TWI285687B - Electrolytic copper plating solutions - Google Patents
Electrolytic copper plating solutions Download PDFInfo
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- TWI285687B TWI285687B TW092122506A TW92122506A TWI285687B TW I285687 B TWI285687 B TW I285687B TW 092122506 A TW092122506 A TW 092122506A TW 92122506 A TW92122506 A TW 92122506A TW I285687 B TWI285687 B TW I285687B
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
Abstract
Description
1285687 而焦磷酸銅和氰化銅係在低至中電流密度時使用以沉積 銅。因為與處理氰化物和氟硼酸相關聯之健康憂慮及與焦 磷酸鹽相關聯之廢物處理事務，最廣泛使用之商業上鍍銅 溶液是硫酸銅。使用硫酸銅溶液來沉積銅塗層在各種基板 上，例如印刷電路板、汽車零件和家用固定裝置。銅離子 濃度自每升約10克變更至每升約75克。硫酸濃度可自每升 約10克變更至每升約300克。關於電子組件之銅鍍敷通常使 用低銅金屬濃度和高自由酸濃度。1285687 While copper pyrophosphate and copper cyanide are used at low to medium current densities to deposit copper. The most widely used commercial copper plating solution is copper sulfate because of the health concerns associated with handling cyanide and fluoroboric acid and the waste disposal associated with pyrophosphate. Copper sulphate solutions are used to deposit copper coatings on a variety of substrates, such as printed circuit boards, automotive parts, and household fixtures. The copper ion concentration was varied from about 10 grams per liter to about 75 grams per liter. The sulfuric acid concentration can vary from about 10 grams per liter to about 300 grams per liter. Copper plating for electronic components typically uses low copper metal concentrations and high free acid concentrations.
使用確酸在電鍍中先前已予敘述。The use of acid is described previously in electroplating.
Proell W. A.在美國專利#2,525,942號中聲稱使用烷磺酸 電解液在電鍍中。然而，僅使用混合之烷磺酸且僅特定聲 稱係為錯、鎳、鎘、銀和鋅而造成。Proell W. A. claims to use an alkane sulfonic acid electrolyte in electroplating in U.S. Patent No. 2,525,942. However, only mixed alkane sulfonic acids are used and only the specific acoustical systems are erroneous, nickel, cadmium, silver and zinc.
Proell W. A.在美國專利#2,525,943號中聲稱明確言之， 使用烷磺酸電解液在電鍍銅中。然而，僅使用混合之烷磺 酸且並未揭示混合物之正確組成。Proell W. A. claims to be expressly stated in U.S. Patent No. 2,525,943, the use of an alkanesulfonic acid electrolyte in electroplated copper. However, only mixed alkane sulfonic acids were used and the correct composition of the mixture was not revealed.
Proell W. A·; Faust，C. L. ; Agruss，B. ; Combs，E. L.在 The Monthly Review of the American Electroplaters Society 1947, 34，541-9中記述自以混合之烷磺酸為基礎之電解液製造用 以鍍銅之較佳調配物。然而，亦是僅使用混合之烷磺酸。Proell W. A.; Faust, CL; Agruss, B.; Combs, EL, in The Monthly Review of the American Electroplaters Society 1947, 34, 541-9, for the production of electrolytes based on mixed alkane sulfonic acids A better formulation of copper plating. However, it is also the use of only mixed alkanesulfonic acids.
Dahms，W.和 Wunderlich, C·在德國專利#4,33 8,148號中揭 示：併入有機硫化合物作為添加劑之以甲磺酸鹽為基礎之 鍍銅系統。Dahms, W. and Wunderlich, C., German Patent No. 4,33,148, discloses a mesylate-based copper plating system incorporating an organic sulfur compound as an additive.
Jiqing，Cai，Diandu Yu Huanbao 1995, 15(2)，20-2揭示使 用以甲磺酸鹽為基礎之鍍銅調配物的某些利益。陳述最大 87506 -6 - 1285687 之利益是優良表面清潔及實際鍍敷步驟前之蝕刻。Jiqing, Cai, Diandu Yu Huanbao 1995, 15(2), 20-2 disclose certain benefits of using a mesylate-based copper plating formulation. The stated benefit of 87506 -6 - 1285687 is the excellent surface cleaning and etching prior to the actual plating step.
Bernards, R. F. ； Fisher, G. ； Sonnenberg, W. ； Cerwonka, E. J. ; Fisher S.，在美國專利#5,051，154號中記述鍍銅之表面 活性添加劑，僅較少述及MS A係許多可能電解液之一。然 而，未包括採用MS A之實例。Bernards, RF; Fisher, G.; Sonnenberg, W.; Cerwonka, EJ; Fisher S., the surface-active additive for copper plating is described in U.S. Patent No. 5,051,154, and only a few of the possible electrolysis of MS A are described. One of the liquids. However, examples using MS A are not included.
Andricacos，P. C·，Cliang，I. C” Hariklia，D.和 Horkans，J· 等在美國專利#5,385,661號中討論經由在電勢不足下沉 積，容許電沉積含有少量的錫和錯之Cu合金的方法。該專 利案中揭示主要是由於甲磺酸/甲磺酸鹽的弱錯合性質， MS A是特別極適合於容許此型的方法適當出現。亦出版關 於此主題之論文（J. Electrochem· Soc· ; 1995, 142(7) ; 2244-2249) 〇 最近，業已使用鍍銅在半導體晶片製造方面來提供晶片 互連。半導體係通過鋁導體予以互連。然而，工業發展要 求提高性能，包括超大型積體（ULSI)和更快速之電路只具 有小至200奈米或更小之互連。在此等小特徵尺寸上，鋁的 電阻率太高不容許電子信號以所需要之速率通過。銅本來 具有小電阻率而因此是一種較為適合之金屬來符合下一代 的半導體裝置之要求。 半導體晶片中鋁互連之一般程序可包括金屬層的離子蝕 刻，例如一種程序包括：金屬沉積、照相石印形成圖型、 通過反應性離子蚀刻之線清晰度和介電體沉積。使用銅在 先進之互連中排除使用反應性離子蝕刻，這是由於缺乏銅 化合物連同足以能視需要能移除銅之蒸氣壓。 87506 1285687 半導體工業中鑲嵌程序已發展成為形成圖型和沉積金屬 敍嵌結構入電子特徵例如溝槽和通路中之方法。該镶嵌程 序自通常利用化學蒸汽沉積碎材料或有機介電體而沉積介 電體開始，接著固或旋轉塗伟石夕材料或無機或有機介 電體。其次’形成圖型係使用照相石印程序而完成，然後 反應性離子⑽〗界定通路和溝槽（互連）在介電體中。將自对 火型材料所造成之障壁層使用化學蒸汽沉積方法沉積入特 徵^將薄㈣源層沉積在障壁層上將導電率授予特徵。 此操作接著鋼電鍍來填充小特徵。過量的姊障壁層材科 可由化學或機械磨光程序移除。 因為欲予鍍敷小電子特徵逐漸形成困難的程度及增加之 電嫂標準，已作成電鍍溶液和技術方面之數項改良。即使 關：電鍍程序之改良，由於不充分之銅填充入通路或溝槽 或迫孔中’仍有可導致電鍍缺陷之某些環境存在。此等缺 陷是不完全填充人通路或通孔中（例如凹座），過度電鍛（例 J丘办成在特欲上）’包括人非金屬以及空例如 中之孔）。 ^ 雖”’：白見之鍍銅系統可能適合於電鍍大至丨微米和甚至 更大例如1至5〇〇微米並具有自小於1:1至約5:丨不等之縱橫 比的通路和溝槽，但是當試圖電鍵具有相當小或低至中等 縱桜比 < 特徵時，使用習見之銅電解液和方法，各種缺陷 例如凹座、過度電鍍、缝、空隙和介入物可能發生。由於 保形之銅電鍍的結果，此等缺陷可能發生，即：必須以相 同速率’用鋼電鍍所有表面之情況。缺陷亦可由於非保形 87506 1285687 填充而？I起，係由鍍銅溶液不充分潤溼電子特徵、吸附氣 泡在特彳政之側壁上，特徵的太快電鍍速率導致過度電鍍之 〜構（由於不均勻吸附含硫之加速劑或凹處在銅填充沉積 物中’因為優先吸附抑制劑添加劑在通路或通孔中）之結 果。 、 了心需要具有新#頁電鍵組合物。特別可能需要具 有新病電鍰鋼之組合物其可有效地電鍍銅（例如無凹處、過 刀私鍍、空隙、介入物和縫）在低（<3:1)縱橫比孔徑中，包 括溝槽和通路或通孔。 - 【發明内容】 頃發現：電鍍銅之組合物能有效電鍍各種物件，包括積 心私路例如具有鑲嵌結構者，印刷電路板及其他電子封裝 裝置。 本务月的組合物含有垸橫酸銅和自由燒續酸，其中自由 鉍具有自约0.05至約2·5〇Μ之濃度。該組合物可另外含有自 物離子，並視需要含有一或數種添加劑例如抑制劑、增 亮劑、平整劑或界面活性劑。此等組合物意欲將微米大I 因/人之溝槽或通路，通孔和微通路金屬化。 【實施方式】 _本發明的組合物和方法特別使用以填充今日和未來半導 :所需要之通路、微通路、溝槽和通孔及經由自含有橫酸 鹽陰離子（和其他酸性陰離子例如硫酸鹽）之電解液可靠電 鍍鋼沉積物而符合印刷電路板製造要求（包括具有至少 0·5:1和至高4:1之縱橫比及0.5微米至約500微米或更大直徑 87506 1285687 的迆路）基本上或完全無凹處、過度電鍍、空隙、介入物或 其他電鍍缺陷。 本發明人發現：較佳使用純烷磺酸鹽溶液而非先前技藝 的混合磧酸鹽落液，因為頃發現··較短鏈之烷磺酸鹽在較 咼足自由酸濃度時沉積較佳而較長碳鏈磺酸鹽在較低之自 由酸濃度時作用較佳。 