120 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 A7 V. Description of the invention (... Forms a copper paste. Suitable reducing agents include, but are not limited to, hydrated hydrazone, collar hydrogen hydride, dithionite steel, borohydride via sodium hydride. 7. Potassium diethylborane, dimethylamine methyl Borane (dimethylamine borane? Ϊ́ > MAU \ ^ ΑΑβ), etc. ϋΜΛβ is the best solvent. Other reducing agents can also be used. Under the acidic conditions, β-renthion should have the same reducing power as DMAB or dream. + a etc. When using a nitride reducing agent, it is preferred that the acid value of the solution be reduced by 5 Mu, and the value of the dampness value should be reduced to the approximate range of the pH value of DMAB. The reducing agent can be advantageously used in group eight and D forms. Use. Although in the colloidal solution

較好含有約1至8g/L，2.5 $ 7 < /T .5g/L ’更好是5g/L之還原 劑，且雖然可超出還原銅鹽所 ^ 、 π而要之I，但是還原劑的含 Ή:比例卻不是那麼的重要。雖 雖然返原劑的混合物並不是較 好，但可以適當使用。 依據上述得知，一插式_ ^ 牙Α 種以上的還原劑與鋼金屬（零 價鋼）之含量比例以重量計約為ln或以上。 本發明的鋼膠含有微量成分 取刀的可離子化鈀。鈀金屬應 足量添加以提高電解銅沉積之覆蓋範圍，如此可將不連續 之部：填塞或連接。大體上’鈀金屬的含量約5至8—， 較好是8至80ppm，更好是12至75ppm，最好是⑼至 50PPm。纪金屬的最低含量取決於所使用的特定離子纪化 合物。 膠質内的鈀金屬之上限值取決於所使用的特定離子鈀 化合物’電鍍電解溶液穩定時的離子鈀化合物之陰離子效 應’與催化膠體本身的穩定度。因此，通常足以使催化（膠 •貝）♦液保持穩定之量之鈀。若鈀的添加量超過8〇ppm，則 本紙張尺度適”關家標準（CNS)A4規格⑽)-----~~____ 91944 --------^---------^ IAWI (請先閱讀背面之注意事項再填寫本頁) 516120 A7It preferably contains about 1 to 8 g / L, 2.5 $ 7 < / T. 5 g / L 'more preferably 5 g / L of reducing agent, and although it can exceed I required by reducing copper salts ^ and π, I, but the reduction The content of the agent: the ratio is not so important. Although the mixture of regenerant is not good, it can be used appropriately. According to the above, the content ratio of one or more types of reducing agents to steel metal (zero-valent steel) is about ln or more by weight. The steel glue of the present invention contains a trace amount of ionizable palladium from a knife. Palladium metal should be added in sufficient amounts to increase the coverage of the electrolytic copper deposits so that discontinuities can be plugged or connected. Generally, the content of the 'palladium metal is about 5 to 8-, preferably 8 to 80 ppm, more preferably 12 to 75 ppm, and most preferably rhenium to 50 PPm. The minimum metal content depends on the specific ionic compound used. The upper limit of the palladium metal in the colloid depends on the specific ionic palladium compound used, the anion effect of the ionic palladium compound when the plating electrolytic solution is stable, and the stability of the catalytic colloid itself. Therefore, it is usually sufficient to maintain a stable amount of palladium. If the added amount of palladium exceeds 80 ppm, then the paper size is suitable for "CNS A4 specification ⑽) ----- ~~ ____ 91944 -------- ^ ------ --- ^ IAWI (Please read the notes on the back before filling out this page) 516120 A7

tr k 8 91944 516120 A7tr k 8 91944 516120 A7

經濟部智慧財產局員工消費合作社印製 9 五、發明說明（9 ) 一般而言，鋼化合物還原的酸鹼值約i 5至4，最佳 則為2至2.5左右。還原反應的溫度並不是非常重要。在 至/m下就可產生反應，但最好還需稍微加熱以致能於8〇 至90°F左右的溫度下產生反應。如果需要，溫度可以更高 一些（120至130°F)，但是反應物之種類與量以及與酸鹼值 是控制反應的主要因素。反應逐漸開始而且要過5至1〇 分鐘才顯現反應。利用磺酸鹽銅就可藉由顏色變化來觀察 反應結果，顏色則由深藍變為淺藍，最後則變為綠色。在 完成由顏色之變化所顯現之第一部份的反應後，則應停止 加熱或攪拌而維持反應混合物的狀態或者再使混和物反應 持續24小時的反應時間。經過24小時之後，就可使用膠 體；但是，置放於密閉容器再經過3至4週之熟化處理會 有最好之效果。一般而言，鋼膠粒子之大小約為1〇至ι〇〇 毫微米（millimicron ιημ)。 此外，在初始反應後，若要使膠質穩定度增強，則可 添加額外的還原劑，諸如水和肼、苯肼、硫酸鹽經胺 (hydroxylamme sulfate)，或甚至再添加DMB(或另一種初 始反應時所使用的其他還原劑）。在膠體經過熟化或存放24 小時之後，可對膠體添加額外之還原劑，但如有需要可於 初始反應結束之後之其他階段添加。 經過24小時熟化之後，膠體的酸鹼值約為7，而可在 此有利的酸驗值下直接使用，但是膠質可在非常廣的駿驗 值範圍使用。視需要酸鹼值可用添加酸性成分（如硫酸）或 驗性成分（如驗性氫氧化物）之方法調整，如熟悉此技藝者 本紙張尺度適用中國國家標準（CNS)A4規格（2】〇χ 297公釐） 91944 --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 516120 A7 五、發明說明（10 所周知。在使用期Fb1，膠體的酸驗值可能下降，但是實際 ► 經濟部智慧財產局員工消費合作社印製 上，膠溶液則會不斷補充，使酸鹼值有回到7之趨勢 性膠質最好保持微鹼性，如酸鹼值維持在7至8左右 好是維持在7·8至8左右。 雖然銅是膠體之較佳選擇’但熟悉此技藝者可知 鎳、鐵、或鈷等其他適合的膠體也可用於本項發明。 本發明的銅膠是用來強化或修補沉積於基板上的金屬 晶種層不連續之部分。—般而言，非連續晶種層與鋼膠接 觸（1至2g/L的銅為最佳），以產生膠體覆蓋面或是強化的 晶種層。此種膠體可用各種方法施加於晶種層，諸如浸潰、 噴務、鉍轉塗敷（spin coating)、溢流塗敷（n〇〇d coding) 等，但以浸潰、噴霧、與螺旋塗敷。基本上，膠體是用來 將晶種層不連續之部分填滿或修補，目的是要使晶種層連 續。因此，銅膠覆蓋或強化的晶種層基本上是連續的。本 發明的銅膠之優點再於其酸鹼值約為7，或是輕鹼性之程 度。也因此，降低了晶種層溶解之情形，如降低晶種層的 金屬氧化物溶解之情形。 經過晶種層上之膠體沉澱之後，可依選擇需求將膠體 覆蓋面以水或活性化溶液做清洗處理。實例的活性化溶液 包含一種還原劑溶液，諸如將任何一種的電離鈀還原為鈀 金屬（零價鈀）。上述任何一種均為適當的還原劑。 鋼膠強化晶種層可用各種金屬電鍍，但一般是用銅來 做電錢處理。電鍍作業可依無電解電鍍或是電解電鍍來處 理。無電解電鍍可用來再強化晶種層。但是該無電解電鍍 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ四7 ) 鹼 較 如 . ^--------^---------線 <請先閱讀背面之注意事項再填寫本頁) 10 91944 經濟部智慧財產局員工消費合作社印製 11 516120 A7 ----------β7__ 五、發明說明（） 處理用於導通孔之實質上之填塞或完全填塞速度很慢。 較佳的方式是，鋼膠強化晶種層的電解電鍍是將足量 的金屬沉積以實際或完全填塞導通孔。本發明的實質上連 續晶種上沉積金屬層用的電解鍍銅溶液一般包含_種或一 種以上的鋼離子源與一種電解液，較好是酸性電解液。電 解電鍍洛液可依據需要含有一種或一種以上的添加劑，諸 如商化物、促進劑（accelerator)或光亮劑、抑制劑、均化劑、 晶粒細化劑、潤濕劑、表面活性劑等。 有許多銅鹽可以採用為電解鍍銅溶液之銅離子源。適 田的鋼鹽包含，但不局限於硫酸鋼、醋酸鹽銅、氟硼酸銅、 葡糖酸鋼、甲酸銅、烷磺酸銅、芳基磺酸鋼、氨基磺酸銅、 磺酸銅、與硝酸銅。硫酸銅五水合物（coppersulfate pentahydrate)則為最適合。這些電解電鍍溶液可含有濃度 耗圍相當廣之銅鹽。較好是電鍍溶液的銅鹽濃度約為丨至 3 00g/L，更好是1〇至225g/L左右，再好是25至 左右。鍍鋼溶液也可含有其他的合金元素，諸如，但不局 限於錫、鋅等，因此，電解鍍銅溶液還可用來做銅合金沉 積之處理。 、適當的電解鍍鋼溶液應含有酸性電解液，酸性溶液可 為-種或-種以上。有機或無機均適宜。可用之無機酸包 含，但不局限於硫酸、碟酸、硝酸、鹵化氫酸（hydrogen hahde acids)、氨基磺酸、氟硼酸等。適當的有機酸包含， 但不局限於烧基磺酸如甲石黃酸；芳基續酸如苯基石黃酸與甲 y 酸與丙酸；鹵代酸如三氟曱磺 ^紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公餐 -— -— 91944 --------^---------線 (請先閱讀背面之注意事項再填寫本頁) 經 濟 部 慧 財 •產 局 員 工 消 費 合 作 社 印 製 12 A7 B7 •五、發明說明（U ) 酸與鹵醋酸（haloacetic acid)等。特別合適的有機酸尤其含 有（CrC1G)烷基磺酸。特別合適的酸類之組合，包括一種咬 以上的無機酸，而無機酸與一種或_種以上的有機酸 或是含兩種或兩種以上的有機酸混合物。若電解液含有兩 種或兩種以上的酸類，則該酸類的比例範圍為99 ··丨至^ ·· "，而較理想則為90: 10至10: 90;而更理想為8〇: 2〇 至 20 : 80 〇 用於本發明的電鍍溶液中之酸總含量約為〇至 35〇g/L。較佳為i至225g/L。熟悉該項技藝應了解，使用 金屬硫酸鹽作為金屬離子源，即使沒有添加酸，也可獲得 酸電解液。因此，在-項實施例中，銅電鍵溶液可以:用 添加酸。 就某些應用上，諸如具有極小孔徑的晶圓電鐘，酸的 總添加量應為低量。，，低量酸，，是指電解液中的酸總添加量 維持約0.4M以下，較佳則為約〇遍以下，又較佳則是維 持約〇_2m。特佳的低量酸電㈣液料不含添加酸、， 即添加酸含量為〇g/L。 銅電解液可視需要含有一種或一種以上的齒化物。氣 化物與溴化物為較佳的鹵化物，而氣化物是更佳的鹵化 物。