TW200915411A - Polishing liquid and polishing method - Google Patents

Abstract

A polishing liquid which is used for chemical mechanical polishing in a planarization process of a semiconductor integrated circuit having a barrier layer, the polishing liquid including (A) colloidal silica particles, (B) a hydrophilic benzotriazole derivative, (C) a hydrophobic benzotriazole derivative, and (D) an oxidizing agent.

Description

200915411 九、發明說明： 【發明所屬之技術領域】 本發明涉及使用於半導體積體電路的製程之硏磨液及 硏磨方法，更詳言之，涉及半導體積體電路的配線步驟之 平坦化中，用於化學機械硏磨之硏磨液及硏磨方法。 【先前技術】 以半導體積體電路（下稱LSI)爲代表之半導體元件的開 發中，爲實現小型化·高速化，有高密度化·高積體化之 推進。因此，近年來對於配線之微細化及積層化的要求愈 來愈高。 製造LSI等半導體積體電路之際，有多層微細配線之形 成，於該各層形成Cu等的金屬配線之際，一般係預先形成 Ta、TaN、Ti、ΤιΝ等阻障金屬。阻障層係爲防止配線材料 往層間絕緣膜（以下或稱「絕緣層」）擴散，或提升配線材 料之密著性而設置。 此金屬配線的形成當中，使用到化學機械硏磨（Chemical Mechanical Polishing，以下或稱“ CMP”）等種種技術。 此CMP係進行絕緣層等之表面平坦化、插塞之形成、埋 沒金屬配線之形成等時之必要技術。基板之平滑化，形成 配線時多餘金屬薄膜之去除、多餘阻障層之去除，係藉由 C Μ P進行。 用於CMP之金屬用硏磨液一般含砥粒（例如氧化鋁、矽 石）與氧化劑（例如過氧化氫、過硫酸）。基本上，其機制應 係金屬表面因氧化劑而氧化’藉砥粒去除該氧化皮膜進行 200915411 硏磨。 CMP之一般方法係貼附硏磨墊於圓形硏磨平台（piaten) 上’以硏磨液浸潤硏磨墊表面，將基板（晶圓）表面按抵於 硏磨墊，自其背面施加特定壓力（硏磨壓力）之狀態下，使 硏磨平台及基板皆旋轉，藉由所產生之機械摩擦將基板表 面平坦化。 爲形成各配線層，一般大致分二階段進行硏磨。 第一階段之硏磨係以CMP去除經鍍敷法等形成之多餘 金屬配線材。以下稱多餘金屬配線材之金屬膜去除步驟爲 「金屬膜CMP」。金屬膜CMP係於1段或經多段施行。 第二階段之硏磨係以CMP去除經第一階段硏磨而露出 表面之該阻障金屬，更進行絕緣層等之表面平坦化。以下 稱此硏磨步驟爲「阻障金屬CMP」。阻障金屬CMP係於1 段或經多段施行。 亦即’該阻障金屬C Μ P主要係同時硏磨金屬配線材與阻 障金屬，將表面平坦化。 此時’使用含固體砥粒之該硏磨液進行阻障金屬cΜΡ 則配線部被快速硏磨，會發生凹陷、侵飽。 因此’於該阻障金屬CMP有調整金屬配線部之硏磨速度 與阻障金屬部之硏磨速度，最終形成凹陷、侵鈾等落差少 之配線層的要求。 亦即，不發生凹陷、侵蝕而能提高絕緣層之硏磨速度至 約略等同於金屬配線材之硏磨速度受到期待。 此外尙有以下其它問題：因使用含有固體砥粒之硏磨 200915411 液，硏磨後，爲去除殘留在半導體面之硏磨液，通常施行 之洗淨步驟複雜，並且，爲處理該洗淨後之液體（廢液）， 必須將固體砥粒沈降分離，因此成本高。 至於如此之含有固體砥粒的硏磨液，已有如下之種種探 討。 