烷磺酸因其物理性質之獨特平衡與硫酸有區別。例如， 燒績酸的降低表面張力能力隨著鏈長而增加❶然而，金屬 烷磺酸鹽的水中溶解度之通常降低亦隨著鏈長而上升。二 本發明的最佳具體實施例集中在c3垸烴績酸及其衍 生物作為電鍍銅之電解液的意外優越性。此等酸具有金屬 烷磺酸鹽溶解度和降低表面張力之能力的最佳平衡。烷磺 酸鹽的較低表面張力增加表面活性，關於電鍍入微米因次 又孔中表面活性甚為重要，而金屬鹽類溶解度通常對於電 鍍甚為重要。磺酸的溶液導電率在當量自由酸濃度時通常 低=基於硫酸之溶液導電率❶此較低之導電率導致將原電 流密度分佈移動至欲以銅予以電鍍之物件上低電流密度區 域，產生更均勻銅沉積物。基於理論，本發明可使用Cl至 C3；fe續酸衍生物予以變更。 本發明的電鍍浴其值得注意的特徵為：包括高濃度的磺 酸鹽陰離子（⑽心不願受任何學說約束，咸信：高續酸 鹽陰離子濃度可調變凹處中之電鍍速率例如通路、溝槽和 通孔。此與傳統之思維反直觀且完全料想不到。因為績酸 瓜陰離子化學上相似於許多商業上酸性銅電解液中所使用 87506 -10· 1285687 之加速劑型添加劑。此類加速劑陰離子通常具有一個硫部 份和一個磺酸部份在相同分子上相似於磺酸鹽陰離子。然 而，代替加速銅沉積入電子組件上之小特徵中而導致缺陷 例如凹處或過度電鏡結構像含硫之加速劑添加劑，續酸鹽 为子调變銅沉積而導致較為均勻、無缺陷之銅沉積物。 更特定言之，本發明的較佳電鍍組合物具有每升電鍍溶 液至少約0.05莫耳之磺酸鹽濃度、更佳每升至少約〇2^耳 之磺酸鹽濃度，更更佳是每升之電鍍溶液至少約〇·4莫耳至 、，力1.0莫耳之飧鉍鹽濃度。使用甚至更高之磺酸鹽濃度，獲 待充分結果，例如，具有每升至少約2 25莫耳的磺酸鹽濃 度之鍍銅浴。 較佳，將〜鉍鹽陰離子濃度維持在砵等高濃度遍及電鍍 循環的全部或至少大體上部份。一部份的酸性陰離子可能 是另外酸性陰離子分子例如硫酸鹽、氟硼酸鹽、胺基磺酸 鹽乙酸鹽、苯基磺酸鹽、酚磺酸鹽、甲苯磺酸鹽、膦酸 鹽和焦磷酸鹽。 除去％酸鹽陰離子以外，鍍浴亦可含有通常使用於酸性 銅電解液中之其他添加劑例如抑制劑添加劑、增亮劑、加 速劑、平整劑和界面活性型劑。出人意料以外，頃發現： 使用與抑制劑、加速劑、增-劑和平整劑之此類磺酸鹽酸 f生陰離子組合可導致通路或溝槽或其他電子特徵之有效 反轉填无"銅電鍍，例如印刷電路板中之通孔而無缺陷例 如凹處、過度電鍍、介入物、縫和空隙。 更特疋έ <，該磺酸鹽酸性陰離子能調變在電子特徵的 87506 -11 - 1285687 底部之電鍍（速）率，容許將銅以大體上"反轉”方式鍍敷整個 孔徑而不會υ導致低銅沉積在孔徑的中央（例如凹處），2) 過早密封孔徑頂部以致可產生介入物或空隙及3)過度電鍍 孔徑而產生過度電鍍結構，隨後必須以機械和化學方式將 其移除。 本發明亦包括製造的物件，包括電子封裝裝置例如印刷 電路板、多晶片模組、半導體積體電路、機械_電子機器裝 置（即MEMS裝置）及含有自本發明的電鍍溶液所產生之銅 沉積物之類似物。本發明的其他方面以下予以討論。二 如上所討論，本發明的電鍍溶液於電鍍具有通路、微通 路、溝槽或具有低(0.5:1至3:1)縱橫比之通孔的各種電子物 件時特別有效。 更特Λ。之本發明的溶液使用以電鏡電子裝置（例如印 刷電路板、微晶片模组包及不明顯之3_因次結構，特定言 之，半導體積體電路和其他電路系統。本發明的電鍍溶液 特別使用來填充銅人此類電子裝置的通路、微通路和通孔 中而無隨著使用基於非姐鹽化學作用之先前化學作用通 常所發現之缺陷。 本發明的較佳電鍍溶液通常包括至少—種可溶性銅鹽、 一種酸性電解液、一種函素離子和添加劑。 更特定言之，本發明的電鍍组合物較佳含有燒基或芳基 碍酸的銅鹽，-種電解液，較佳—種酸性水溶液例如續酸 溶液連同氯化物或其他函化物離子源；及一或數種添加劑 例如增亮劑、抑制劑和平整劑及類似物。 87506 •12- 1285687 可採用各種銅垸鹽在主題電鍍溶液中其中，將鋼鹽的陰 離子邵份之烷磺酸及任何自由酸引入成為具有下式的燒基 或芳基磺酸： R”c·Andricacos, P. C., Cliang, I. C. Hariklia, D., and Horkans, J. et al., U.S. Patent No. 5,385,661, the disclosure of which is incorporated herein by reference to the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of U.S. Pat. The method disclosed in this patent is mainly due to the weakly mismatched nature of methanesulfonic acid/methanesulfonate, MS A is particularly suitable for allowing this type of method to appear properly. A paper on this subject is also published (J. Electrochem·Soc· ; 1995, 142(7) ; 2244-2249) 〇 Recently, copper interconnects have been used to provide wafer interconnects in semiconductor wafer fabrication. Semiconductors are interconnected by aluminum conductors. However, industrial development requires improved performance. , including ultra-large integrated bodies (ULSI) and faster circuits with only interconnects as small as 200 nanometers or less. On these small feature sizes, the resistivity of aluminum is too high to allow electronic signals to be needed. The rate passes. Copper has a small resistivity and is therefore a suitable metal to meet the requirements of next-generation semiconductor devices. The general procedure for aluminum interconnects in semiconductor wafers can include ion etching of metal layers. For example, a procedure includes: metal deposition, lithographic patterning, line definition by reactive ion etching, and dielectric deposition. The use of copper in advanced interconnects eliminates the use of reactive ion etching due to the lack of copper compounds. Together with the vapor pressure sufficient to remove copper as needed. 87506 1285687 The damascene process in the semiconductor industry has evolved into a method of forming patterned and deposited metal embedded structures into electronic features such as trenches and vias. Chemical vapor deposition of the material or organic dielectric begins with the deposition of the dielectric, followed by solid or spin coating of the material or inorganic or organic dielectric. Secondly, the formation pattern is completed using a photolithographic process, then reactivity Ions (10) define the vias and trenches (interconnects) in the dielectric. The barrier layer caused by the pyrophoric material is deposited into the feature using a chemical vapor deposition method. The thin (iv) source layer is deposited on the barrier layer to conduct electricity. Rate award feature. This operation is followed by steel plating to fill small features. Excess 姊 barrier layer material can be polished by chemical or mechanical Order removal. Because of the difficulty of plating small electronic features and the increasing power standards, several improvements have been made in plating solutions and techniques. Even if the plating process is improved, due to insufficient copper filling There are still some environments in the access path or trench or forced hole that can cause plating defects. These defects are not completely filled in the human path or through hole (such as the recess), excessive electric forging (such as J In the special desires, 'including human non-metal and empty holes such as holes.' ^ Although "': the white copper plating system may be suitable for electroplating as large as 丨 micron and even larger such as 1 to 5 〇〇 micron and have From less than 1:1 to about 5: 通路 unequal aspect ratio channels and trenches, but when attempting to have a relatively small or low to medium aspect ratio of the key, use the copper electrolyte and method of the various, various Defects such as dimples, overplating, seams, voids, and interventions can occur. As a result of conformal copper plating, such defects may occur, i.e., all surfaces must be plated with steel at the same rate. Defects can also be filled due to non-conformal 87506 1285687? From the copper plating solution, the