可適用的虐化物離子濃度的使用範圍 化物離子的條件下），諸如電鍛溶液中加入約0(未(使用= 物離子）至⑺卟㈣的齒化物離子，而最佳的含量為約25 至約Wpm。所添加的齒化物，便可作為相對應的南化氫 酸或是任何一種合適的鹽 本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公爱） 91944 I---------^--------- (請先閱讀背面之注意事項再填寫本頁) M6120 經濟部智慧財產局員工消費合作社印製 13 A7 五、發明說明（l3 / 許多包含已知光亮劑盘佔；隹态 儿A，、促進劑之光亮劑及促進劑，均 可用於銅電链溶液。一般的光亮劑均含有-種或-種以上 的硫原子:典型地並無包含任何氮原子且其分子量約]_ 或以下。光1劑化合物最好是能含有硫化物及/或確酸基， 以包括分子式R，各R_s〇3X基之化合物較佳，r為視需要 經取代之燒基（包含環烧基）、視需要經取代之雜院基、視 而要丄取代之方基、或視需要經取代之雜脂環；X為平衡 離子，如鈉或鉀，R，為氫或是化學鍵（諸如_s_r_s〇3X或較 大化合物之取代基）。一般的院基具有1至約16個碳，且 體而言為1至約8或12個碳。雜烷基為其鏈中具有一種或 一種以上的雜原子(N、〇或S)，較佳的則為1至約16個 礙’具體而言為1至約8或12個碳。碳環芳基-般均為芳 基’如苯基與萘基。雜芳基亦為合適的芳基，典型地係含 有1至約3個N、〇或s原子與！至3個獨立環或稠環， 並包含香豆素基（coumarinyl)、喹啉基、吡啶基、吡嗪基、 嘧咬基、口夫喃基、Π比洛基、噻嗯基、噻唾基、嗜唾基、曙 二唑、***、咪唑基、吲哚基、苯并呋喃基、苯井噻唑基 等。雜脂環族一般含有i至3個N、〇或s原子與i至3 個獨立環或稠環’並包含四氫呋喃基、噻嗯基、四氫吡喃 基哌。疋基、嗎啉基、吡咯烷基等。經取代之烷基、雜烷 基、芳基或雜脂環基的取代基包含Ci8烷氧基、CM烷基、 鹵素’尤其是F、C1與Br、氰基、硝基等。 具體而言，可用之光亮劑，包含具有下列分子式者：Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9 V. Description of the invention (9) Generally speaking, the pH value of steel compound reduction is about i 5 to 4, and the best is about 2 to 2.5. The temperature of the reduction reaction is not very important. The reaction can occur at up to / m, but it is best to heat it slightly so that the reaction can occur at a temperature of about 80 to 90 ° F. If desired, the temperature can be higher (120 to 130 ° F), but the type and amount of reactants and the pH value are the main factors controlling the reaction. The reaction started gradually and it took 5 to 10 minutes for the reaction to appear. With copper sulfonate, you can observe the reaction result by changing the color, the color changes from dark blue to light blue, and finally to green. After completing the first part of the reaction as indicated by the color change, the heating or stirring should be stopped to maintain the state of the reaction mixture or the mixture should be allowed to react for a reaction time of 24 hours. After 24 hours, the gel is ready for use; however, it is best to leave it in an airtight container for another 3 to 4 weeks of curing. Generally speaking, the size of the steel colloid particles is about 10 to 100 nanometers (millimicron μm). In addition, after the initial reaction, if you want to enhance the stability of the colloid, you can add additional reducing agents, such as water and hydrazine, phenylhydrazine, hydroxylamme sulfate, or even DMB (or another initial Other reducing agents used in the reaction). After the colloid has been aged or stored for 24 hours, additional reducing agents can be added to the colloid, but it can be added at other stages after the initial reaction if necessary. After 24 hours of maturation, the pH value of the colloid is about 7, which can be used directly under this favorable acid test value, but the gum can be used in a very wide range of test values. If necessary, the acid-base value can be adjusted by adding acidic components (such as sulfuric acid) or test components (such as test hydroxide). If you are familiar with this technique, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (2). χ 297 mm) 91944 -------------------- Order --------- line (Please read the precautions on the back before filling this page) 516120 A7 V. Description of the invention (10 is well known. During the use of Fb1, the acid value of the colloid may decrease, but in fact ► printed on the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the glue solution will be continuously replenished to make the pH value There is a tendency to return to 7, the colloid is best to keep slightly alkaline, such as the pH value is maintained at about 7 to 8 is better to maintain at about 7.8 to 8. Although copper is a better choice of colloids, but familiar with this art It is known that other suitable colloids such as nickel, iron, or cobalt can also be used in the present invention. The copper paste of the present invention is used to strengthen or repair the discontinuous part of the metal seed layer deposited on the substrate. Generally speaking, non- The continuous seed layer is in contact with the steel glue (1 to 2g / L copper is preferred) to produce a colloidal coverage or reinforced Seed layer. This colloid can be applied to the seed layer by various methods, such as dipping, spraying, bismuth spin coating, nod coding, etc. Spray and spiral coating. Basically, the colloid is used to fill or repair the discontinuous part of the seed layer in order to make the seed layer continuous. Therefore, the seed layer covered or reinforced by copper glue is basically Continuous. The advantage of the copper paste of the present invention is that the acid-base value is about 7, or the degree of light alkalinity. Therefore, the dissolution of the seed layer is reduced, such as the metal oxide of the seed layer is reduced. After the colloidal precipitation on the seed layer, the colloidal surface can be washed with water or an activated solution as required. The activated solution of the example includes a reducing agent solution, such as reducing any of the ionized palladium to Palladium metal (zero valence palladium). Any of the above are suitable reducing agents. The steel cement reinforced seed layer can be electroplated with various metals, but copper is usually used for electricity treatment. The electroplating operation can be based on electroless plating or electrolytic Plating The electroless plating can be used to further strengthen the seed layer. However, the paper size of the electroless plating is applicable to the Chinese National Standard (CNS) A4 (21〇χ 四 7). The alkali is the same. ^ -------- ^ --------- line < Please read the notes on the back before filling out this page) 10 91944 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 516120 A7 ---------- β7__ 5. Description of the invention () The processing for the filling or complete filling