200427827 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種金屬研磨組成物（metal p〇Ushi叫 composition) 〇 【先前技術】 晚近主要使用化學機械研磨（chemical mechanical200427827 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a metal polishing composition (metal p0Ushi called composition) 〇 [Previous technology] Chemical mechanical polishing is mainly used recently
Polishing，後文偶而縮寫為CMp)用來研磨半導體基材表 面。 相反地，目前由LSI高效能觀點，佈線材料由鋁轉成 具有低電阻的銅，佈線間之絕緣膜由氧化矽薄膜改成且有 較低介電常數之低介電常數膜。此外，正在研究形成二種 佈線結構，其中㈣氮化组組成之位障膜形成於銅與低介 電常數膜間，用來防止銅擴散人低介電常數膜。隨著此種 佈線材料、低介電常數膜及位障膜材料的改變，需要有一 種金屬研磨組成物，其可以高速研磨佈線，可用於c肿具 有研磨後於基材表面之高洗滌效率。 例如提示一種金屬研磨組成物，該組成物含有金屬氧 化物如二氧化矽或氮化矽作為研磨磨料，以及硝酸銨等銨 化合物作為無機鹽（JP_N〇. 1〇_31〇766A);以及提示一種含 有二氧化矽粒子作為研磨磨料、第一界面活性劑及第二^ 面活丨生劑之金屬研磨組成物（JP-A No. 2002-155268)。jp— A No· 1 0-310766所述之金屬研磨劑用於低介電常數膜之 洗務效率不足，而JP_AN〇. 2〇〇2_155268所述之金屬研磨 劑研磨金屬如研磨叙之速率不足，且其儲存穩定性不足。 315816 5 200427827 【發明内容】 本發明之目的係提供一 可以南速研磨銅及|旦等金屬 高洗滌效率，安定性絕佳， 料（儲存穩定性絕佳）。 種金屬研磨組成物，該組成物 ，對疏水低介電常數膜具有較 且於儲存期間不會沉殿研磨磨 ::亡魏從事研究’結果發現一種金屬研磨組成 :二、=子含有2個或2個以上陰離子官能基之陰離 ==活性劑’研磨磨料及無機鹽，該組成物可以高速研 磨金屬例如，儲存穩定性隸率絕佳。此 外’發明人發現研磨速率或儲存穩定性可藉進—步含 離子界面活性劑加以改良，因而完成本發明。 換言之，本發明提供一種金屬研磨組成物，包含每分 子含有2個或2個以上陰離子官能基之陰離子界面活性 劑，研磨磨料，無機鹽及水。 【實施方式】 將進一步舉例說明本發明之細節如後。 本發明使用之陰離子界面活性劑每分子 個以上之陰離子官能基。 次2 所用方、此處，陰離子官能基為於水中解離而具有陰離子 f貝之基團，陰離子官能基例如包括磺酸基、膦酸基、磷 酸基、羧酸基及此等官能基之鹽。 本卷明使用之陰離子界面活性劑為每分子含有2個或 y個以上耵述陰離子官能基之界面活性劑，且可含有該陰 料S能基以外之官能基，但整體而言該界面活性劑於水 315816 6 ZUU42V«27 中具有負電荷。 . 每一分子結構含有2 _十〇 / ^ β ^個或2個以上陰離子官能基之陰 、 肖子"面活性副例如包括伸垸基二石黃酸或伸烧基二石黃酸鹽 例如伸烧基一夂一麵鹽、伸芳基二石黃酸或伸芳基二石黃酸 鹽如伸芳基二石黃酸二納臨、笼_ 、一 — I π — $頁酸福馬林細合物或奈二 續酸福馬林縮合物鹽例如萘二確酸福馬林縮合物二鈉鹽、· 酚二磺酸福馬林縮合物其中下式（4)之χ為氫，以及酚二磺 酸福馬林縮合物鹽例如酚二磺酸福馬林縮合物二鈉鹽，其 中下式（Α)之X為鈉，以及苯酚二磺酸福馬林縮合物其中下馨 式（Β)之X為氫’以及苯紛二確酸福馬林縮合物鹽例如苯盼 二磺酸福馬林縮合物二鈉鹽，其中於下式（Β)之X為鈉。 0ΗPolishing (hereinafter occasionally abbreviated as CMP) is used to polish the surface of a semiconductor substrate. In contrast, from the viewpoint of high performance of LSI, the wiring material is changed from aluminum to copper with low resistance, and the insulating film between wirings is changed from a silicon oxide film to a low dielectric constant film with a lower dielectric constant. In addition, two types of wiring structures are being formed. A barrier film composed of a hafnium nitride group is formed between copper and a low-dielectric-constant film to prevent copper from diffusing into the low-dielectric-constant film. With the change of such wiring materials, low dielectric constant films, and barrier film materials, there is a need for a metal polishing composition that can grind wiring at high speed and can be used for c-swells with high washing efficiency on the surface of the substrate after polishing. For example, a metal polishing composition is suggested, which contains a metal oxide such as silicon dioxide or silicon nitride as an abrasive, and an ammonium compound such as ammonium nitrate as an inorganic salt (JP_N0.1.10_31〇766A); and a prompt A metal polishing composition containing silicon dioxide particles as an abrasive, a first surfactant, and a second surfactant (JP-A No. 2002-155268). jp— The metal abrasive described in A No · 1 0-310766 is insufficient for the cleaning efficiency of low dielectric constant films, and the metal abrasive described in JP_AN 0.2200-2155268 is insufficient in the rate of polishing metal such as grinding. , And its storage stability is insufficient. 315816 5 200427827 [Summary of the invention] The purpose of the present invention is to provide a high-speed washing efficiency, excellent stability, and excellent storage stability. Metal polishing composition, the composition has a relatively low hydrophobic permittivity film and does not sink during storage. Grinding grinding :: Wei Wei engaged in research 'results found a metal polishing composition: two, = 2 Or anion of 2 or more anionic functional groups == active agent 'abrasive abrasive and inorganic salt, the composition can grind metal at high speed. For example, it has excellent storage stability. In addition, the inventors have found that the milling rate or storage stability can be improved by borrowing a step-containing ionic surfactant, thus completing the present invention. In other words, the present invention provides a metal abrasive composition comprising an anionic surfactant containing two or more anionic functional groups per molecule, an abrasive, an inorganic salt, and water. [Embodiment] The details of the present invention will be further illustrated as follows. The anionic surfactant used in the present invention has more than one anionic functional group per molecule. The method used here, here, the anionic functional group is a group that dissociates in water and has an anion f. The anionic functional group includes, for example, a sulfonic acid group, a phosphonic acid group, a phosphate group, a carboxylic acid group, and a salt of such a functional group. . The anionic surfactant used