electronic characteristics are not sufficiently wetted, and the adsorption bubbles are on the side wall of the special government. The characteristic too fast plating rate leads to over-plating of the structure (due to uneven adsorption of sulfur-containing accelerators or recesses) The result of copper-filled deposits 'because preferential adsorption inhibitor additives are in the vias or vias. It is necessary to have a new #page key composition. In particular, it may be desirable to have a composition of new diseased steel that is effective in electroplating copper (e.g., without recesses, knife plating, voids, interposals, and seams) in a low (<3:1) aspect ratio aperture, Includes trenches and vias or vias. - [Summary] It has been found that the electroplated copper composition can effectively plate various articles, including self-contained circuits such as those having a mosaic structure, printed circuit boards and other electronic packaging devices. The composition of this month comprises copper beryllate and free-burning acid, wherein the free hydrazine has a concentration of from about 0.05 to about 2.5 Å. The composition may additionally contain autoion ions and, if desired, one or more additives such as inhibitors, brighteners, levelers or surfactants. These compositions are intended to metallize the vias or vias, vias and microvias. [Embodiment] The compositions and methods of the present invention are particularly useful for filling today's and future semiconductors: the desired pathways, microchannels, trenches, and vias, and via the self-contained anion anion (and other acidic anions such as sulfuric acid) The electrolyte of the salt) reliably galvanizes the steel deposit to meet the printed circuit board manufacturing requirements (including an aspect ratio of at least 0. 5:1 and a height of 4:1 aspect ratio and a diameter of 0.5 micron to about 500 microns or more 87506 1285687) Basically or completely free of recesses, overplating, voids, interposers or other plating defects. The inventors have found that it is preferred to use a pure alkane sulfonate solution instead of the prior art mixed phthalate drop, since it has been found that shorter chain alkane sulfonates are better deposited at a higher free acid concentration. Longer carbon chain sulfonates work better at lower free acid concentrations. Alkanesulfonic acids differ from sulfuric acid due to their unique balance of physical properties. For example, the ability to reduce surface tension of calcining acid increases with chain length. However, the usual decrease in solubility of metal alkane sulfonates in water also increases with chain length. The best embodiment of the invention focuses on the unexpected advantages of c3 sulfonate acid and its derivatives as electrolytes for electroplating copper. These acids have an optimum balance of metal alkane sulfonate solubility and ability to reduce surface tension. The lower surface tension of the alkane sulfonate increases the surface activity, which is important for electroplating into the micron-caused surface, and the solubility of the metal salt is often important for electroplating. The conductivity of the solution of the sulfonic acid is usually low at the equivalent free acid concentration = the conductivity of the solution based on sulfuric acid. The lower conductivity results in moving the original current density distribution to the low current density region of the object to be electroplated with copper. More uniform copper deposits. Based on theory, the present invention can be modified using Cl to C3; The electroplating bath of the present invention is characterized in that it includes a high concentration of sulfonate anion ((10) is unwilling to be bound by any theory, and the electroplating rate of the polyanionate can be adjusted in the recess, such as the passage. , grooves and through-holes. This is counter-intuitive and completely unexpected with traditional thinking, because the melon anion is chemically similar to the accelerator-type additive used in many commercially acidic copper electrolytes 87506 -10· 1285687. The accelerator anion typically has a sulfur moiety and a sulfonic acid moiety similar to the sulfonate anion on the same molecule. However, instead of accelerating the deposition of copper into the small features on the electronic component, defects such as recesses or over-electron structures are caused. Like the sulfur-containing accelerator additive, the sulphonate is a sub-modulated copper deposit resulting in a relatively uniform, defect-free copper deposit. More specifically, the preferred electroplating composition of the present invention has at least about 0.05 per liter of plating solution. The concentration of the sulfonate of the molar, more preferably at least about ^2 ^ sulfonate concentration per liter, more preferably at least about 〇 4 moles per liter of the plating solution, A 1.0 molar molar salt concentration. Even higher sulfonate concentrations are used to obtain sufficient results, for example, a copper plating bath having a sulfonate concentration of at least about 2 25 moles per liter. ~ 铋 salt anion concentration is maintained at all or at least a substantial portion of the bismuth concentration throughout the plating cycle. A portion of the acidic anion may be another acidic anionic molecule such as sulfate, fluoroborate, amine sulfonate acetate , phenyl sulfonate, phenol sulfonate, toluene sulfonate, phosphonate and pyrophosphate. In addition to the % acid salt anion, the