of via holes is very slow. Preferably, the electrolytic plating of the steel cement-reinforced seed layer is to deposit a sufficient amount of metal to actually or completely fill the via hole. The electrolytic copper plating solution for depositing a metal layer on a substantially continuous seed crystal of the present invention generally comprises one or more steel ion sources and an electrolyte, preferably an acid electrolyte. The electrolytic plating solution may contain one or more additives, such as commercial compounds, accelerators or brighteners, inhibitors, leveling agents, grain refiners, wetting agents, surfactants, etc., as needed. There are many copper salts that can be used as a source of copper ions for electrolytic copper plating solutions. The steel salt of Shida includes, but is not limited to, steel sulfate, copper acetate, copper fluoborate, steel gluconate, copper formate, copper alkane sulfonate, steel aryl sulfonate, copper sulfamate, copper sulfonate, With copper nitrate. Copper sulfate pentahydrate is the most suitable. These electrolytic plating solutions may contain copper salts in a wide range of concentrations. The copper salt concentration of the plating solution is preferably about 1-1 to 300 g / L, more preferably about 10 to 225 g / L, and even more preferably about 25 to about. The steel plating solution may also contain other alloying elements such as, but not limited to, tin, zinc, etc. Therefore, the electrolytic copper plating solution can also be used for the treatment of copper alloy deposition. 2. An appropriate electrolytic steel plating solution should contain an acidic electrolyte, and the acidic solution may be-or more. Both organic and inorganic are suitable. Useful inorganic acids include, but are not limited to, sulfuric acid, dishic acid, nitric acid, hydrogen hahde acids, sulfamic acid, fluoboric acid, and the like. Appropriate organic acids include, but are not limited to, sulfonic acids such as methoxanthinic acid; aryl continuous acids such as phenylphosphinoic acid and formic acid and propionic acid; halogenated acids such as trifluorosulfonium ^ Paper dimensions apply to China National Standard (CNS) A4 Specification (21〇x 297 Meals----91944 -------- ^ --------- Line (Please read the precautions on the back before filling this page ) Printed by the Consumer Goods Cooperative of the Ministry of Economic Affairs and Industry Bureau of the Ministry of Economic Affairs of the People's Republic of China 12 A7 B7 • Fifth, the invention description (U) acid and haloacetic acid, etc. Particularly suitable organic acids especially contain (CrC1G) alkyl sulfonic acid. Special A suitable combination of acids includes one or more inorganic acids, and the inorganic acid and one or more organic acids or a mixture containing two or more organic acids. If the electrolyte contains two or more Acid, the ratio of the acid ranges from 99 ·· 丨 to ^ ··, and more preferably 90: 10 to 10: 90; and more preferably 80: 20 to 20: 80. The total acid content in the electroplating solution of the present invention is about 0 to 350 g / L. Preferably it is i to 225 g / L. To be familiar with this technology Using a metal sulfate as a source of metal ions, an acid electrolyte can be obtained even without adding an acid. Therefore, in one embodiment, the copper bond solution can: use an acid. For some applications, such as those with extremely small pore sizes Wafer clock, the total amount of acid should be low., Low acid, means that the total amount of acid in the electrolyte is maintained below about 0.4M, preferably about 0 times or less, and more preferably It maintains about 0_2m. The special low-acid electrolyzed liquid material does not contain added acid, that is, the added acid content is 0g / L. Copper electrolyte can contain one or more dentate as required. Gas and bromine The halide is the better halide, and the gaseous halide is the better halide. The applicable range of the concentration of the halide ion is under the condition of the use of the halide ion, such as adding about 0 to the electric forging solution (not used) ) To dentate ion, and the optimal content is about 25 to about Wpm. The added dentate can be used as the corresponding hydrogenated acid or any suitable salt. This paper is suitable for China National Standard (CNS) A4 Specification (21 0 X 297 public love) 91944 I --------- ^ --------- (Please read the precautions on the back before filling out this page) M6120 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation 13 A7 V. Description of the invention (l3 / Many containing a known brightener disk account; 隹 state A, brightener and accelerator of the accelerator can be used in copper electrical chain solution. General brighteners contain- Or-more than one sulfur atom: typically does not contain any nitrogen atom and its molecular weight is about or less. It is preferred that the 1-dose compound can contain a sulfide and / or acid group to include the molecular formula R, each R_s 〇3X-based compounds are preferred, r is an optionally substituted alkyl group (including a cycloalkyl group), an optionally substituted heteroradical group, an optionally substituted square group, or an optionally substituted heterolipid. Ring; X is a counterion, such as sodium or potassium, and R is hydrogen or a chemical bond (such as _s_r_s033 or a substituent of a larger compound). Typical hospitals have 1 to about 16 carbons, and in particular 1 to about 8 or 12 carbons. A heteroalkyl group has one or more heteroatoms (N, 0, or S) in its chain, preferably 1 to about 16 barriers, specifically 1 to about 8 or 12 carbons. Carbocyclic aryl groups are generally aryl 'such as phenyl and naphthyl. Heteroaryl groups are also suitable aryl groups, typically containing from 1 to about 3 N, 0 or s atoms and! Up to 3 independent rings or fused rings, and contains coumarinyl, quinolinyl, pyridyl, pyrazinyl, pyrimidinyl, haloyl, Πbilyl, thienyl, thiasalyl Base, sialyl, oxadiazole, triazole, imidazolyl, indolyl, benzofuranyl, benzothiazolyl, and the like. The heteroalicyclic group generally contains i to 3 N, 0 or s atoms and i to 3 independent or fused rings' and contains tetrahydrofuryl, thienyl, tetrahydropyranylpiperyl. Fluorenyl, morpholinyl, pyrrolidinyl and the like. The substituted alkyl, heteroalkyl, aryl or heteroalicyclic substituents include Ci8 alkoxy, CM alkyl, halogen ', especially F, C1 and Br, cyano, nitro and the like. Specifically, usable brighteners include those having the following molecular formula:

X〇3S-R-SH 本紙張尺度適用中國國家標準（CNS)A4規格（21〇x297公釐） 91944 -an n n n n ϋ ·ϋ 1_ n tmme K mmmmmm · n n n n βϋ I n·-，a n n ϋ ϋ a— I ·ϋ I 唁 矣 (請先閱讀背面之注意事項再填寫本頁) 516120 經 濟 部 -智 慧 財 Λ 局 員 工 消 費 合 作 社 印 製 14 A7 、五、發明說明（u ) x〇3s-r-s-s-r-so3x 以及X〇3S-R-SH This paper size applies to China National Standard (CNS) A4 (21〇x297 mm) 91944 -an nnnn ϋ · ϋ 1_ n tmme K mmmmmm · nnnn βϋ I n ·-, ann ϋ ϋ a — I · ϋ I 唁 矣 (Please read the precautions on the back before filling out this page) 516120 Printed by the Consumer Cooperatives of the Ministry of Economic Affairs and the Bureau of Intellectual Property Λ14 A7, V. Invention Description (u) x〇3s-rssr-so3x as well as

X03S_Ar-S-S_Ar-S03X 其中，上述分子之R為視需要經取代之烧&，此外該 烷基較佳具有1至6個碳原子，該烧基又較佳係具有丄至 4㈣原子^為視需要經取代之芳基，諸如視需要經取 代之苯基或萘基；X為合適的平衡離子，諸如鈉或鉀。 私特別合適的光亮劑包含N，N_二甲基_二硫代氨基甲酸 -(3-續丙基）醋；3_氫硫基-丙基續酸_(3_績丙基）醋；％氮硫 基丙基％酸（鈉鹽），具有3-氫硫基丙烷磺酸（鉀鹽）碳酸 -二硫代·〇·乙基m旨；雙續丙基二硫化物；3_(苯并嚷嗤 基-S-硫代）丙基磺酸（鈉鹽）；吡啶鍚丙基磺三甲銨乙内酯； 1-鈉-3-氫硫基丙烷磺酸酯；揭露於美國專利第 3,778,357號之磺烷基硫化合物；二烷基胺基-硫代-甲基· 烷磺酸的氧化生成物之過氧化物；以及上述化合物之結 •合。其他合適的光亮劑也揭露於美國專利3,77〇,598 ; 4,374,7〇9 ; 4,376,685 ; 4,555,315 ;與 4风469，均將其 併入作為此處的參考資料。用於本發明之電鍍成分之較佳 光亮劑為N，N-二甲基-二硫代氨基甲酸_(3_磺丙基）酯與雙 鈉-磺酸·丙基二硫化物。 銅電鍍浴中的促進劑含量範圍為約〇丨至約 lOOOppm。該促進劑化合物之量以約〇 5至約3〇〇ppm為 佳’較佳為約1至約100ppm，又更佳為約2至約5〇ppm 左右。較佳之電鐘溶液包含大於等於1 5mg/L之一種或一 種以上之光亮劑。 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐 91944 ---------------------訂--------* (請先閱讀背面之注意事項再填寫本頁)X03S_Ar-S-S_Ar-S03X wherein R of the above-mentioned molecule is substituted as necessary, and the alkyl group preferably has 1 to 6 carbon atoms, and the alkyl group preferably has 丄 to 4㈣ atoms ^ If desired, substituted aryl, such as optionally substituted phenyl or naphthyl; X is a suitable counterion, such as sodium or potassium. Particularly suitable brighteners include N, N_dimethyl_dithiocarbamic acid- (3-continyl) vinegar; 3-hydrothio-propyl-continuous acid_ (3_propyl) vinegar; % Nitrogenthiopropyl% acid (sodium salt) with 3-hydrothiopropanesulfonic acid (potassium salt) carbonic acid-dithio ··· ethyl m purpose; di-continyl propyl disulfide; 3- (benzene Pyridinyl-S-thio) propylsulfonic acid (sodium salt); Pyridinylpropylsulfonyltrimethylammonium lactone; 1-Sodium-3-hydrothiopropanesulfonic acid ester; disclosed in US Patent No. 3,778,357 Sulfoalkyl sulfur compounds; peroxides of oxidation products of dialkylamino-thio-methyl · alkanesulfonic acids; and combinations and combinations of the above compounds. Other suitable brighteners are also disclosed in U.S. Patents 3,77〇, 598; 4,374,709; 4,376,685; 4,555,315; and 4 Feng 469, all of which are incorporated herein by reference. Preferred brighteners for use in the electroplating composition of the present invention are N, N-dimethyl-dithiocarbamate (3-sulfopropyl) ester and disodium-sulfonic acid · propyl disulfide. The accelerator content in the copper electroplating bath ranges from about 0.1 to about 1,000 ppm. The amount of the accelerator compound is preferably about 0.05 to about 300 ppm ', more preferably about 1 to about 100 ppm, and still more preferably about 2 to about 50 ppm. A preferred electric clock solution contains one or more brighteners of 15 mg / L or more. This paper size applies to China National Standard (CNS) A4 specification (21 × 297 mm 91944 --------------------- Order -------- * (Please read the notes on the back before filling this page)

經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 15 用於銅m緞冷中的抑 取代為佳，較佳為氧鏠。—二為聚合原料，以具有雜原子 聚醚，如下列分子式所$ •'理心的抑制劑為高分子量的 R °^°ΧΥ〇Χύό) Η 其中，R為Η或含有 η 、、、勺2至20個碳馬+的笔 基；X、Y、X，、Y，分別獨· 原子的方基或烷 為風，燒基，以甲美、 或丙基為佳；芳基，如笨其·— ^ 基、 基，方燒基，如I甲其· 多個X、Y、X，與γ，為氫 本甲土，以一或 、子乂佳，及η為5至1〇〇 〇〇〇 + „ 的整數。較佳者，R為乙烯 ’ 間 烯，η為大於12,000的整數。 該抑制劑的含量範圍自 數 固目約〇·1至約l000ppm。較 抑制劑化合物的含量自約〇 5 ’ 至約5〇〇ppm左右，又較佳 自約1至約200ppm。 仅住 表面活性劑可視需要加 _ & 列电級冷中。該表面活性劑 所添加的濃度範圍以該電铲：六 ^ ^电鍍洛液之重量計自約1至 10,卿PPm為佳’以約5至1〇〇〇〇ppm較佳。較適合之表 面活性劑為市售可得之聚乙二醇共聚物，包含聚乙二醇: 聚物。該聚合物可購自，例如BA b 彻 P + ^ 1ETR〇Nic ” PlUR〇N!c商標來銷售），而共聚物可購自chemax。 /均化劑可視需要加至鋼電鍍浴中。本發明的電錢較佳 系使用#或一種以上的均化劑化合物。所使之均化劑的 :可自約0.01至50ppm左右。適當的勻化劑之實例係揭 露亚提出於美國專利第 3,77〇,598; 4,374,709; 4,376,685 ，，:、4,673，459號。一般而言，有用的均化劑包含 ，含有經取代^胺基諸知具有R-N-R，的化合物，R與R，分 本紙張尺度_中國®i^^NS)A4規格⑽χ 297公髮）--’、 91944 -------------Φ--------訂---------線^_ (請先閱讀背面之注音？事項再填寫本頁} 516120 經濟部智慧財產局員工消費合作社印製 16 A7 ----------E__—_ —__ .五、發明說明（16 ) 獨立為經取代或未經取代的烷基或經取代或未經取代的芳 基。一般的烷基具有1至6個碳原子，牲中/ 符疋s之係具有i 至4個碳原子。適當的芳基包含經取代或未經取代的苯基 或萘基。經取代之烷基與芳基的取代基可為，例如烷基: 鹵素與烷氧基。 & 具體而言，適當的均化劑包含，但不局限於羥乙 >基）-2-伸乙基硫脲；4_氫硫基吡啶；2_氫硫基噻唑啉；Z烯 硫脲；硫脲；烷化聚烯亞胺；揭露於美國專利第3，， 084的吩嗪氮鎗化合物；含N•雜芳香族環的聚合物；四級 化丙烯聚合胺；聚乙烯基氨基曱酸鹽；吡咯烷酮；與咪唑。 較佳的均化劑則為丨气八羥乙基）-2_伸乙基硫脲。 將晶種層與上述的電鍍溶液接觸，可進行本發明實質 連續晶種層之電鍍或金屬。一般而言，晶種層接觸電鍍溶 液一段時間，並且以一足夠的電流密度使金屬在晶種層上 ^沈積至所需的厚度。使用銅電鍍溶液之溫度範圍可自室溫 以下至室溫以上，例如高至65°c (或）以上。在此期間，電 鍍溶液較佳係以空氣噴佈器、機械攪拌（w〇rk pieee agitation)、衝擊或是其他適當方法攪拌。依據基板特性， 電鍍處理的電流範圍自1至40ASF。依據欲電鍍物件的困 難度’電鍍時間範圍可自約2分鐘至1小時或以上。 呈上述’許多基板可以用本發明之組成物進行電錢。 本發明的組成物特別適用於較難電鍍之電鍍物件，諸如直 徑小的電路板之基版，高深寬比的微導通孔與其他孔徑。 本發日月之電鍍成分亦特別適用於積體電路元件，諸如形成 I紙張尺度適用中關家標準（CNS)A4規格（21G X 297公爱) " " 91944 ^ --------^---------線 (請先閱讀背面之注意事項再填寫本頁) 516120 A7 B7 五、發明說明（Π 半導體元件等之電鑛。本發明的方 深寬比的微導通孔與溝槽，例如深寬比、=具有高 基板，提供實質上連續之。 為4」或以上之 f 呈上述，深寬比至少為4 :〗，鍍 以下，且本發明的實質連續晶種層上毫：=。⑽或 束檢測無空隙或雜質為標準）。