in this volume is a surfactant that contains 2 or more than y of the above-mentioned anionic functional groups per molecule, and may contain functional groups other than the S energy group of the feminine material, but the interface activity as a whole The agent has a negative charge in water 315816 6 ZUU42V «27. . Each molecule structure contains 2 _ 10 / ^ β ^ 2 or more anionic functional groups of yin, xiaozi " surface active side, such as including arsenyl diaxanthate or arsenyl diaxanthate such as Dextrin base salt, Dextrin diaphtholic acid or Dextrin diaxanthinate, such as Dextrin diaphthyl oxalate dinaline, cage_, one — I π — $ 页 酸 福马林A fine compound or a neonic acid formalin condensate salt such as a disodium naphthalate diformalin condensate, a phenol disulfonate formalin condensate where χ of the following formula (4) is hydrogen and phenol disulfonate Formalin acid condensate salts such as the disodium salt of phenol disulfonic acid formalin, where X of the following formula (A) is sodium, and phenol disulfonic acid formalin condensate where X of the following sweet formula (B) is hydrogen 'And the benzoic acid formalin condensate salt, such as the disodium salt of the phenanthrene disulfonic acid formalin condensate, in which X in the following formula (B) is sodium. 0Η
[入」 〇3Χ (A) (X為氫或鹼金屬） 籲[入] 〇3χ (A) (X is hydrogen or an alkali metal)
(Β) (X為氫或驗金屬） 315816 7 200427827 由所得研磨組成物之儲存穩定性觀點，較佳本發明使. 用之陰離^界面活性劑為分子内進一步有喊鍵聯之陰離子、 界面活性劑。一個分子結構含有醚鍵聯連同2個或2個以 上陰離子官能基之陰離子界面活性劑例如包括烷基二苯基 醚二磺酸、烷基二苯基醚二膦酸、烷基二笨基醚二羧酸1 其鹽。 一其中以烷基二苯基醚二磺酸或其鹽為佳。例如以十二. ?基二苯基醚二磺酸二鈉鹽、十二烷基二苯基醚二磺酸二. 銨鹽、：二烷基二苯基醚二磺酸二三乙醇胺鹽為佳。 · 、此等陰離子界面活性劑可單獨使用《組合兩種或兩種 以上使用。 本發明使用之研磨磨料可為無機粒子或有機粒子中之 任:者。無機粒子例如包括含有金屬氧化物作為主要成分 ，粒子’金屬氧化物例如為二氧化石夕、氧化錄、氧化欽、 氮切、碳化石夕及二氧化鍾。其中以二氧化石夕為佳，以煙 二氧化石夕及膠體氧化石夕為更佳。由所得金屬研磨組成物儲 子期間可抑制沉、粒子直徑均句、以及可防止於銅表面或 政’丨％ ¥數膜表面刮傷觀點，又以膠體氧化矽為更佳。 有機粒子為含有有機聚合物化合物作為主要成分之粒 幻士匕括有機聚合物化合物例如甲基丙烯酸系樹脂如 酚樹脂、蜜胺樹脂、聚苯乙烯樹脂及聚碳酸酯樹脂， 、入由乳化聚合獲得之乙烯化合物聚合物，以及可吸附特定 離子交換樹脂及螯合樹脂。其中由可控制佈線、低 1兒系數膜及位障膜之研磨速度觀點，以可吸附如銅及钽 315816 8 200427827 等孟屬之離子父換樹脂及螯合樹脂為佳。 由研磨後抑制表面出現舌丨廢， m見W展硯點，研磨粒子平均粒子 直徑較佳為10微米或以下，更 「文仏為〇· 1微米或以下。 =夕卜’由研磨速率觀點，平均粒子直徑更 ⑽5 械米或以上。 σ使用具有均勾粒子直徑之研磨磨料，或可使用經由 具有不时均粒小直徑之研磨粒子。例如可使用具 0]=子m.1微米之研磨粒子與具有平均粒子直徑 〇· 1破米之研磨粒子混合物。 〃至於本發明使用之無機鹽，以無機酸如墙酸、碟酸、 3酸及额錢隸氫氧㈣H餘、烧醇胺及 I基胺中之任一者生成之鹽為佳。 一燒基録氫氧化物例如包括四甲基銨氫氧化物及四乙基 叙11氧化物；絲胺例如包括甲基胺、乙基胺、丙基胺及 丁基胺；烷醇胺例如包括一乙醇胺、二乙醇胺、三 及2-(2-胺基乙氧基）乙醇W基胺包括㈣駭Ν，Ν_ —乙基髮基胺。 …此等無機鹽中以硝酸鹽為佳。石肖酸鹽例如包括四甲基 銨氫氧化物硝酸鹽、硝酸銨、硝酸一乙醇胺、及硝酸羥基 胺。其中以硝酸銨為佳。 此等無機鹽可單獨使用或組合2種或2種以上使用。 無機鹽可經由混合前述無機酸與院基銨氫氧化物、氨、烧(B) (X is hydrogen or metal detection) 315816 7 200427827 From the standpoint of storage stability of the obtained grinding composition, it is preferably used in the present invention. The anionic surfactant used is an anion, which further has a shouting linkage in the molecule, Surfactant. Anionic surfactants whose molecular structure contains an ether linkage together with 2 or more anionic functional groups include, for example, alkyl diphenyl ether disulfonic acid, alkyl diphenyl ether diphosphonic acid, alkyl dibenzyl ether Dicarboxylic acid 1 and its salts. One of them is preferably alkyldiphenyl ether disulfonic acid or a salt thereof. For example, dodecyl diphenyl ether disulfonic acid disodium salt, dodecyl diphenyl ether disulfonic acid di. Ammonium salt, and dialkyl diphenyl ether disulfonic acid ditriethanolamine salt are good. · These anionic surfactants can be used alone or in combination of two or more. The abrasive used in the present invention may be any of inorganic particles or organic particles. The inorganic particles include, for example, a metal oxide as a main component, and the particles' metal oxides are, for example, stone dioxide, oxide, oxide, nitrogen cut, carbide, and bell dioxide. Among them, stone dioxide is preferred, and tobacco dioxide and colloidal oxide are more preferred. From the viewpoint that the obtained metal abrasive composition can be deposited during storage, uniform particle diameters can be prevented, and can be prevented from being scratched on the copper surface or the film surface, and colloidal silicon oxide is more preferred. Organic particles are granules containing organic polymer compounds as the main component. Organic polymers such as methacrylic resins such as phenol resins, melamine resins, polystyrene resins, and polycarbonate resins are polymerized by emulsion polymerization. The obtained ethylene compound polymer can adsorb specific ion exchange resins and chelate resins. Among them, from the viewpoint of controlling the polishing speed of the wiring, the low-coefficient film and the barrier film, it is better to adsorb the parent ion-exchange resin and chelate resin such as copper and tantalum 315816 8 200427827. The surface of the tongue is prevented from being scrapped after grinding. The average particle diameter of the abrasive particles is preferably 10 micrometers or less, more preferably, the average particle diameter of the abrasive particles is 10 micrometers or less. , The average particle diameter is more than 5 mechanical meters or more. Σ Use an abrasive with a uniform particle diameter, or use abrasive particles with a small diameter from time to time. For example, you can make appliances 0] = sub m.1 micron grinding A mixture of particles and abrasive particles having an average particle diameter of 0.1 dm. 