plating bath may also contain other additives commonly used in acid copper electrolytes such as inhibition. Agent additives, brighteners, accelerators, leveling agents and interfacial active agents. Unexpectedly, it has been found that: the combination of such sulfonic acid hydrochloride and anion can be used with an inhibitor, an accelerator, an enhancer and a leveling agent. This results in an effective reversal of vias or trenches or other electronic features. Copper plating, such as through holes in printed circuit boards, without defects such as recesses, overplating, implants, seams, and voids. In particular, the sulfonic acid hydrochloride anion can modulate the electroplating (speed) rate at the bottom of the electronically characterized 87506 -11 - 1285687, allowing the copper to be plated in a substantially "reverse" manner without the entire aperture Will cause low copper deposition in the center of the aperture (eg, a recess), 2) prematurely seal the top of the aperture so that it can create intervening or voids, and 3) over-plating the aperture to create an over-plated structure that must then be mechanically and chemically The invention also includes articles of manufacture, including electronic packaging devices such as printed circuit boards, multi-chip modules, semiconductor integrated circuits, mechanical-electronic devices (ie, MEMS devices), and electroplating solutions containing the present invention. Analogs of copper deposits produced. Other aspects of the invention are discussed below. As discussed above, the plating solutions of the present invention have vias, microvias, trenches or have low (0.5:1 to 3:1) plating. The various aspect ratios of the vias are particularly effective for various electronic objects. More special. The solution of the present invention uses an electron microscope electronic device (for example, a printed circuit board, a microchip module package, and an inconspicuous structure, in particular, a semiconductor integrated circuit and other circuit systems. The plating solution of the present invention is particularly Used to fill the vias, microvias, and vias of such electronic devices as copper humans without the drawbacks typically found with the use of prior chemistry based on non-salt salt chemistry. The preferred plating solutions of the present invention typically include at least - a soluble copper salt, an acidic electrolyte, a functional ion and an additive. More specifically, the electroplating composition of the present invention preferably contains a copper salt of an alkyl or aryl acid, an electrolyte, preferably - An acidic aqueous solution such as a continuous acid solution together with a chloride or other functional ion source; and one or more additives such as brighteners, inhibitors, leveling agents, and the like. 87506 • 12- 1285687 Various copper strontium salts can be used in the subject matter In the electroplating solution, the anionic alkanesulfonic acid of the steel salt and any free acid are introduced into the alkyl or arylsulfonic acid having the formula: R"c·
II
Ra- C -(S〇2〇H)y .1 . R，b . 其中a+b + c+y等於4 ; R ’ R/和Rn是相同或不同，每一者獨立可能是氫，苯基，^、 F、Br、I、CF3或低碳烷基基團例如（CH2)n其中n是自i至7 7 車父佳1至3及其係未經取代或由氧、（^1、1^、81*、1、〇?；3、-8〇2〇^[ 所取代。車父佳之燒基續酸是甲燒續酸、乙燒續酸和丙燒續 ’而k基聚％酸是甲燒二績酸、一氯甲垸二續酸、二氯 甲烷二磺酸、1，1-乙烷二磺酸、2-氯-1，1-乙烷二磺酸、Li 二氯-1，1-乙烷二磺酸、1，1-丙烷二磺酸、3_氯_1，1-丙烷二磺 酸、1，2-伸乙基二磺酸、1，3-伸丙基二磺酸、三氟甲烷磺酸、 丁規％故、全氟丁乾續酸、戊燒績酸，而芳基績酸是苯基 磺酸、酚磺酸和甲苯基磺酸。 其他銅鹽亦可能在銅電解液中例如硫酸銅、乙酸銅、氟 硼銅、胺基％酸銅、硝酸銅或膦酸銅。甲績酸銅是一種 特佳之銅鹽。銅鹽可以相當廣泛濃度範圍適當存在於本發 明之電鍍組合物中。銅鹽較佳可以每升之電鍍溶液自約1〇 至約300克之濃度採用，更佳是每升之電鍍溶液自約25至約 200克之濃度’更更佳是每升之電鍍溶液自約4〇至約175克 之濃度。 87506.doc -13- 1285687 另外，本發明中，頃發現：隨著碳鏈長度之增加，伴隨 之自由敵'減少產生無缺陷之沉積物。乙續酸和丙績酸溶液 在較低之自由酸濃度時（少於L50 Μ自由酸）操作最佳。較低 之自由酸濃度將銅種源層的腐蚀減至最少而導致電鍍之銅 層中甚少缺陷。與硫酸比較，磺酸鹽亦沉積較平滑之鋼塗 層-三氟曱烷磺酸鹽溶液產生商業上合格塗層遍廣泛自由 酸濃度範圍，Proell並未揭示。 電解液亦可含有自由酸以增加溶液導電率。較佳之自由 具有與銅鹽陰離子相同陰離子但是自由酸的混合物亦在 本發明的範圍内。較佳之烷基磺酸是甲烷磺酸、乙烷磺酸 和丙燒績酸’而烷基聚磺酸是甲烷二磺酸、一氯甲烷二磺 酸、二氯甲烷二磺酸、1，1 -乙烷二磺酸、2-氯-1，1 _乙烷二磺 酸、1，2-二氯-ΐ，ι_乙烷二磺酸、丨，^丙烷二磺酸、、氯-^一 丙烷二磺酸、1，2-伸乙基二磺酸、ip伸丙基二磺酸、三氟 甲烷％酸、丁烷磺酸、全氟丁烷磺酸、戊烷磺酸，而芳基 磺酸是苯基磺酸和甲苯基磺酸。自由酸濃度範圍係每升之 電鍍落液自約1克至約300克，更佳在每升之電鍍溶液自約 25至約200克、更更佳是每升之電鍍溶液自約4〇至約ι75克。 本發明亦包括大體上或完全不含所添加之磺酸之電鍍浴 且可能是中性或基本上是中性（例如pH值至少小於約7或 7.5)。此類電鍍組合物適合以與本文中所揭示之其他組合物 (但是無所添加之磺酸）之相同方式具有相同組份而製備。 本發明的電鍍浴較佳採用酸性電解液，其一般是一種酸 性水落液且其較佳含有一種_化物離子源，特定言之，一 87506.doc -14- 1285687 種氯化物離子源。甘八+ 、/、他適當齒化物的實例包括溴化物和蛾Ra- C -(S〇2〇H)y .1 . R,b . wherein a+b + c+y is equal to 4; R ' R/ and Rn are the same or different, each of which may be hydrogen, benzene a group, ^, F, Br, I, CF3 or a lower alkyl group such as (CH2)n wherein n is from i to 7 7 car fathers 1 to 3 and their systems are unsubstituted or by oxygen, (^1 , 1^, 81*, 1, 〇?; 3, -8 〇 2 〇 ^ [ replaced by the car father Jiazhi burning base acid is a burning acid, B-burning acid and C-burning and k-based The % acid is a calcined acid, a chloroformin acid, dichloromethane disulfonic acid, 1,1-ethane disulfonic acid, 2-chloro-1,1-ethane disulfonic acid, Li two Chloro-1,1-ethanedisulfonic acid, 1,1-propanedisulfonic acid, 3-chloro-1,1-propanedisulfonic acid, 1,2-extended ethyl disulfonic acid, 1,3-stretch Propyl disulfonic acid, trifluoromethanesulfonic acid, butyl hexanthrene, perfluorobutylic acid, succinic acid, and aryl acid is phenyl sulfonic acid, phenol sulfonic acid and toluene sulfonic acid. It is also possible to use copper electrolyte such as copper sulfate, copper acetate, copper fluoroboron, copper amide, copper nitrate or copper phosphonate. Copper sulphate is a particularly good copper salt. Copper salts can be widely distributed. It is suitably present