基板上之、晶種疫以離子 ΓΓ以下’一下，以及5:心^ 之深寬比’甚至高達15:1或以上，這此都可利 用本發明有效地強 二郁了利 之臭相Μ m，、有018吨或是更小的孔徑 之基板，本發明均可修補該基板上的晶種層。 因此，本發明提供一種將金屬層電沉基於晶種層之表 面的方法，包含下列步驟：將基板上所沉積的金屬晶種層 與鋼踢組成物接觸，以形成實質上連續的晶種層，宜中， 銅膠組成物含有少量的可離子化纪化合物以及大量的鋼膠 拉子，以及將基板與電鑛溶液接冑，該溶液含有一種或一 種以上金屬離子及電解液。 本發明還提供另一種製造電子裝置的方法，該方法包 含下列步驟：將電子裝置基板上所沉積的金屬晶種層與鋼 膠組成物接觸，以形成實質上連續的晶種層，其中，鋼膠 ’、且成物3有少置可離子化把化合物與大量的銅膠粒子；以 及將晶種層與電鍍溶液接觸，該溶液包含一種或_種以上 的金屬離子與電解質。該電子裝置最好是一種積體電路。 另外’電子裝置基板最好是製造積體電路所使用的晶圓。 J_此外’本發明還提供一種含有一種或一種以上的孔獲. 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐) "' ^ 17 91944 516120 A7 B7 經濟部智慧財產局員工消費合作社印製 一 18 •五、發明說明（π ) 之％子裝置基板，每一種孔徑均含有上述之方法所強化的 晶種層沉積。 根據本發明的晶種層修補處理之後，將基板與習知的 金屬化電鍍溶液接觸，諸如酸性鋼電鍍溶液，以填塞或實 質上填塞孔徑。在金屬化處理後，也就是將金屬填入孔徑 之後，晶圓的基板最好能進行化學機械平坦化處理 (“CMP”）。該項處理程序是依據下列發明而進行。 將晶圓固定於晶圓載體’使晶圓推向移動樾光塾之表 面。抛光塾可為習知的平滑拋光墊或是溝槽化拋光墊。溝 槽化拋光墊為該項技藝中已知，可購自美國德拉威州 (Delaware)，紐瓦克（Newark)的Rodel公司。拋光墊可放置 於習知的壓板上，該壓板可旋轉拋光墊。抛光墊可藉由固 定方法例如，但不侷限於黏著物，如雙面膠帶固定於該壓 板。 將拋光液或泥漿灌入至拋光墊上。晶圓載體可置於拋 光墊上不同的位置。利用任何一種適當的固定方法，可將 晶圓固定於適當位置，固定媒介方法例如，但不侷限於晶 圓固定益’真空或液體張力，諸如，但不侷限於流體，諸 如，但不侷限於水。如果採用真空作為固定方法，則最好 能具備一種接至晶圓載體的空心軸。此外，空心軸可以調 節氣壓，諸如，但不侷限於空氣或者惰性氣體，或者利用 真空先固定晶圓。氣體或真空會由空心軸流至載體。氣體 可促使μ圓推向抛光塾以獲得所需之外形。真空可先將晶 圓固定於晶圓載體中的適當位置。當晶圓放置於拋光墊上 本紙張尺度適用中國國豕標準（CNS)A4規格（210x 297公爱） 91944 -------------裝--------訂--------•線 (請先閱讀背面之注意事項再填寫本頁) 516120 五、發明說明（I9 ) =二真空會釋放出來，氣屡會使晶圓推向拋光塾。 =將：除過多或不需要的銅。虔板與晶圓载體可獨立地 此’晶圓的旋轉方向可能與相同或不同速度的拖 尤墊一樣，也可能不一樣。 發明提供—種利用化學機械平坦化製程，自 導胜明圓中去除多餘物質，該製程包含：使半導體晶圓 /、凝轉拋光墊接觸，以去除半導體晶圓中多餘物質;並中， +導體晶圓所含的晶種層已依據上述方法先進行強化。 本發明所提供之另-種方法是利用化學機械平坦化製 二自+導體晶圓中去除多餘物質，而該半導體晶圓具有 义個大小的孔徑，其中，該平坦化製程包含. 圓與旋轉抛光塾接觸，以自半導體晶圓中去除 ;匕餘的物f ’·晶種層所含之孔徑已依據上述方法先進行強 發明係針對鋼電鑛浴說明’但熟悉該項技藝者 應了解本發明實質上連續的晶種層可藉由多種不同的電鏟 冷來進行電鍍，諸如錫、錫合金、鎳、鎳。 第1實你丨_ 消 依據美國專利4,68I5630(Brasch)的實例4，加入氯化 =以製備鋼膠電鍍溶液。矽晶圓基板具有非連續物理蒸 虱况積(“PVD”)銅晶種層，該晶種層覆蓋於氮化鈕(、 =障層；於3Gt使該以圓基板與銅膠電鍍溶液接觸1〇 刀鐘。之後再以去離子水將晶圓基板洗淨，再與活化溶液 j如t釋的氟硼酸1錢溶液）接觸30秒，前項_ 4 ^氏張尺度適用(CNS^^721Qx 297公爱）---、儿成 19 訂 線 91944 經 濟 部 .、智 慧 財 產 局 消 費 合 作 社 印 製 516120 A7 ----— _B7 ____ 五、發明說明（2〇 ) 後’再將該基板洗淨，並與電鍍銅溶液接觸，該溶液係 Shipley公司（馬博羅，麻州）以U]ltrafill 2001商標銷售。 經銅沉積與空隙填塞成之後，再將基 板洗淨，並做下一步之處理。 實例2 依據美國專利4,681，630斤1^(^)的實例4，加入氯化 錢把以製備鋼膠電鍍溶液。矽晶圓基板具有非連續物理蒸 氣;儿積（PVD )鋼晶種層’該晶種層覆蓋於TaN阻障層； 於30°C使該矽晶圓基板與銅膠電鍍溶液接觸1〇分鐘。之 後再以去離子水將晶圓基板洗淨，再與活化溶液（諸如稀釋. 的氟硼酸電鍍溶液）接觸30秒，前項處理完成後’再將該 基板洗淨，並以標準的緩慢速度與電鍍銅溶液接觸。25它 電鍍1 〇分鐘後，在晶圓基板上則形成i 〇〇%的銅。在洗淨 處理後’將晶圓置於熱平板，在含氧量低的環境下放置 秒的時間，以便做锻鍊處理。熱平板的溫度為20『c。之 後，將晶圓基板由熱平板移開並冷卻。每次冷卻， 圓基板做金屬化處理’方式是將晶圓基板與電鍍鋼溶液= 觸，該溶液係Shlpiey公司（馬博羅，麻州）以商 讀鎖售。將晶圓基板置於電鍍溶液達 ::肌 、丨W 1、 权兄份的時問， ^形成所需之銅層。再將該晶圓基板由電鍍溶液中 以去離子水洗淨，並著手下一步處理。 汗 本紙張尺度適用^^標準（CNS)‘規格⑽x 297公复 91944 --------^ --------I (請先閱讀背面之注意事項再填寫本頁) 20Printed by the Consumer Affairs Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs 15 It is better to use it in copper satin cooling, and more preferably oxygen. —Two is the raw material for polymerization, with polyethers with heteroatoms, as shown in the following formula: • Reasonable inhibitor is high molecular weight R ° ^ ° ΧΥ〇Χύό) Η where R is Η or contains η ,,, or 2 to 20 carbon horse + pen bases; X, Y, X, and Y, respectively. Atomic square or alkane is wind, and the base is preferably methyle, or propyl; aryl, such as benzene Its ^ groups, radicals, and radicals, such as I, and a number of X, Y, X, and γ, are hydrobromide, preferably one or two, and 乂 is 5 to 100. 〇〇〇 + Integer. Preferably, R is ethylene 'm-ene, and η is an integer greater than 12,000. The content of the inhibitor ranges from about 0.1 to about 1,000 ppm. The content of the inhibitor compound is more than that of the inhibitor compound. From about 0.05 'to about 500 ppm, and more preferably from about 1 to about 200 ppm. Only the surfactant can be added to the electrical grade cooling as needed. The concentration range of the surfactant is The electric shovel: the weight of the electroplating solution is from about 1 to 10, preferably PPm is better, about 5 to 1000 ppm. A more suitable surfactant is a commercially available polymer. Glycol copolymers comprising polyethylene glycol: copolymer The polymer is commercially available from, for example, BA b Toru P + ^ 1ETR〇Nic "trademark sold PlUR〇N c), and copolymers commercially available from chemax.!. The leveling agent can be added to the steel plating bath as required. The electricity bill of the present invention preferably uses # or more than one leveling agent compound. The leveling agent used can be from about 0.01 to 50 ppm. Examples of suitable leveling agents are disclosed in U.S. Pat. Nos. 3,77,598; 4,374,709; 4,376,685, 4,673,459. In general, useful leveling agents include compounds containing substituted ^ amino groups known to have RNR, R and R, paper size _China® i ^^ NS) A4 size ⑽χ 297 issued)- ', 91944 ------------- Φ -------- Order --------- line ^ _ (Please read the phonetic on the back? Matters before filling in this Page} 516120 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 16 A7 ---------- E __—_ —__. V. Description of the Invention (16) Independently substituted or unsubstituted alkyl or A substituted or unsubstituted aryl group. A typical alkyl group has 1 to 6 carbon atoms, and the / symbol system has i to 4 carbon atoms. Suitable aryl groups include substituted or unsubstituted Phenyl or naphthyl. Substituents of substituted alkyl and aryl may be, for example, alkyl: halogen and alkoxy. &Amp; Specifically, suitable leveling agents include, but are not limited to, hydroxyethyl >;))-2-Ethylthiourea;4-Hydroxythiopyridine;2-Hydroxythiothiazoline; Zene thiourea; thiourea; alkylated polyeneimine; disclosed in US Patent No. 3 ,, Phenazine nitrogen gun compound of 084; N • heteroaromatic ring-containing polymer Quaternary propylene polymerized amines; polyvinylaminophosphonates; pyrrolidone; and imidazole. The preferred leveling agent is octahydroxyethyl) -2_ethyl thiourea. By contacting the seed layer with the above-mentioned plating solution, electroplating or metal of the substantially continuous seed layer