〃 As for the inorganic salt used in the present invention, inorganic acids such as wall acid, dish acid, 3 acid and formic acid hydroxide, H, amine, and alcohol The salt generated by any of the I-based amines is preferred. Monobasic hydroxides include, for example, tetramethylammonium hydroxide and tetraethylammonium oxide; serine includes, for example, methylamine and ethylamine. , Propylamine, and butylamine; alkanolamines include, for example, monoethanolamine, diethanolamine, tris, and 2- (2-aminoethoxy) ethanol. W-based amines include N, N-ethylethylamino. ... Nitrate is preferred among these inorganic salts. Schott salts include, for example, Ammonium hydroxide nitrate, ammonium nitrate, monoethanolamine nitrate, and hydroxylamine nitrate. Among them, ammonium nitrate is preferred. These inorganic salts can be used alone or in combination of two or more. The inorganic salts can be mixed by the foregoing. Inorganic acid and amine ammonium hydroxide, ammonia, burning
基胺、料胺及㈣胺巾之任—者而製備；或市售無機鹽 可就此使用。 I 315816 9 200427827 由改良對金屬膜如叙等位障金屬膜之研磨速度觀點， 以硝酸銨為佳。 本發明之金屬研磨組成物除了前述無機酸之外，可含 有有機I或其鹽。有機酸例如包括羧酸如乙酸、擰檬酸、 乳馱丙—I、酒石酸、丁二酸、草酸、胺基酸、正壬酸、 正癸酸、正辛酸、2一乙基己酸、"基庚酸、2_正丙基_ 正戊酉夂2, 2 —甲基正戊酸、正庚酸、2_甲基己酸、5-甲 基己酸、第三丁基乙酸、正己酸、2, 2_二甲基—正丁酸、3, 3_ 正丁酸、2-甲基-正戊酸、3_甲基_正戊酸、4_曱基_正戊酸、 2甲基-正丁酸、2-乙基-正丁酸、異戊酸、DL_2_甲基丁酸、 特戊酸★、正戊酸及正了酸。可使用—般市售之有機酸。 此等有機酸中，由改良對金屬膜之洗膝效率觀點，以 乳酸、酒石酸、丁二酸、草酸、正辛酸、2, 2-二甲基正戊 酉文正庚3义5甲基己酸、第三丁基乙酸、正己酸、2, 2_ 甲基正丁 g欠及2-甲基-正丁酸及其鹽為佳。鹽例如包 括四甲基銨氫氧化物鹽、銨鹽、—乙醇胺鹽、及經基胺鹽。 其中，以銨鹽為特佳。以草酸銨為最佳。 此等有機酸可單獨使用或組合2種或2種以上使用。 本發明之金屬研磨組成物含有非離子界面活性劑。 使用之非離子界面活性劑包括含於f知金屬研磨劑之 非離子界面活性劑。例如以下式⑴表示之非離子界面 劑為佳： Y 〇-(CaH2aO)b-(CxH2x〇)y—z (I) (其中a、b、X及y分別為正整數，以及γ及z分別為氫原 J158】6 10 7827 子或含有9至19個碳數之烴基）。 當Y及Z中之一或-去及”、 ..w 飞—者係以烴基表示時，烴基較佳為 飽和煙基。烴基之碳數為9 丄〇或丨2。 至19，較佳為9至12，更佳為 式（I)中，X及y表示π:敕奴 μ ^^ 丁正整數，X與a可相異或相同。 由水中溶解度觀點，x較佳Λ "丁， 平又1土為10或1〇以下，更佳為5或5 以下。X較佳為3或3以上， 及更佳為3。由後述低介電常 數、、，邑、、彖族間之濕潤性觀點， y敉佳為ίο或ίο以下，及更 佳為5或5以下。通常y為1或1以上。 …a為2至5,較佳為2或3 ’及更佳為2。由水溶液之 /谷解度觀點，b較佳為4 < 4 u i Φ u & π Λ目士 勹Α4以上，及更佳為5或5以上。 由二有疏水表面之低介電常數臈之濕潤性觀點，以2〇或 以下為佳，以10或10以下為更佳。 〆 Α八H非離子界面活性劑例如包括聚氧伸乙基聚氧伸丙 “基越、聚氧伸乙基聚氧伸丙基月桂基驗、聚氧伸乙美 聚氧=基録虫默基喊、聚氧伸乙基聚氧伸丙基硬月旨基/ 、及聚氧伸乙基聚氧伸丙基油基醚。其中以聚 氧伸丙基癸基㈣聚氧伸乙基聚氧伸丙基月桂基縣= =(1)中a等於x(a=x)之情況可以下式⑴）表示： Y-0 - (CmH2m〇)nj (⑴ i其中〇1及n為相同或相異且為正整數，以及丫及z定義如 前）。 式（H)中，m為2至5 ’較佳2或3，且更佳A 9 , 水溶液之溶解度觀點，,較佳為4或4以上，且更佳為5 ]] 315S}6 200427827 或5以上。由疏水膜之濕潤性觀點，以2〇或2〇以下為佳 且以10或1 0以下為更佳。 至於式(II)表示之非離子界面活性劑例如以聚氧伸乙 基癸基ϋ、聚氧伸乙基月桂基喊、聚氧伸乙基鯨蠟基鱗、 純伸乙基硬脂㈣、及聚氧伸乙基油基趟為佳。其中以 聚氧伸乙基癸基醚及聚氧伸乙基月桂基醚為更佳。 前述非離子界面活性劑可使用其中一種或兩種或多 種。當使用兩種或多種時，較佳至少一種為上式⑴）表示 之非離子界面活性劑。 泡 本發明之金屬研磨組成物含有防餘劑、氧化劑及消 劑等成分。 防蝕劑例如包括一般使用之防蝕劑，如唑類如丨2 3一 苯并三唑、鄰-甲苯基三唑、間_甲苯基三唑、對-甲苯基三 嗤:缓基苯并三唾、卜經基苯并三[硝基苯并三唾t及 一 t基丙基苯并二唑；毓基化合物如硫乙醇酸、硫二甘醇、 硫们由、2 一疏基味唾啉、2-魏基乙醇及魏基丙酸；以及芳 香族It基化合物如料類如甘露糖醇及葡萄冑 連苯三I其中較佳為U，3-苯并三錢苯并三㈣生 -此寺防㈣1可單獨使用或組合兩種或兩種以上使用 經由含括防蝕劑，可避免研磨後於表面出現到痕及凹陷 傾向。 由進-步改良研磨速率觀點’本發明之金屬研磨組 物可含有氧化劑。 、、> 315816 12 200427827 氧化劑例如包括過氧化氫 氮為特佳。 峨酸及峨酸鹽 以過氧化 此等氧化劑可單獨使用或組合兩種或兩種以上使用 消泡劑例如包括乳化劑及水溶性醇如多種乳化劑 醚類乳化劑、商品名為亞德卡諾（AdeG_1)LG_i35之㈣ 酷類乳化劑（旭電工公司製造）、乳化型乳化劑、以石夕為主 之乳化型乳化劑、商品名亞德卡諾LG_674之特殊非離子型 礼化劑（旭電工公司製造）、以及聚氧化石夕類乳化劑，·以及 水溶性醇類且通常已知可抑制發泡，例如甲醇、乙醇、工 丙醇、2-丙醇、2-曱基-！ 一丙醇及2_甲氧基乙醇。—、— 本發明之金屬研磨組成物包含前述研磨磨料、益機 鹽、陰離子界面活性劑及水。此外’若有所需可添加氧化 劑、防触劑及消泡劑至其中。 金屬研磨組成物中，研磨磨料、無機鹽與陰離子界面 活性劑之總量通常為〇.丨重量％至4〇重量％，以及水為6〇 重量％至9 9. 9重量％。當添加氧化劑、防蝕劑、及消泡劑等 其它成分時，添加劑總量通常占金屬研磨組成物之〇 〇〇1 重量％至15重量％。 * 研磨磨料、無機鹽及陰離子界面活性劑之總量中，研 磨磨料含量係占〇· 05重量％至50重量％，較佳占〇 a重量 %至50重量％。無機鹽含量為〇.〇1重量％至25重量％，且= 佳為0.25重量％至25重量％ •，以及陰離子界面活性劑含^ 為0.001重量％至25重量％，且較佳為〇·25重量％至25重 量％。 315816 13 200427827 磨紐成物含有前述非離子界 料界面活性劑與非離子界面 ：, 陰離子界面活性劑含晉相n〜 〜里較佳係於雨述 同之範圍°陰離子界面活性劑血 烚離子界面活性劑總量中 離子界面活性劑。_離子x G重量％或以上為陰 之界面活性劑與非離子界面活性劑 之比杈佳係於1:0.01至1:1之範圍。 =明：金屬研磨劑含有有機酸時，有機酸含量通 吊係占孟屬研磨組成物之0.001至1〇重量％。 當含有氧化劑、㈣劑及消泡卿其它成分時，此等 成/刀之含量為氧化劑通常占金屬研磨組成物之〇】至π 重量％，以及防蝕劑通常占0.01至5.0重量％。 當添加前述研磨磨料、無機鹽、陰離子界面活性劑及 欠以及it #添加其它成分例如氧化劑、防钱劑及消泡 劑時’其添加順序並無特殊限制。為了分散前述成分，可 使用均質器、超音波、濕介質研磨等。 本發明之金屬研磨組成物之pH較佳為3至12，更佳 ^ 3至9，及又更佳為7至9。金屬研磨組成物之pH係於 前述各個成分混合之後，經由添加無機酸或有機酸 '如鹼 金屬及銨之無機驗或如有機胺之有機鹼而調整pH。無機酸 例如包括硝酸、磷酸及硫酸；無機鹼例如包括氫氧化銨； 及有機鹼包括胺類。較佳此等無機酸、無機鹼及有機驗不 含金屬離子。 此外，當本發明之金屬研磨組成物含有氧化劑時，進 行研磨時，氧化劑較佳混合入組成物。 315816 14 200427827 提示可製備含高濃度前述各項成分之溶液，可於 研磨時以水稀釋使用。 本發明之金屬研磨組成物適合用於研磨半導體基材表 面」於該基材表面暴露於低介電常數膜、作為低介電常數 保相之覆蓋層膜、作為佈線間之層間絕緣膜之絕緣膜等 中之任-者。此外，組成物較佳用於研磨半導體基材表面， =其上暴露低介電常數膜、覆蓋層膜、層間絕緣膜、銅佈· 線膜、位障鈕或氮化鈕膜等。 ▲ 低介電常數膜及低介電常數保護膜例如包括無機膜如# FSG(含氟二氧切）、⑽（含碳二氧切）、&⑽（含氮二 氧化外SiC、SlN及SiCN其係藉CVD方法製成；聚有機 軋化錢膜如MSQ(甲基縣半氧烧）、HSQ(氫碎倍半氧 及MHSQ(甲基化氫石夕倍半氧燒）此等膜係藉塗覆及培燒而凡 形成於基材上；芳香族膜如PAE(聚芳基⑹及卿（二 基氧化石夕烧音苯并環丁烯）；及有機膜例如⑽及多孔 欲藉本發明金屬研磨組成物研磨之佈線間之層間 膜例如包括⑽系列之叫膜，其係經由使用四乙氧基石夕 坑（TE0S)或料氣體製成；卿_叫膜其係利用高密度電 漿製成；以及BPSG膜，其中二氧化矽膜摻雜硼或磷等。 