in the electroplating composition of the present invention. The copper salt is preferably used in a concentration of from about 1 Torr to about 300 gram per liter of the plating solution, more preferably from about 25 to about 200 gram per liter of the plating solution. More preferably, the plating solution per liter is from about 4 Torr to about 175 gram. 87506.doc -13- 1285687 In addition, in the present invention, it is found that as the length of the carbon chain increases, the free enemy' is reduced. Defect-free deposits. The ethyl acid and the acrylic acid solution work best at lower free acid concentrations (less than L50 Μ free acid). The lower free acid concentration minimizes corrosion of the copper provenance layer. The resulting copper layer has few defects. Compared with sulfuric acid, the sulfonate also deposits a smoother steel coating-trifluorosulfonate solution to produce a commercially acceptable coating over a wide range of free acid concentrations, Proell and The electrolyte may also contain a free acid to increase the conductivity of the solution. Preferably, a mixture having the same anion as the copper salt anion but a free acid is also within the scope of the invention. Preferably, the alkyl sulfonic acid is methanesulfonic acid, Ethane Acid and propylene calcined acid and the alkyl polysulfonic acid is methane disulfonic acid, monochloromethane disulfonic acid, dichloromethane disulfonic acid, 1,1-ethane disulfonic acid, 2-chloro-1,1 _ethane disulfonic acid, 1,2-dichloro-indole, ι-ethane disulfonic acid, hydrazine, propane disulfonic acid, chloro-propane disulfonic acid, 1,2-extended ethyl Sulfonic acid, ip propyl disulfonic acid, trifluoromethane acid, butane sulfonic acid, perfluorobutane sulfonic acid, pentane sulfonic acid, and aryl sulfonic acid is phenyl sulfonic acid and tolyl sulfonic acid. The free acid concentration ranges from about 1 gram to about 300 grams per liter of electroplating solution, more preferably from about 25 to about 200 grams per liter of plating solution, and more preferably from about 4 Torr per liter of plating solution. About ι75 grams. The invention also includes electroplating baths that are substantially or completely free of added sulfonic acid and which may be neutral or substantially neutral (e.g., having a pH of at least less than about 7 or 7.5). Such electroplating compositions are suitably prepared in the same manner as the other compositions disclosed herein (but without the added sulfonic acid). The electroplating bath of the present invention preferably employs an acidic electrolyte which is generally an acid aqueous liquid and which preferably contains a source of ions, in particular, a source of chloride ions of 87506.doc -14 - 1285687. Examples of Gan-8+, /, his appropriate dentate include bromide and moth
化物。可適當利用庳I 廣大靶圍的商化物離子濃度（如果採用卣 化物離子）在電护、、办、★山， 又/合’夜中例如自約〇(於此情況未採用齒化物 離子）至200百萬公士辦/ （ppm)的鹵化物離子，更佳自約1〇至 約75 ppm的鹵化物離子。 :除，銅鹽、電解液和南素離子以外，本發明的電鍵浴視 而要可έ有各種的其他組份，包括有機添加劑例如抑制 劑：加速劑、平整劑及其類似物。併用抑制劑與加速劑或 增党劑添加劑特佳，且出人意料外提供加強之電鍵性能，- 特別在底部填充電鑛小直桎及/或低至中等縱橫比之通路 或微通路和通孔時。 不願又任何學說所約束，咸信：此加強之底部填充電鍍 可能由於作為通過通路、微通路或通孔長度之擴散效應之 結果，將通路或微通路的底部上或通孔以内抑制劑的濃度 相當降低而發生。經降低之抑制劑添加劑濃度導致增加之 鍍銅速率在通路、微通路區域的底部部份上或在通孔的中 央。在欲予電鍍之特徵的表面上（在通路或微通路之頂上或 印刷電路板之表面上），抑制劑濃度依然相當高且相對於通 路、微通路底部區域或通孔的中央係恆定。因此，因為相 對於欲以銅電鍍之物件的底部部份，増加之抑制劑濃度， 欲予電鍍之特徵的頂區域具有相當抑制或緩慢之電鍍速 率。供使用於本發明組合物中心之較佳抑制劑是聚合物 質，較佳具有高原子取代，特別是氧鍵合。 較佳之抑制劑是高分子量聚醚，例如具有下式者： 87506.doc -15- 1285687Compound. It is possible to appropriately utilize the concentration of the commercial ion of the 靶I target range (if using a telluride ion) in the electric protection, the office, the mountain, or the night, for example, from the 〇 (in this case, the tooth ion is not used) 200 million ounces / (ppm) of halide ions, more preferably from about 1 〇 to about 75 ppm of halide ions. In addition to the copper salt, the electrolyte and the nitrite ion, the electric bath of the present invention may have various other components including organic additives such as an inhibitor: an accelerator, a leveling agent and the like. It is especially effective with inhibitors and accelerators or extender additives, and unexpectedly provides enhanced bond performance, especially when filling the bottom of the mine with small straight and/or low to medium aspect ratio vias or microvias and vias. . Unwilling to be bound by any doctrine, it is believed that this enhanced underfill plating may be due to the effect of diffusion through the length of the via, microvia or via, on the bottom of the via or microvia or within the via. The concentration occurs quite slowly. The reduced concentration of the inhibitor additive results in an increased rate of copper plating on the bottom portion of the via, microchannel region, or at the center of the via. On the surface of the feature to be plated (on top of the via or microvia or on the surface of the printed circuit board), the inhibitor concentration is still quite high and constant relative to the path, the bottom region of the microvia, or the center of the via. Therefore, because of the concentration of the inhibitor added to the bottom portion of the article to be electroplated with copper, the top region of the feature to be plated has a relatively suppressed or slow plating rate. A preferred inhibitor for use in the center of the compositions of the present invention is a polymeric material, preferably having a high atomic substitution, particularly an oxygen linkage. Preferred inhibitors are high molecular weight polyethers, for example having the formula: 87506.doc -15- 1285687