of the present invention can be performed. Generally, the seed layer is in contact with the plating solution for a period of time, and the metal is deposited on the seed layer to a desired thickness with a sufficient current density. The temperature of the copper plating solution can range from below room temperature to above room temperature, for example, up to 65 ° c (or above). During this period, the electroplating solution is preferably stirred by an air sprayer, mechanical pieee agitation, impact, or other appropriate methods. Depending on the characteristics of the substrate, the current of the plating process ranges from 1 to 40 ASF. Depending on the difficulty of the object to be plated, the plating time can range from about 2 minutes to 1 hour or more. Many of the substrates described above can be used to make electricity using the composition of the present invention. The composition of the present invention is particularly suitable for electroplated objects which are difficult to be electroplated, such as the base plate of a small-diameter circuit board, micro-vias with high aspect ratios, and other apertures. The plating composition of this sun and the moon is also particularly suitable for integrated circuit components, such as forming the I paper size and applying the Zhongguanjia Standard (CNS) A4 specification (21G X 297 public love) " " 91944 ^ ------ -^ --------- Line (Please read the precautions on the back before filling out this page) 516120 A7 B7 V. Description of the invention (Π semiconductor components, etc.) The square aspect ratio of the invention Micro-vias and trenches, such as aspect ratio, = have a high substrate, provide substantially continuous. F is 4 ″ or more, as described above, and the aspect ratio is at least 4: 〖, plating below, and the essence of the present invention On the continuous seed layer: =. ⑽ or beam detection without voids or impurities as standard). On the substrate, the seed crystals are below the ion ΓΓ, and the aspect ratio of 5: heart ^ is even as high as 15: 1 or more. This can be effectively used to effectively depress the odorous phase Μ m For substrates having a diameter of 018 tons or smaller, the present invention can repair the seed layer on the substrate. Therefore, the present invention provides a method for electrodepositing a metal layer based on the surface of a seed layer, comprising the following steps: contacting a metal seed layer deposited on a substrate with a steel kick composition to form a substantially continuous seed layer In Yizhong, the copper glue composition contains a small amount of ionizable compounds and a large amount of steel rubber sliders, and the substrate is connected with the electric ore solution, and the solution contains one or more metal ions and an electrolyte. The present invention also provides another method for manufacturing an electronic device. The method includes the following steps: contacting a metal seed layer deposited on a substrate of the electronic device with a steel glue composition to form a substantially continuous seed layer, wherein the steel The glue 3 and the product 3 have a small amount of ionizable compounds and a large amount of copper glue particles; and a seed layer is contacted with a plating solution, the solution containing one or more metal ions and an electrolyte. The electronic device is preferably an integrated circuit. In addition, the electronic device substrate is preferably a wafer used for manufacturing an integrated circuit. J_In addition, the present invention also provides one or more types of holes obtained. This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) " '^ 17 91944 516120 A7 B7 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative Co., Ltd. 18 • Fifth, the invention's description (π) of the sub-device substrate, each aperture contains the seed layer deposition strengthened by the above method. After the seed layer repair process according to the present invention, the substrate is contacted with a conventional metallizing plating solution, such as an acid steel plating solution, to fill or substantially fill the pores. After the metallization process, that is, after the metal is filled into the aperture, the substrate of the wafer may preferably be subjected to chemical mechanical planarization ("CMP"). This processing procedure is performed according to the following invention. The wafer is fixed to the wafer carrier 'so that the wafer is pushed toward the surface of the mobile wafer. The polishing pad may be a conventional smooth polishing pad or a grooved polishing pad. Grooved polishing pads are known in the art and are available from Rodel, Newark, Delaware, USA. The polishing pad can be placed on a conventional platen, which can rotate the polishing pad. The polishing pad may be fixed to the platen by a fixing method such as, but not limited to, an adhesive such as a double-sided tape. Fill the polishing pad with polishing solution or mud. The wafer carrier can be placed in different positions on the polishing pad. The wafer can be fixed in place using any suitable fixing method, such as, but not limited to, wafer fixing, such as vacuum or liquid tension, such as, but not limited to, fluid, such as, but not limited to water. If a vacuum is used as the fixing method, it is preferable to have a hollow shaft connected to the wafer carrier. In addition, the hollow shaft can adjust the air pressure, such as, but not limited to, air or inert gas, or use a vacuum to hold the wafer first. Gas or vacuum will flow from the hollow shaft to the carrier. The gas can cause the μ circle to be pushed towards the polishing pad to obtain the desired profile. The vacuum first holds the wafer in place in the wafer carrier. When the wafer is placed on the polishing pad, the paper size