本發明金屬研磨組成物適合研磨表面具有鋼作為佈線 材料之半導體裝置(如LSI)，具有组或氮化㈢為金屬使 用之位障膜、以及具有疏水表面而具有使用水之劣化濕潤 性作為佈線間之絕緣膜之低介電常數膜、或具有疏水表面 315816 15 200427827 形成於低介電常數膜上來保護低介電常數膜之 層膜，或於研磨處理期間前述薄縣 、^面之覆蓋 實施例 …出之表面。 —將參照實施例說明本發明，但本發明絕非為 貫施例1 (組成物之製備） 、厅限。 於0.3重量％氧化石夕、u重量酸錢、1〇重 -烧基二苯基醚二續酸二銨、4重量％過氧化氫及〇 〇旦 %苯并三唾，加水至總量1GG重量％，將各材料混合。添力里口 硝酸至混合物調整至pH 4(後文稱之為組成物1)。、、 實施例2 广組成物係根據實施例丨之相同方式製備，但〇·丨重量％ 聚，伸乙基月桂基驗進—步添加至組成物i至總量為剛 重虽％ ’混合各材料（後文稱之為組成物2 )。 實施例3 广組成物係根據實施例丨之相同方式製備，但〇1重量％ 聚氧伸乙基月桂基醚添加至組成物丨至總量為丨〇〇重量％， 混合各材料，然後添加氫氧化銨至混合物而獲得pH 8. 5(後 文稱之為組成物3)。 實施例4 組成物係根據實施例2之相同方式製備，但額外添办 〇· 04重草酸銨至組成物2,材料混合至總量100重量％， 然後添加氫氧化銨至混合物獲得pH 8. 5 (後文稱之為組成物4)。 比較例1 16 315816 200427827 組成物係根據實施例1之相同方式製備，但使用只具 有一個陰離子官能基之二丁基萘磺酸鹽作為陰離子界面活 性劑，來取代十二烧基二苯基縫H錄（後文稱之為比 較組成物1)。 比較例2 組成物係根據比較例1之相同方式製備，但使用聚氧 伸乙基ys-萘基喊酸醋納鹽來替代二丁基蔡姐鹽（後文 稱之為比較組成物2)。 比較例3 組成物係根#比較例1之相同方式製冑，但使用聚氧 伸乙基十三烷基醚硫酸酯鈉鹽來替代二丁基萘磺酸鹽（後 文稱之為比較組成物3)。 比較例4 、組成物係根據實施例κ相同方式製備，但未添加界 面活性劑（後文稱之為比較組成物4)。 比較例5 組成物係根據實施例1之相同方式製備，但未添加界 面活性劑及硝酸銨（後文稱之為比較組成物5)。 實驗例1 使用組成物卜2、3及4及比較組成物卜2、3、4 f 5 ’評比儲存穩定性、研磨速率、以及研磨完成後去除 黏附於低介電常數膜、銅膜及組膜之研磨粒子之去除效 率 0 [研磨條件] 315816 17 200427827 研磨機：葉型CMP裝置CMS-200M(紐富雷爾（NuFlare) 技術公司製造） 研磨墊：聚胺甲酸酯類 墊面板轉速：78 rpm 夾持欲研磨晶圓之平台轉速：75 rpm 研磨壓力·· 15 Kpa 研磨漿液流速：150毫升/分鐘 洗務步驟：輕刷洗、錯筆刷洗、巨音波絲，以及使 用超純水以此順序進行離心脫水。 [组膜研磨速率之量測] 曰。1d頌料造！續於㊉日日日圓上，㈣㈣為欲研々 圓來根據如述研磨條件進行研磨。於研磨前及研磨後， ，用電子顯微鏡測定薄膜厚度。研磨前與研磨後之薄膜々 度i除以研磨時間，求得研磨速率。 [粒子去除速率之計算] 人使用藉CVD(化#氣相沉積）方法製作於石夕晶圓上之低 Ί吊數膜（Sac膜）、藉鑛覆法製作於石夕晶圓上之銅膜、 i = f鍍法製作於梦晶®上之组膜來作為欲研磨之晶圓， 二月|j述研磨條件進行研磨來附著研磨粒子至薄膜。洗蘇 八5 麦使用粒子測量裝置[WM-1500(托普康（T〇PC〇N) ::Γ造)]於晶圓測定粒子直徑為G.2微米或以上之黏附 方=H條前及洗㈣之黏附粒子數目，根據如下 王式求出藉洗滌去除粒子速率。 粒子去除速率計算方法 315816 ]8 200427827 去除粒子速率= —(洗滌後黏附粒子數目）/(洗滌前黏 附粒子數目）]X 1 g g 於洗滌前，於低介電常數膜上衍生自金屬研磨劑之粒 子數目約為1 0000至1 2000。 [儲存穩定性之評比] 於組成物1、2、3及4及比較組成物1、2、3、4及5， 測定恰於製備後以及讓其放置隔夜後（約8小時）之研磨粒 子平均粒子直徑’來评比各組成物之粒子穩定性。使用 NIKKISO公司製造之微轨（Micro Track)UPA來測定平均粒 子直徑。 315816 19 200427827 薛+適 恰於混料後研磨 粒子之平均粒子 直徑（奈米） 薄膜粒子 去除比率 (%) 钽膜研磨速率 (埃/分鐘） Sh 砘 P? cn 5*- σ\ D CP 〇 |界面活性劑B *3 逵 > IO 草酸敍（重量％〉 墙酸銨（重量％) 氧化叾夕(重量％) ㈠ 卬 o P SiOC 00 KD ① LH VD cn \D vr> cn 520 K1 〇 1—* 〇 ο U) 組成物1 ΚΩ ① LH VD LP KD VD 办 640 〇 Μ Μ Ο l·-1 〇 ο OJ 組成物2 H-1 ro VD LP 'vD LP V£) VD 么 520 〇 h-1 h-1 Ο Η ο ο u> 組成物3 μ kD KD KD KO VP 办 580 〇 Ι-» I-1 ο 〇 〇 h-1 ο ο (jj 組成物4 未測定 VD LP ΚΩ VD Ln KD KD U> 520 1—» 〇 ο ο U) 比較組成物 1 未測定 未測定1 1 1 1 1 Μ Ο Η-» ο ο Οϋ 比較組成物 2 未測定 未測定 1 1 1 1 1 h-i 〇 I—1 ο ο LO 比較組成物 3 00 KD K) U) V£> K) (-* KD 〇 -o 563 h-> ο ο ϋϋ 比較組成物 4 00 00 ① ro VD Ln CD CO I—1 00 ro ο UJ 比較組成物 5 20 315816 / Ο Δ / / Ο Δ / 膠體氧化矽， 自w· R·葛瑞士（w· 米 以商品名「魯多士（Ludox) SM-30」得 R_ Grace)公司，平均粒子直徑·· 7奈 陰離子界面活性劑， 銨，具有鍵聯以二::二燒基二苯基二續酸二 *3 ^ 及兩個陰離子官能基。 非離子界面活性劑 〇 及其中於前述式(11)中：：來乳伸乙基月桂基醚’以 基，. 為月桂基作為含碳數12之烴 悬二為,’η為8’以及z為氯。 月桂基Si界I =(’其係呈聚氧伸乙基聚氧伸丙基 之煙基，&為2，b 4、/nY為月桂基作為/碳數12 Μ陰離子界面活性劑，盆係呈^ 虱。· 個陰離子官能基。 、、一丁基奈嶒酸且含有一 乙基/5 -萘基醚硫 乙基十三烷基醚 陰離子界面活性劑，其係呈聚氧伸 酸SI，鹽且含有—個陰離子官能基。 ”陰離子界面活性劑，其係呈聚氧伸 硫酸醋萘鹽且含有一個陰離子官能基。 膜上具有高度粒子去除能二 料。此外，於制偌尨T么山 3黏附之研磨磨 、：肴後不會出現沉澱’儲存穩定性絕佳。 能力此外’减物4於研磨後對金屬膜具有極佳粒子去除 相反地， 使用只含有一 即使於使用陰離子界面 個陰離子官能基之陰離 活性劑之情況下，於 子界面活性劑之組成 315816 2】 200427827 物’例如比較組成物I，雖然研磨速率及洗滌效率類似组 成物1至4，但於製備後，研磨粒子聚集，聚集體沉澱， 如此有儲存穩定性問題。又於比較組成物2及3，其係使 用具有一個陰離子官能基之陰離子界面活性劑，研磨磨料 聚集，聚集體沉澱，如此儲存穩定性不足。此外，不含界 面活性劑之比較組成物4 ’因低介電常數膜間之濕潤性低 劣，表面即刻乾燥，故隨後之洗滌效率不足；以及於不含 硝酸鹽之比較組成物5，鈕研磨速率低。 一把據本&月*供_種金屬研磨組成物，該組成物可 以南速研磨銅及ϋ金屬 蘇效率’安定性絕佳，且：吊數:先 子/月間不會沉殿研磨磨料。 315816It can be prepared from any of amines, amines and ammonium towels; or commercially available inorganic salts may be used for this purpose. I 315816 9 200427827 From the viewpoint of improving the polishing speed of metal films such as Syrian barrier metal films, ammonium nitrate is preferred. The metal polishing composition of the present invention may contain organic I or a salt thereof in addition to the aforementioned inorganic acid. Organic acids include, for example, carboxylic acids such as acetic acid, citric acid, lactam-1, tartaric acid, succinic acid, oxalic acid, amino acids, n-nonanoic acid, n-decanoic acid, n-octanoic acid, 2-ethylhexanoic acid, " Heptanoic acid, 2-n-propyl-n-pentanoic acid 2, 2-methyl-n-pentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid, third butylacetic acid, n-hexane Acid, 2, 2-dimethyl-n-butanoic acid, 3, 3-n-butyric acid, 2-methyl-n-valeric acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2 methyl -N-butyric acid, 2-ethyl-n-butyric acid, isovaleric acid, DL_2-methylbutyric acid, pivalic acid ★, n-valeric acid and n-acrylic acid. Use can be made of commercially available organic acids. Among these organic acids, lactic acid, tartaric acid, succinic acid, oxalic acid, n-octanoic acid, 2, 2-dimethyl-n-pentanyl, n-heptyl 3-hexyl 5-methylhexanoic acid , Tert-butylacetic acid, n-hexanoic acid, 2,2-methyl-n-butylg and 2-methyl-n-butyric acid and salts thereof are preferred. The salt includes, for example, a tetramethylammonium hydroxide salt, an ammonium salt, an ethanolamine