R-〇-(CXYCX'YO)nH 其中R是含有自約2至約20個碳原子之芳基或烷基基團；每 一個X、Y、X’和Y’各自是氫；烷基較佳是曱基、乙基或丙 基；芳基例如苯基；芳烷基例如苯甲基而較佳χ，γ，χ，和 Υ’之一或多個是氫，而η是5至100,000間之一個整數。較佳， R是伸乙基而η是大於5000但小於75,〇〇〇。 如上又中所討論，頃發現··經由使高磺酸鹽陰離子濃度 超過一般加速劑型添加劑之習用含量，現在可能均勻電鍍 特別低至高縱橫比之通路和微通路及其他難以電鍍之電子 特徵例如印刷電路板中之通孔。 可採用廣泛種類的增亮劑，包括所熟知之增亮劑在本名 明的電鍍銅組合物中。一般之增亮劑含有一或多個硫原^ 且一般不含任何氮原子及約1500或更小之分子量。通常β 具有硫化物及/或磺酸基團之增白劑化合物較佳，特定1 之'，包括一組的式ms〇3X之化合物其中汉是視需^ 代之燒基（其包括環燒基），视需要取代之雜燒基、視需要耳 代之芳基基團或視需要取代之雜脂環：技―個平衡離子伯 A •内或鉀而R是氫或一個化學鍵（即·· _s_R〜s〇3x或 較大化合物之取代基）。一般之燒基基團可具有自！至約2( 個碳原子，更—般是丨至約6或_碳原子。雜垸基基困可 具有一或數個雜原子（Ν’ 0或5)在鏈中，較佳具有自！至約 個碳原+，更一般具有！至約8幻2個碳原子。幾環之芳 基基圏—般是芳基錢，例如苯基和«。雜芳族基團亦 可能是適當之芳基基圏且-般含有1至約3個N，〇或S原子 87506 -16 - 1285687 及卜3個分開或稠合環其包括薰草基、喳啉基、吡啶基、吡 畊基、嘧啶基、呋喃基、吡咯基、噻吩基、嘍唑基、呤唑 基、呤一唑基、二唑、咪唑基、吲哚基、笨并呋喃基、笨 並嘧唑基及其類似物。雜脂環基團一般可具有丨至3個N，〇 或S原子及自1至3個分開或稠合環，包括例如四氫呋喃基、 嘧吩基、四氫哌喃基、六氫吡啶基、嗎福啉基、吡咯啶基 及其類似物。經取代之烷基、雜烷基、芳基或雜脂環等基 團的取代基例如包括Cm烷氧基；Cl_8烷基、函素特別是F、 Cl和Br，氯基、硝基及其類似物。 更明確言之，有用之增亮劑包括具有下列各式者：R-〇-(CXYCX'YO)nH wherein R is an aryl or alkyl group containing from about 2 to about 20 carbon atoms; each of X, Y, X' and Y' is hydrogen; Preferably, it is an indenyl group, an ethyl group or a propyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group and preferably one, a plurality of γ, γ, χ, and Υ' are hydrogen, and η is 5 to 100,000 An integer between. Preferably, R is an ethyl group and η is greater than 5,000 but less than 75 Å. As discussed above and again, it has been discovered that by making the high sulfonate anion concentration above the conventional level of conventional accelerator type additives, it is now possible to uniformly plate particularly low to high aspect ratio vias and microvias and other electronic features that are difficult to plate, such as printing. Through holes in the board. A wide variety of brighteners can be employed, including the well-known brighteners in the electroplated copper compositions of the present specification. Typical brighteners contain one or more sulphur and generally do not contain any nitrogen atoms and a molecular weight of about 1500 or less. Generally, a whitening agent compound having a sulfide and/or a sulfonic acid group is preferred, and a specific one, including a group of compounds of the formula ms〇3X, wherein the Han is an on-demand base (which includes a ring burn) a heteropolyalkyl group, optionally an aryl group or an optionally substituted heteroalicyclic ring: a balanced ion A or a potassium and R is a hydrogen or a chemical bond (ie, · _s_R~s〇3x or a substituent of a larger compound). A typical alkyl group can have a self! Up to about 2 (carbon atoms, more generally 丨 to about 6 or _ carbon atoms. Heteroquinone groups can have one or several heteroatoms (Ν'0 or 5) in the chain, preferably with! Up to about one carbonogen +, more generally! to about 8 magical 2 carbon atoms. The aryl group of several rings is generally aryl, such as phenyl and «. Heteroaromatic groups may also be suitable An aryl group and generally containing from 1 to about 3 N, a sulfonium or S atom 87506 -16 - 1285687 and 3 separate or fused rings including a oxacillin, a porphyrin group, a pyridyl group, a pyridinyl group, Pyrimidinyl, furyl, pyrrolyl, thienyl, oxazolyl, oxazolyl, oxazolyl, diazole, imidazolyl, indolyl, benzofuranyl, benzopyrazolyl and the like. Heteroalicyclic groups may generally have up to 3 N, oxime or S atoms and from 1 to 3 separate or fused rings including, for example, tetrahydrofuranyl, pyrenyl, tetrahydropyranyl, hexahydropyridyl, a morpholinyl group, a pyrrolidinyl group, and the like. The substituent of the substituted alkyl, heteroalkyl, aryl or heteroalicyclic group includes, for example, a Cm alkoxy group; a Cl-8 alkyl group, a hydroxyl group, particularly F, Cl and Br, chlorine, nitro and the like. More specifically, useful brighteners include those having the following formulae:
XOsS-R-SH X〇3S-R_S_S-R-S03X 及 X〇3 - Ar_S-S-Ar_S03X 上述各式中R是一個視需要所取代之烷基基倒，較佳是具有 自1至6個碳原子之烷基基團，更佳是具有自1至4個碳原子 之燒基基團；Ar是一個视需要所取代之芳基基團例如視需 要所取代之苯基或莕基；而X是一個適當之平衡離子例如 銨、納或J甲。 某些特定適當之增亮劑例如，包括n，n-二甲基-二硫代胺 基甲酸-(3-磺酸基丙基）酯、3-巯基-丙基磺酸-(3-磺酸基丙 基）酯；3-巯基丙基磺酸（鈉鹽）；碳酸-二硫代-〇_乙酯酯 連同3-豉基-1-丙（烷）磺酸（鉀鹽）；雙磺酸基丙基二硫化物、 3-(苯并嘍唑基-S-硫代）丙磺酸（鈉鹽）；吡啶鏘丙基磺酸基甜 菜鹼、1_鈉-3-巯基丙烷·1-磺酸鹽；美國專利第3,778,357號 87506 •17· 1285687 中揭示之橫酸基坑基硫化物化合物；二燒胺基_硫酮基-曱硫 基烷磺酸的過氧化物氧化產物及上述之組合。另外適當增 亮劑亦記述於美國專利第3,770,598 ; 4,374,709 ; 4,376,685 ; 4,555,315和4,673,469等號中，所有之專利案以引用之方式 併入本文中。供使用於本發明的電鏡組合物中之特佳增亮 劑是n，n-二甲基-二硫代胺基甲酸_(3_磺酸基丙基）酯及雙_ 鋼-績酸丙基二硫化物。 使用一或數種平整劑在本發明的電鍍浴中通常較佳。就 大體而論’有用之平整劑包括含有一個取代之胺基基團者 例如具有式R-N-R’之化合物其中每一個尺和R，各自是一個 經取代或未經取代之燒基基團或是一個經取代或未經取代 之芳基基團。一般，烷基基團具有自丨至8個碳原子，更一 般自1至4個奴原子。適當之芳基基图包括經取代或未經取 代之苯基或莕基。經取代之烷基和芳基基團的取代基，舉 例而T ’可能是垸基、卣代和燒氧基。更明確言之，適當 之平整劑包括例如1-(2-羥乙基）-2-咪唑啉硫酮；仁巯基吡 啶；2-鲩基嘍唑啉；伸乙基硫脲；硫脲；烷基化之聚伸烷 基亞胺；美國專利第3,956,084號中所揭示之二甲基苯基吡 唑酮基化合物，含有N-雜芳香環之聚合物；第四化，丙烯 酸系，聚合胺；聚乙烯基胺基甲酸酯、吡咯烷酮和咪唑。 一種特佳之平整劑是1-(2-羥乙基）_2•咪唑啉硫酮。平整劑的 一般濃度範圍是每升之電鍍溶液自約〇〇5至15毫克。將適 奇平整劑冗述並特舉出在美國專利第3,77〇,598 ,· 4,374’709 ’ 4,376,685 ; 4,555,315及4,673,459等號中。 87506 -18- 1285687 使用於本發明中之界面活性劑包括例如胺類，例如乙氧 土 ' 水氧伸烷基胺和烷醇胺；醯胺類；聚乙二醇刑 潤滢劑例如聚乙二醇、聚烷二醇和聚氧伸烷基二醇;高分 子=聚醚、氧乙燒（分子量⑽，咖至3百萬）；聚氧块缔 的後段共聚物；垸基聚醚績酸鹽；錯合之界面活性劑例如 燒氧基化之二胺。本發明的錢組合物之特別適當界面活 性d疋市售《聚乙二醇共聚物，包括聚乙二醇共聚物。以 美國專利中請案扇顧⑽^中所述之界面活性劑為特 佳。-般將界面活性劑以基於浴的重量範圍自約i至2〇,咖 PPm濃度添加至電鍍銅之溶液，更佳約5至12，綱啊。 本發明亦包括使用銅或亞銅離子之錯合劑在錢銅電解 液中’其包括單㈣、二羧酸和三祕例如檸檬酸、酒石 酸、酒石酸鈉鉀、草酸和膦酸。 如本說明書當中所使用者，術語"電鐘銅"包括電鍛銅和 銅合金。銅合金包括來自周期表中第1B、2B、3A、3B、4A、 4B、5B、6B、7B和8各族之金屬。 本發明的電鍍浴較佳在或高μ溫下採用，例如至高和 略高於65。〇在使用期間較佳將電鍍組合物攪拌，例如使用 :具空氣噴佈器、1作件之實際㈣，衝射溶液或其他適 當方法。基於基板特性，電鍍較佳在範圍自〇丨至^❶A” 之電流時實施。基於工作件之困冑’電鍍時間可能範圍係 自約5分鐘至Π、時或更久。通常參閱下列實例關於例示之 較佳步驟。 所述之發明亦包括使用直接脈衝或周期性電流波形來有 87506.doc -19- 1285687 效沉積無缺陷之銅層在電子特徵中。 