is applicable to China National Standard (CNS) A4 (210x 297). -------- • Wire (please read the precautions on the back before filling this page) 516120 V. Description of the invention (I9) = Two vacuums will be released, and the gas will often push the wafer towards the polishing pad. = Will: remove excess or unwanted copper. The plate and the wafer carrier may be independent. The rotation direction of the wafer may be the same as or different from the moving pad at the same or different speed. The invention provides a chemical mechanical planarization process that removes excess material from the guide circle. The process includes: contacting a semiconductor wafer / condensation polishing pad to remove the excess material from the semiconductor wafer; and, + The seed layer contained in the conductor wafer has been strengthened according to the above method. Another method provided by the present invention is to use chemical-mechanical planarization to remove excess material from a two-conductor + conductor wafer, and the semiconductor wafer has a pore size of one size, wherein the planarization process includes a circle and a rotation. Polished 塾 contact to remove from the semiconductor wafer; the pores contained in the residual material f '· seed layer have been strongly invented according to the method described above for the description of the steel and electric bath' but those familiar with this technology should understand The substantially continuous seed layer of the present invention can be electroplated by a variety of different electric shovel cooling, such as tin, tin alloy, nickel, nickel. No. 1 丨 __Consumption According to Example 4 of U.S. Patent No. 4,68I5630 (Brasch), chlorinated = was added to prepare a steel rubber plating solution. The silicon wafer substrate has a discontinuous physical vapor deposition ("PVD") copper seed layer, which is covered with a nitride button (, = barrier layer; the circular substrate is brought into contact with the copper paste plating solution at 3Gt 10 knife minutes. After that, the wafer substrate is washed with deionized water, and then contacted with the activation solution j such as t-released fluoroboric acid solution for 30 seconds. The foregoing item _ 4 ^ Zhang scale is applicable (CNS ^^ 721Qx 297 Public Love) ---, Ercheng 19 Order line 91944 Ministry of Economic Affairs, Intellectual Property Bureau Consumer Cooperatives printed 516120 A7 -------- _B7 ____ V. Description of the invention (2〇) 'The substrate is then cleaned And in contact with a copper electroplating solution, which is sold by Shipley Corporation (Marboro, Mass.) Under the U] Ultrafill 2001 trademark. After copper deposition and void filling, the substrate is washed and processed for the next step. Example 2 According to Example 4 of U.S. Patent No. 4,681,630 kg 1 ^ (^), a chlorinated handle was added to prepare a steel cement plating solution. The silicon wafer substrate has a discontinuous physical vapor; a PVD steel seed layer 'the seed layer covers the TaN barrier layer; the silicon wafer substrate is brought into contact with the copper paste plating solution at 30 ° C for 10 minutes . After that, the wafer substrate is washed with deionized water, and then contacted with an activating solution (such as a dilute fluoroboric acid plating solution) for 30 seconds. After the foregoing process is completed, the substrate is washed again, and at a standard slow speed, Contact with copper plating solution. 25 After plating for 10 minutes, 100% copper was formed on the wafer substrate. After the cleaning process, the wafer is placed on a hot plate and placed in a low-oxygen environment for a period of seconds for the forging chain process. The temperature of the hot plate is 20 ° c. After that, the wafer substrate is removed from the hot plate and cooled. For each cooling, the round substrate is metallized 'by contacting the wafer substrate with an electroplated steel solution. The solution is sold by Shrlpiey Company (Marboro, Mass.) Under commercial read lock. When the wafer substrate is placed in the plating solution for a period of time: 1: muscle, weight, weight, and formation of the desired copper layer. The wafer substrate was washed with deionized water from the plating solution, and the next step was processed. Sweat This paper size applies ^^ Standard (CNS) ‘Specifications ⑽ x 297 public copy 91944 -------- ^ -------- I (Please read the precautions on the back before filling this page) 20

Claims (1)

M6120M6120 申請專利範圍 經濟部智慧財產局員工消費合作社印製 種強化沉積於基板上的非連績金屬晶種層之方法，該 :法包：下列步驟:將沉積於基板上的金屬晶種層與： 膠組成物接觸，以形成實質上連續的晶種層，其中，該 鋼谬組成物包括少量的可離子化把化合物及大量的鋼 膠粒子。 2.如申請專利範圍第1項 甘士 晶種層。 '、、中’金屬晶種層係鋼 3·:申請專利範圍第1項之方法，其中，纪化合物之含旦 充份地提供自約50至約8〇ppm的飽金屬。 里 Hi專利範圍第1項之方法，其中，鋼膠組成物包括 銅金屬之量係自膠瑢液之U8g/L。 括 5.如申請專利範圍第i項之方 用浸潰，噴霧血旋韓㈣古“ H曰種層係利 …請專利範圍、第項之二 7至約8。 方法，其中，銅踢的阳值為約 %種Λ?層電沉積至晶種層表面之方法，該方法包括 欠驟.將沉積於基板上的金屬晶種層 接觸，以形成實質上連續的晶種層，其中，該铜= ==少量的可離子化把化合物及大量的銅膠教V: 基板與電鍍溶液接觸’該溶液包括-種或-種“ 的金屬離子與電解質。 上 8. 如申請專利範圍第7項之方法 晶種層。 ，、甲*屬-種層係鋼 9. 如申請專利範圍帛7項之方法’其中，鈀化合物… (請先閱讀背面之注意事項再填寫本頁} · !丨 1 ί I 訂-!丨 表紙張尺度通財關家標準（ciiG規格⑽x 297¾ ^ 1U1Z.U ^ 1U1Z.U 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 係充份地提供自約5 10如由咬奎& » 主约S〇Ppm的鈀金屬。 H).如肀凊專利範圍篦 ^ 、方法，其中，銅膠組成物包括 鋼金屬之量係自朦、六 牙目膠/谷液之1至8g/L。 11. 如申凊專利範圍第7 、 、之方法，其中，銅膠的pH值為 約7至約8。 12. 如申請專利範圍第7項 方法，其中，一種或一種以上 的金屬離子係選自硫酸鋼、醋酸銅、說删酸銅、葡轉酸 鋼甲***確酸鋼、芳基確酸銅、續酸銅、或梢酸 鋼。 、 13·如申請專利範圍第7 項之方法，其中，電解質為酸性6 14·如申請專利範圍第7 古 項之方法，其中，電鍍溶液復包括 :種或-種以上的添加劑，該添加劑係選自鹵化物，光 ah]抑制剑、均化劑、晶粒細化劑、潤濕劑、或表面 活性劑。 \5·如申請專利範圍第“項之方法，丨中，光亮劑的含量 為1.5mg/L或以上。 16-種製造電子裝置之方*，該方*包括下列步驟：將沉 積於電子裝置基板上的金屬晶種層與銅膠組成物接 觸，以形成銅膠表面，其中，該鋼膠組成物包括少量的 可離子化鈀化合物及大量的銅膠粒子；以及將基板與電 鍍丨谷液接觸，該溶液包括一種或一種以上的金屬離子及 電解質。 17·如申請專利範圍第16項之方法，其中，金屬晶種層係 鋼晶種層。 ______________--------^-------!線 {請先閱讀背面之注意事項再填寫本頁) ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 22 91944 六、申請專利範圍 專利範圍第16項之方法，其中，鈀化合物之含 Ί:9〉由^地提供自約5至約8〇Ppm的纪金屬。 •如申請專利範圍第 (請先閱讀背面之注意事項再填寫本頁) 括鋼金屬之、r ώ 、之方法，其中，銅膠組成物包 钔金屬之薑係自膠溶液之1至8g/L。 20.如申請專利範圍第16 奶， 項之方法，其中，銅膠的pH值為 約7至約8。 21:ΠΓ範圍第16項之方法，其中，-種或-種以 酸Γ=係選自硫酸鋼、醋酸銅、氟蝴酸鋼、葡糖 酸:m㈣酸銅、芳基《銅、韻飼、或確 22. 如申請專利範圍第16項之 9. , , ^ ^ 次吳甲電解質為酸性。 23. 如申凊專利範圍第Μ項之 杯一接斗 項之方法，其中，電鍍溶液復包 t一種或一種以上的添加劑，該添加劑係選自i化物、 光亮劑、抑制劑、均化劑、晶粒細化劑、潤濕劑、或表 面活性劑。 24. 如申請專利範圍第23項之方法，其_，光亮劑的含量 為1.5mg/L或以上。 25. 如申請專利範圍第16項之方法，其，，電子裝置係積 體電路。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 23 91944Scope of patent application: The method of printing seed strengthened non-continuous metal seed layer deposited on the substrate by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics, the method: the following steps: the metal seed layer deposited on the substrate and The rubber composition is contacted to form a substantially continuous seed layer, wherein the steel composition includes a small amount of ionizable compound and a large amount of steel rubber particles. 2. As in the scope of patent application, item 1 Ganshi seed layer. ',,' The metal seed layer steel 3: The method of claim 1 in which the scope of the patent compound is sufficient to provide a saturated metal from about 50 to about 80 ppm. The method of item 1 of the Hi patent scope, wherein the amount of the steel rubber composition including copper metal is U8g / L from the rubber paste. Including 5. If you apply for impregnation in item i of the patent scope, spray blood spin Han Hangu "H said seed layer system benefits ... please patent scope, item bis 7 to about 8. Method, where the copper kick A method for electrodepositing a seed layer to the surface of a seed layer with a positive value of about%. The method includes a step. The metal seed layer deposited on a substrate is contacted to form a substantially continuous seed layer. Copper = == A small amount of ionizable compounds and a large amount of copper glue. V: The substrate is in contact with the plating solution. The solution includes-or-a type of metal ions and electrolyte. Top 8. The method as in item 7 of the patent application scope. Seed layer. A, genus-seed layer steel 9. If the method of applying for patent scope 帛 7 method 'Among them, palladium compounds ... (Please read the precautions on the back before filling out this page} ·! 丨 1 ί I order-! 丨Table Paper Standards Standards for Wealth Management (ciiG specifications ⑽ x 297¾ ^ 1U1Z.U ^ 1U1Z.U Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of patent applications is fully provided from about 5 10 »» Mainly about palladium metal of S0Ppm. H). For example, the scope of the patent 篦 ^, method, wherein the amount of copper plastic composition including steel metal is from 1 to 8g of halo, hexadontant gum / cereal. / L. 11. The method of claim 7 in the patent scope, wherein the pH of the copper paste is about 7 to about 8. 12. The method of claim 7 in the patent scope, wherein one or more metals The ion system is selected from the group consisting of sulfuric acid steel, copper acetate, copper acid, gluconic acid steel, self-fired acid steel, copper aryl acid, copper acid, or acid steel. 13. If the scope of patent application is the seventh The method of item 7, wherein the electrolyte is acidic The plating solution includes: one or more additives, the additive is selected from the group consisting of halide, light ah] inhibitor sword, leveling agent, grain refiner, wetting agent, or surfactant. \ 5 · For example, in the method of applying for the “item of the patent scope”, the content of brightener is 1.5 mg / L or more. 16-Methods for manufacturing electronic devices *, which method includes the following steps: The metal seed layer is in contact with the copper paste composition to form a copper paste surface, wherein the steel paste composition includes a small amount of ionizable palladium compound and a large amount of copper paste particles; and the substrate is contacted with the plating solution and the valley solution. The solution includes one or more metal ions and an electrolyte. 17. The method according to item 16 of the scope of patent application, wherein the metal seed layer is a steel seed layer. ______________-------- ^ ---- ---! Line {Please read the notes on the back before filling out this page) ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 22 91944 VI. Scope of patent application No. 16 of the patent scope Method, wherein palladium-containing rhenium : 9〉 The metal materials from about 5 to about 80 pm are provided by ^. If the scope of patent application (please read the precautions on the back before filling in this page), including the methods of steel metal, r addy, and methods, of which The copper gum composition contains 1 to 8 g / L of metal-coated ginger based gum solution. 20. The method according to item 16 of the patent application, wherein the pH of the copper gum is about 7 to about 8. 21 : Method of item 16 in the range of ΠΓ, in which-species or-species is selected from the group consisting of sulfuric acid steel, copper acetate, fluorophosphate steel, gluconic acid: copper methane, aryl "copper, rhyme, Probably 22. If the scope of the patent application No. 16 of 9.,, ^ ^ Wujia electrolyte is acidic. 23. For example, the method of cup one of item M of the patent application scope, wherein the electroplating solution includes one or more additives, the additives being selected from the group consisting of ions, brighteners, inhibitors, and leveling agents. , Grain refiner, wetting agent, or surfactant. 24. If the method according to item 23 of the patent application is applied, the content of brightener is 1.5 mg / L or more. 25. The method of claim 16 in which the electronic device is an integrated circuit. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 23 91944
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