salt, and an ammonium salt. Among them, ammonium salts are particularly preferred. Ammonium oxalate is the best. These organic acids can be used alone or in combination of two or more. The metal polishing composition of the present invention contains a non-ionic surfactant. The nonionic surfactants used include nonionic surfactants contained in metal abrasives. For example, the non-ionic interface agent represented by the following formula 为 is preferred: Y 〇- (CaH2aO) b- (CxH2x〇) y-z (I) (where a, b, X, and y are positive integers, respectively, and γ and z are respectively Proton J158] 6 10 7827 or a hydrocarbon group containing 9 to 19 carbon numbers). When one of Y and Z or-and ", ..w fly" is represented by a hydrocarbyl group, the hydrocarbyl group is preferably a saturated nicotinyl group. The carbon number of the hydrocarbyl group is 9 丄 or 丨 2. to 19, preferably It is 9 to 12, and more preferably in formula (I), X and y represent π: 敕 Nu μ ^^ D positive integers, X and a may be different or the same. From the viewpoint of solubility in water, x is preferably Λ " D , Pingyi 1 soil is 10 or 10 or less, more preferably 5 or 5 or less. X is preferably 3 or 3 or more, and more preferably 3. From the low dielectric constant mentioned later, In terms of wettability, y 敉 is preferably ίο or ο or less, and more preferably 5 or less. Usually y is 1 or more.… A is 2 to 5, preferably 2 or 3 ′ and more preferably 2 From the viewpoint of the solution / valley resolution of the aqueous solution, b is preferably 4 < 4 ui Φ u & π Λ 目 士 勹 A4 or more, and more preferably 5 or more. From the low dielectric constant of the hydrophobic surface From the viewpoint of moisturizing properties, 20 or less is preferable, and 10 or less is more preferable. 〆A Eight H nonionic surfactants include, for example, polyoxyethylene polyoxyethylene, polyoxyethylene, polyoxyethylene Ethyl polyoxypropyl laurate test Mo Ji = group call record insects, polyoxyethylene polyoxypropylene extension extending ethyl propyl group aims hard month / and polyoxyethylene polyoxypropylene extension extending ethyl propyl ether oil. Among them, the case where a is equal to x (a = x) in poly (oxydecyldecyl), polyoxyethyl (polyoxyethylene) lauryl county = = (1) can be expressed as follows: Y-0- (CmH2m〇) nj (where i and n are the same or different and are positive integers, and y and z are as defined above). In formula (H), m is 2 to 5 ′, preferably 2 or 3, and more preferably A 9. From the viewpoint of solubility of the aqueous solution, 4 or more is preferable, and 5 is more preferable.]] 315S} 6 200427827 or 5 or more. From the viewpoint of the wettability of the hydrophobic film, 20 or less is preferable, and 10 or 10 or less is more preferable. As for the non-ionic surfactant represented by the formula (II), for example, polyoxyethylene decyl hydrazone, polyoxyethyl laurate, polyoxyethyl cetearyl scale, pure ethyl stearyl fluorene, And polyoxyethylated oil is better. Among them, polyoxyethyl decyl ether and polyoxyethyl lauryl ether are more preferred. As the aforementioned nonionic surfactants, one kind or two or more kinds can be used. When two or more kinds are used, preferably at least one kind is a nonionic surfactant represented by the above formula (i)). Foam The metal polishing composition of the present invention contains components such as an anti-remainder, an oxidizing agent, and a sterilant. Anticorrosives include, for example, commonly used anticorrosives, such as azoles such as 2 3 -benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole: retarderbenzotrisal Benzylbenzotris [nitrobenzotrisialt and monopropylpropylbenzodiazoles; fluorenyl compounds such as thioglycolic acid, thiodiglycol, thiobenzyl, 2 thiobenzoyl sialine, 2 -Weyl alcohol and Weyl propionic acid; and aromatic It-based compounds such as materials such as mannitol and grape pyrene triphenyl I, preferably U, 3-benzotrisylbenzotribenzidine-this temple Anti-knock 1 can be used singly or in combination of two or more. Through the inclusion of an anti-corrosive agent, the surface can be prevented from forming marks and depressions after grinding. From the viewpoint of further improving the polishing rate, the metal polishing composition of the present invention may contain an oxidizing agent. It is particularly preferred that the oxidant includes hydrogen peroxide and nitrogen, for example. Peroxidic acid and eric acid salts can be used alone or in combination of two or more of these oxidants. Antifoaming agents include, for example, emulsifiers and water-soluble alcohols such as various emulsifiers. Ether-based emulsifiers. (AdeG_1) LG_i35 35 Cool emulsifier (made by Asahi Electric Co., Ltd.), emulsifier emulsifier, emulsifier emulsifier mainly based on Xixi, special non-ionic etiquette (trade name: Yadecano LG_674) Manufactured