所述之發明亦可使用可溶 合注銅〶極或不落性或惰性陽極 材料。 如上又中所討論，可將廣泛種類的基板用本發明的組合 物電鍍。本發明的組合物特別使用來電鏡困難工作件例如 具有小直徑和低縱橫比通路或通孔之電路板基板，具有低 縱橫比通路之積體電路、具有高形狀定類微通路之積體電 路及其他電子特徵。本發明的電鍍組合物亦可特別使用於 電鐘積體電路裝置，例如所形成之半導體裝置及其類似物。 如上又中所討論，使用本發明之電鍍溶液，業已有效銅 鑛/、有至V 0.5.1至約3.1的低縱橫比，具有約1至5〇〇微米或 更大直徑的通路或通孔而無缺陷（例如無利用離子束檢驗 可探測之空隙或介入物）。使用本發明之電鍍溶液可將具有 直徑低於0·5微米或甚至低於約〇 2微米及4:卜6:1、7卜ι〇ι 或更大且甚至至高約1 5:1或更大縱橫比之微通路有效電錢 (例如，無利用離子束檢驗可探測之空隙或介入物）。 本發明的前述敘述僅是其舉例說明，當然，只要不脫離 本發明之範圍或要旨（如下列申請專利範圍中所特舉出），可 實施變更和修正。本發明提供更為有效地使殺生物劑之新 頭方法。經由將一般殺生物劑與本文中所述之烷醇胺聯 合’可獲得較不含烷醇胺可獲得之微生物控制好得多之微 生物控制（以每單位的殺生物劑而論）。 87506 -20 -XOsS-R-SH X〇3S-R_S_S-R-S03X and X〇3 - Ar_S-S-Ar_S03X In the above formula, R is an alkyl group which is optionally substituted, preferably from 1 to 6 An alkyl group of a carbon atom, more preferably an alkyl group having from 1 to 4 carbon atoms; Ar is an optionally substituted aryl group such as a phenyl or an anthracenyl group optionally substituted; X is a suitable counterion such as ammonium, sodium or J. Certain particularly suitable brightening agents include, for example, n,n-dimethyl-dithiocarbamic acid-(3-sulfopropyl)ester, 3-mercapto-propylsulfonic acid-(3-sulfonate) Acid propyl) ester; 3-mercaptopropyl sulfonic acid (sodium salt); carbonic acid-dithio-indole-ethyl ester along with 3-mercapto-1-propane sulfonic acid (potassium salt); Sulfosylpropyl disulfide, 3-(benzoxazolyl-S-thio)propanesulfonic acid (sodium salt); pyridinium propyl sulfobetaine, 1-sodium-3-mercaptopropane a sulfonate salt; a sulphate-based sulfide compound disclosed in U.S. Patent No. 3,778,357; Combination of the above. Further suitable brighteners are also described in U.S. Patent Nos. 3,770,598, 4,374, 709, 4, 376, 685, 4, 555, 315, and 4, 673, 469, each of which is incorporated herein by reference. A particularly preferred brightening agent for use in the electron microscopy compositions of the present invention is n,n-dimethyl-dithiocarbamic acid _(3-sulfonatepropyl) ester and bis-steel-producing acid C Disulfide. It is generally preferred to use one or more leveling agents in the electroplating bath of the present invention. In general, a useful leveling agent includes a compound having a substituted amine group such as a compound of the formula RN-R' wherein each of the ruthenium and R is each a substituted or unsubstituted alkyl group or It is a substituted or unsubstituted aryl group. Typically, the alkyl group has from 丨 to 8 carbon atoms, more typically from 1 to 4 slave atoms. Suitable aryl maps include substituted or unsubstituted phenyl or fluorenyl groups. The substituents of the substituted alkyl and aryl groups, by way of example, may be fluorenyl, deuterated and alkoxy. More specifically, suitable leveling agents include, for example, 1-(2-hydroxyethyl)-2-imidazolinthione; mercaptopyridine; 2-mercapto oxazoline; ethyl thiourea; thiourea; a polyalkyleneimine; a dimethylphenylpyrazolone-based compound disclosed in U.S. Patent No. 3,956,084, a polymer containing an N-heteroaromatic ring; a fourth, acrylic, polymeric amine; Polyvinyl urethane, pyrrolidone and imidazole. A particularly preferred leveling agent is 1-(2-hydroxyethyl)_2•imidazolinethione. The leveling agent generally has a concentration range of from about 5 to 15 mg per liter of plating solution. The singularity of the leveling agent is exemplified and is exemplified in U.S. Patent Nos. 3,77,598, 4,374,709, 4,376,685, 4,555,315 and 4,673,459. 87506 -18- 1285687 The surfactants used in the present invention include, for example, amines such as ethoxylates, hydroxylalkylamines and alkanolamines; guanamines; polyethylene glycols, such as polyethylidene Glycol, polyalkylene glycol and polyoxyalkylene glycol; polymer = polyether, oxyethene (molecular weight (10), coffee to 3 million); polyoxygen block back-end copolymer; a salt; a mismatched surfactant such as an alkoxylated diamine. Particularly suitable interfacial activity of the money compositions of the present invention is the commercial use of polyethylene glycol copolymers, including polyethylene glycol copolymers. Surfactants as described in the U.S. Patent Application (10)^ are preferred. The surfactant is typically added to the electroplated copper solution, preferably from about 5 to about 12, based on the weight of the bath, from about i to about 2 Torr. The present invention also encompasses the use of a copper or cuprous ion complexing agent in a copper electrolysis solution which comprises mono-(tetra), dicarboxylic acid and a minor such as citric acid, tartaric acid, potassium sodium tartrate, oxalic acid and phosphonic acid. As used in this specification, the term "electric clock copper" includes electrically wrought copper and copper alloys. The copper alloy includes metals from the respective groups 1B, 2B, 3A, 3B, 4A, 4B, 5B, 6B, 7B and 8 of the periodic table. The electroplating bath of the present invention is preferably employed at or at a high μ temperature, for example, at a high level and slightly above 65. Preferably, the electroplating composition is agitated during use, for example, using: an air jet, an actual (4), a spray solution or other suitable method. Based on the substrate characteristics, electroplating is preferably carried out in the range of currents from 〇丨 to ❶A". Based on the embarrassment of the workpiece, the plating time may range from about 5 minutes to Π, hr, or longer. Generally refer to the following examples. Illustrative preferred steps. The invention also includes the use of direct pulse or periodic current waveforms to deposit a defect-free copper layer in