by Asahi Electric Co., Ltd.), and poly-oxide-based emulsifiers, and water-soluble alcohols, which are generally known to inhibit foaming, such as methanol, ethanol, propylene alcohol, 2-propanol, 2-fluorenyl-! Monopropanol and 2-methoxyethanol. ———— The metal abrasive composition of the present invention includes the aforementioned abrasive abrasive, organic salt, anionic surfactant, and water. In addition, if necessary, an oxidizing agent, an anti-contact agent and an antifoaming agent may be added thereto. In the metal abrasive composition, the total amount of the abrasive, the inorganic salt and the anionic surfactant is usually from 0.1% to 40% by weight, and the water is from 60% to 9.9% by weight. When other ingredients such as oxidants, corrosion inhibitors, and defoamers are added, the total amount of the additives usually accounts for 001 to 15% by weight of the metal grinding composition. * In the total amount of abrasive abrasive, inorganic salt and anionic surfactant, the abrasive abrasive content is 0.05 to 50% by weight, preferably 0 to 50% by weight. The content of the inorganic salt is from 0.01 to 25% by weight, and is preferably from 0.25% to 25% by weight, and the anionic surfactant contains 0.001 to 25% by weight, and preferably 0. 25% to 25% by weight. 315816 13 200427827 The milled product contains the aforementioned non-ionic boundary surfactant and non-ionic interface :, the anionic surfactant contains Jin phase n ~ ~ li is preferably in the same range as described in the above description ° anionic surfactant active blood ions Ionic surfactants in total surfactants. The ratio of the ionic x G weight% or more anionic surfactant and non-ionic surfactant is preferably in the range of 1: 0.01 to 1: 1. = Ming: When the metal abrasive contains organic acid, the content of the organic acid is 0.001 to 10% by weight of the Meng abrasive composition. When containing an oxidizing agent, an elixir, and other ingredients of the antifoaming agent, the content of these ingredients / knife is that the oxidizing agent usually accounts for 0% to π% by weight of the metal abrasive composition, and the anticorrosive agent usually accounts for 0.01 to 5.0% by weight. When the aforementioned abrasives, inorganic salts, anionic surfactants and additives are added and it # is added with other ingredients such as oxidants, money inhibitors and defoamers, there is no particular limitation on the order of addition. In order to disperse the aforementioned components, a homogenizer, an ultrasonic wave, a wet medium grinding, or the like can be used. The pH of the metal abrasive composition of the present invention is preferably 3 to 12, more preferably 3 to 9, and still more preferably 7 to 9. The pH of the metal polishing composition is adjusted by adding an inorganic acid or an organic acid such as an alkali metal and ammonium or an organic base such as an organic amine after mixing the foregoing components. Inorganic acids include, for example, nitric acid, phosphoric acid, and sulfuric acid; inorganic bases include, for example, ammonium hydroxide; and organic bases include amines. It is preferred that these inorganic acids, inorganic bases and organic solvents do not contain metal ions. When the metal polishing composition of the present invention contains an oxidizing agent, the oxidizing agent is preferably mixed into the composition during polishing. 315816 14 200427827 Tips can be prepared with a high concentration of the aforementioned ingredients, which can be diluted with water and used during grinding. The metal polishing composition of the present invention is suitable for polishing the surface of a semiconductor substrate. The substrate is exposed to a low dielectric constant film on the surface of the substrate, as a cover film with a low dielectric constant, and as an interlayer insulation film between wirings. Any one of the film. In addition, the composition is preferably used for polishing the surface of a semiconductor substrate, on which a low dielectric constant film, a coverlay film, an interlayer insulating film, a copper cloth wire film, a barrier button or a nitride button film are exposed. ▲ The low dielectric constant film and the low dielectric constant protective film include, for example, inorganic films such as # FSG (fluorine-containing dioxygen), osmium (carbon-containing dioxygen), & ⑽ (nitrogen-containing outer SiC, SlN, and SiCN is made by CVD method; poly-organic rolled money films such as MSQ (methyl sesquioxane), HSQ (hydrogen sesquioxide and MHSQ (methyl hydride sesquioxane)) It is formed on the substrate by coating and firing; aromatic films such as PAE (polyarylpyrene and succinyl (diary oxide oxalate burned benzocyclobutene)); and organic films such as osmium and porous The interlayer film between the wirings polished by the metal polishing composition of the present invention includes, for example, a film of the thallium series, which is made by using a tetraethoxy stone pit (TE0S) or a material gas; the film is called a high-density film. Made of plasma; and BPSG film, in which the silicon dioxide film is doped with boron or phosphorus, etc. The metal polishing composition of the present invention is suitable for polishing semiconductor devices (such as LSI) with steel as wiring material on the surface, Barrier film for metal use, and degraded wettability with water as water-repellent surface as wiring room Low dielectric constant film of insulating film, or a layer film having a hydrophobic surface 315816 15 200427827 is formed on the low dielectric constant film to protect the low dielectric constant film, or the aforementioned thin layer and surface covering embodiments during the grinding process ... The surface will be described. The invention will be described with reference to the examples, but the invention is by no means the same as in Example 1 (the preparation of the composition) and the limits. At 0.3% by weight of oxidized stone, u weight of acid, 10 weight- Alkyl diphenyl ether diammonium dibasic acid, 4% by weight of hydrogen peroxide, and 00% by weight of benzotrisalyl, add water to a total of 1GG% by weight, and mix the materials. Add nitric acid to the mixture to pH 4 (hereinafter referred to as Composition 1)., Example 2 The wide composition was prepared in the same manner as in Example 丨, but the weight percent poly, ethynyl lauryl was tested-added step by step to The composition i to the total amount is just the weight, although the materials are mixed (hereinafter referred to as the composition 2). Example 3 A wide composition was prepared in the same manner as in Example 丨, but 0.1% by weight of polyoxyethylene Ethyl lauryl ether was added to the composition to a total amount of 〇〇〇wt%, The materials were mixed, and then ammonium hydroxide was added to the mixture to obtain pH 8.5 (hereinafter referred to as Composition 3). Example 4 The composition was prepared in the same manner as in Example 2, but with the additional addition of 0.04 Ammonium bioxalate was added to composition 2, the materials were mixed to a total weight of 100%, and then ammonium hydroxide was added to the mixture to obtain pH 8.5 (hereinafter referred to as composition 4). Comparative Example 1 16 315816 200427827 The composition is based on Example 1 was prepared in the same manner, but dibutylnaphthalenesulfonate with only one anionic functional group was used as an anionic surfactant to replace the dodecyldiphenyl crack.物 1). Comparative Example 2 The composition was prepared in the same manner as in Comparative Example 1, except that polyoxyethylene ethyl ys-naphthyl sodium acetate was used instead of dibutyl tsai salt (hereinafter referred to as Comparative Composition 2). . Comparative Example 3 The composition was prepared in the same way as in Comparative Example 1 except that polyoxyethylene tridecyl ether sulfate was used instead of dibutylnaphthalenesulfonate (hereinafter referred to as the comparative composition).物 3). Comparative Example 4 The composition was prepared in the same manner as in Example κ, but no surfactant was added (hereinafter referred to as Comparative Composition 4). Comparative Example 5 The composition was prepared in the same manner as in Example 1, except that a surfactant and ammonium nitrate were not added (hereinafter referred to as Comparative Composition 5). Experimental Example 1 Compositions 2, 3, and 4 and Comparative Compositions 2, 3, and 4 f 5 'were used to evaluate storage stability, polishing rate, and removal of adhesion to the low-dielectric-constant film, copper film, and group after polishing was completed. Removal efficiency of film abrasive particles 0 [Grinding conditions] 315816 17 200427827 Grinder: Leaf-type CMP device CMS-200M (manufactured by NuFlare Technology Co., Ltd.) Polishing pad: Polyurethane-based pad Panel speed: 78 rpm Rotating speed of the platform holding the wafer to be polished: 75 rpm Grinding pressure · 15 Kpa Grinding slurry flow rate: 150 ml / min Washing steps: light scrubbing, wrong brush scrubbing, giant wave silk, and using ultrapure water in this order Centrifugal dehydration. [Measurement of group film polishing rate]. 