the electronic features of 87506.doc-19-1285687. The invention may also be soluble. Coupling of copper ruthenium or non-leading or inert anode materials. As discussed above, a wide variety of substrates can be electroplated with the compositions of the present invention. The compositions of the present invention particularly use a difficult-to-operate workpiece such as a small diameter. And a low-Aspect Ratio Path or Through Hole Circuit Board Substrate, an Integral Circuit with a Low Aspect Ratio Path, an Integrated Circuit with a High Shaped Micropass, and Other Electronic Features. The electroplating composition of the present invention can also be particularly useful for An electric clock integrated circuit device, such as a formed semiconductor device and the like. As discussed above, using the electroplating solution of the present invention, an effective copper ore has been Low aspect ratio from V 0.5.1 to about 3.1, with vias or vias of about 1 to 5 microns or more in diameter without defects (eg, no voids or intervenes detectable by ion beam inspection). The electroplating solution of the present invention can have a diameter of less than 0.5 micrometers or even less than about 2 micrometers and 4:b: 6:1, 7b ι〇ι or greater and even up to about 15:1 or greater The aspect ratio of the microchannel effective money (for example, without the use of ion beam inspection detectable voids or interposers). The foregoing description of the invention is merely illustrative thereof, of course, without departing from the scope or gist of the invention (eg Modifications and modifications can be implemented in the scope of the patent application. The present invention provides a new method for more effective biocides by combining a general biocide with an alkanolamine as described herein. Microbiological control (in terms of biocide per unit) that is much better controlled by microorganisms than can be obtained without alkanolamines. 87506 -20 -
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40395402P | 2002-08-16 | 2002-08-16 | |
| US10/620,042 US20040045832A1 (en) | 1999-10-14 | 2003-07-15 | Electrolytic copper plating solutions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200415263A TW200415263A (en) | 2004-08-16 |
| TWI285687B true TWI285687B (en) | 2007-08-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW092122506A TWI285687B (en) | 2002-08-16 | 2003-08-15 | Electrolytic copper plating solutions |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20040045832A1 (en) |
| EP (1) | EP1529126A4 (en) |
| JP (1) | JP2005535787A (en) |
| CN (1) | CN1592800A (en) |
| AU (1) | AU2003259049A1 (en) |
| CA (1) | CA2465363A1 (en) |
| TW (1) | TWI285687B (en) |
| WO (1) | WO2004016829A2 (en) |
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| KR101705734B1 (en) * | 2011-02-18 | 2017-02-14 | 삼성전자주식회사 | Copper electroplating solution and method of copper electroplating using the same |
| EP2530102A1 (en) | 2011-06-01 | 2012-12-05 | Basf Se | Additive and composition for metal electroplating comprising an additive for bottom-up filling of though silicon vias |
| MY168658A (en) | 2011-06-01 | 2018-11-28 | Basf Se | Composition for metal electroplating comprising an additive for bottom-up filling of though silicon vias and interconnect features |
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| CN104762643A (en) * | 2014-12-17 | 2015-07-08 | 安捷利电子科技（苏州）有限公司 | Copper plating solution capable of realizing co-plating of through hole, blind hole and circuit |
| CN107532324A (en) * | 2015-04-27 | 2018-01-02 | 株式会社杰希优 | The management method of copper sulfate bath |
| CN116068849A (en) * | 2015-09-29 | 2023-05-05 | 大日本印刷株式会社 | Mold for imprinting and method for manufacturing the same |
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| CN108914171B (en) * | 2018-07-19 | 2020-05-19 | 广东工业大学 | Additive for accelerating copper deposition and preparation method and application thereof |
| CN110983389B (en) * | 2019-12-31 | 2020-11-13 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper electroplating solution for steel parts and preparation method thereof |
| CN113279026B (en) * | 2021-04-25 | 2022-09-02 | 厦门理工学院 | Liquid medicine for copper foil blind hole filling |
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| DE19545231A1 (en) * | 1995-11-21 | 1997-05-22 | Atotech Deutschland Gmbh | Process for the electrolytic deposition of metal layers |
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-
2003
- 2003-07-15 US US10/620,042 patent/US20040045832A1/en not_active Abandoned
- 2003-08-08 CA CA002465363A patent/CA2465363A1/en not_active Abandoned
- 2003-08-08 CN CN03801591.9A patent/CN1592800A/en active Pending
- 2003-08-08 JP JP2004529271A patent/JP2005535787A/en not_active Abandoned
- 2003-08-08 EP EP03788347A patent/EP1529126A4/en not_active Withdrawn
- 2003-08-08 WO PCT/US2003/024747 patent/WO2004016829A2/en active Application Filing
- 2003-08-08 AU AU2003259049A patent/AU2003259049A1/en not_active Abandoned
- 2003-08-15 TW TW092122506A patent/TWI285687B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004016829A2 (en) | 2004-02-26 |
| JP2005535787A (en) | 2005-11-24 |
| US20040045832A1 (en) | 2004-03-11 |
| TW200415263A (en) | 2004-08-16 |
| AU2003259049A1 (en) | 2004-03-03 |
| AU2003259049A8 (en) | 2004-03-03 |
| CA2465363A1 (en) | 2004-02-26 |
| WO2004016829A3 (en) | 2004-04-29 |
| CN1592800A (en) | 2005-03-09 |
| EP1529126A2 (en) | 2005-05-11 |
| EP1529126A4 (en) | 2006-07-05 |
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