1d praises made! Continuing on the next day, the Japanese yen, grinding is performed according to the grinding conditions described above. Before and after grinding, the film thickness was measured with an electron microscope. The film thickness i before and after polishing is divided by the polishing time to determine the polishing rate. [Calculation of Particle Removal Rate] People use low-hanging film (Sac film) produced on Shixi wafer by CVD (chemical #vapor deposition) method, and copper produced on Shixi wafer by ore coating method Film, i = f plating method is used to produce a group of films on Mengjing® as a wafer to be polished, and the polishing conditions described in February | j are polished to attach the abrasive particles to the film. Wash Suba 5 wheat using a particle measurement device [WM-1500 (TOPCON (T〇PC〇N) :: Γ made)] on the wafer to determine the particle diameter of G. 2 microns or more adhesion side = H before And the number of particles adhered to the washing, the rate of removing particles by washing was obtained according to the following king formula. Method for calculating particle removal rate 315816] 8 200427827 Particle removal rate = — (number of adhered particles after washing) / (number of adhered particles before washing)] X 1 gg Before washing, the low dielectric constant film is derived from a metal abrasive. The number of particles is about 10,000 to 12,000. [Comparison of storage stability] In Compositions 1, 2, 3, and 4 and Comparative Compositions 1, 2, 3, 4, and 5, the abrasive particles were measured just after preparation and after leaving them to stand overnight (about 8 hours). The average particle diameter 'is used to evaluate the particle stability of each composition. Microtrack UPA manufactured by NIKKISO was used to determine the average particle diameter. 315816 19 200427827 Xue + Suitable Average particle diameter of abrasive particles after mixing (nanometer) Thin film particle removal ratio (%) Tantalum film grinding rate (Angstroms / minute) Sh 砘 P? Cn 5 *-σ \ D CP 〇 | Surfactant B * 3 逵 > IO oxalate (wt%> ammonium wall acid (wt%) oxidized oxide (wt%)) ㈠o P SiOC 00 KD ① LH VD cn \ D vr > cn 520 K1 〇 1— * 〇ο U) Composition 1 KΩ ① LH VD LP KD VD Office 640 Μ Μ Ο l · -1 〇ο Composition 2 H-1 ro VD LP 'vD LP V £) VD Mod 520 〇h -1 h-1 Ο Η ο ο u > Composition 3 μ kD KD KD KO VP Office 580 〇Ι- »I-1 ο 〇〇h-1 ο ο (jj Composition 4 Undetermined VD LP κΩ VD Ln KD KD U > 520 1— »〇ο ο U) Comparative composition 1 not determined but not determined 1 1 1 1 1 Μ Ο Ο-» ο ο Οϋ Comparative composition 2 not determined but not determined 1 1 1 1 1 hi 〇I— 1 ο ο LO Comparative composition 3 00 KD K) U) V £ > K) (-* KD 〇-o 563 h- > ο ο ϋϋ Comparative composition 4 00 00 ① ro VD Ln CD CO I—1 00 ro ο UJ Comparative composition 5 20 315816 / Ο Δ / / Ο Δ / colloidal silica, available from w · R · Ge Switzerland (w · m under the trade name "Ludox SM-30" by R_ Grace) , Average particle diameter · 7 naphthalene anionic surfactant, ammonium, with two ::: dialkyl diphenyl dicarboxylic acid di * 3 ^ and two anionic functional groups. Non-ionic surfactant 〇 and among them In the foregoing formula (11): lactamyl ethyl lauryl ether is a base,. Is lauryl as a hydrocarbon having 12 carbon atoms, 'η is 8', and z is chlorine. Lauryl Si boundary I = ('It is a polyoxyethylene ethyloxy nicotinyl group, & is 2, b 4, / nY is lauryl as / anion surfactant with a carbon number of 12 M, the pot system is ^ lice An anionic functional group, a monobutyl neonic acid and containing monoethyl / 5-naphthyl ether thioethyl tridecyl ether anionic surfactant, which is a polyoxyacid SI, salt and Contains an anionic functional group. "Anionic surfactant, which is a polyoxyethylene acetic acid naphthalene salt and contains an anionic functional group. The film has a high degree of particle removal energy. In addition, the grinding mill adhered to the production of T Moshan 3: No precipitation occurs after the 'excellent storage stability. In addition,' Subtract 4 'has excellent particle removal on the metal film after grinding. In contrast, an anionic active agent containing only one anionic functional group even when using an anionic interface In the case, the composition of the sub-surfactant 315816 2] 200427827 For example, comparing composition I, although the grinding rate and washing efficiency are similar to compositions 1 to 4, after preparation, the abrasive particles are aggregated and the aggregates are precipitated. It has storage stability problems. In comparison to Compositions 2 and 3, which uses an anionic surfactant with an anionic functional group, the abrasive abrasive aggregates, and the aggregates precipitate, so the storage stability is insufficient. In addition, it does not contain a surfactant Comparative composition 4 'due to poor wettability between the low dielectric constant films, the surface immediately dried, so the subsequent washing efficiency was insufficient; Compared with the nitrate-free comparative composition 5, the grinding rate of the button is low. According to this & month * for _ a kind of metal grinding composition, the composition can grind copper and samarium metal at a high speed. Good: And the number of hanging: first son / month will not sink in the temple abrasive abrasive. 315816