各有例如，高速硏磨而幾無硏磨損傷發生之CMP硏磨劑 及硏磨方法（參考例如專利文獻1 )，提升CMP之洗淨性的 硏磨組成物及硏磨方法（參考例如專利文獻2)，以及，防止 硏磨砥粒凝集之硏磨用組成物（參考例如專利文獻3)的提 議。 然而現況，雖有如上之硏磨液，在硏磨阻障層之際，可 充分抑制凹陷、侵蝕之發生的技術尙未可得。 專利文獻1特開2003 - 1 7446號公報 專利文獻2特開2003 - 1 424 35號公報 專利文獻3特開2000-8483 2號公報 【發明內容】 發明所欲解決之課題 本發明之目的在提供具有阻障層之半導體積體電路@ 平坦化步驟中，用於化學機械硏磨之含固體砥粒的硏磨 液，可抑制凹陷及侵蝕之發生的硏磨液及硏磨方法。 用以解決課題之手段 本發明人作了精心探討，結果發現使用下述硏磨液即可 解決該課題。 本發明之硏磨液係用於具有阻障層之半導體積體電足各 200915411 的平坦化步驟中之化學機械硏磨的硏磨液，其特徵爲含有 (A)膠體矽石粒子、（B )親水性之苯并***衍生物、（C )疏水 性之苯并***衍生物及（D)氧化劑。 該（B)親水性之苯并***衍生物係以具有羥基、胺基、羧 基或磺酸基爲佳。 該（C)疏水性之苯并***衍生物係以具有非取代之烷 基、碳原子數10以上之烷氧基、碳原子數15以上之烷氧 羰基、碳原子數15以上之羰醯胺基或碳原子數15以上之 胺羰基爲合適。 本發明之硏磨液更以含有胺基酸爲佳，含有水溶性高分 子亦係一合適樣態。 本發明中，（B)親水性之苯并***衍生物與（C)疏水性之 苯并***衍生物之合計濃度係以0.005質量％以上且5質量 %以下爲合適。 (B)親水性之苯并***衍生物與（C)疏水性之苯并***衍 生物之含有比率以係質量比2 : 1〜1 : 5爲合適。 本發明之硏磨液其pH係以2〜5爲佳。 本發明之硏磨方法係，使用含有（A)膠體矽石粒子、（B) 親水性之苯并***衍生物、（C)疏水性之苯并***衍生物及 (D)氧化劑之硏磨液，化學機械硏磨具備阻障層之半導體積 體電路的硏磨方法。 本發明之硏磨方法適用於任何阻障層之硏磨，較佳者爲 以Mn、Ti、Ru或該等之衍生物形成的該阻障層之硏磨；於 如此之阻障層，本發明亦可奏效。 200915411 發明效果 依本發明可提供，具有阻障層之半導體積體電路的平坦 化步驟中’用於化學機械硏磨之使用固體砥粒的硏磨液， 可抑制凹陷及侵蝕之硏磨液及硏磨方法。 【實施方式】 以下說明本發明之具體樣態。 本發明之硏磨液，係用以化學機械硏磨半導體積體電路 的阻障層之硏磨液，其特徵爲含有（A)膠體矽石粒子、（B) 親水性之苯并***衍生物、（C)疏水性之苯并***衍生物及 (D)氧化劑’必要時亦可含任意成分。本發明之硏磨液所含 有之各成分可以1種單獨使用，亦可倂用2種以上。 以下或稱（B)「親水性之苯并***衍生物」爲「親水性苯 並***衍生物」或「親水性B T A衍生物」。（C)「疏水性之 苯并***衍生物」亦或稱爲「疏水性苯并***衍生物」或 「疏水性BTA衍生物」。 本發明中，「硏磨液」不僅指使用於硏磨之際的硏磨液 (亦即必要時經稀釋之硏磨液），亦指硏磨液之濃縮液。 濃縮液或經濃縮之硏磨液指調製成溶質濃度高於使用 在硏磨之際的硏磨液者；使用於硏磨之際者係以水或水溶 液等稀釋，用於硏磨者。稀釋倍率一般係1~20倍體積。本 說明書中’「濃縮」及「濃縮液」係用以指比使用狀態「濃」 及該「較濃之液」而作慣用表達，其用法異於伴隨蒸發等 物理濃縮操作之一般用語。 以下詳細說明構成本發明之硏磨液的各成分。 200915411 (A)膠體矽石粒子 使用於本發明之硏磨液含有膠體矽石粒子做爲構成成 分。膠體矽石粒子係做爲硏磨粒子（砥粒）。 該膠體矽石粒子之製法可係經由溶膠凝膠法的例如 Si(OC2H5)4、Si(sec-OC4H9)4、Si(OCH3)4、Si(OC4H小等烷氧 化矽化合物的水解。如此之第1、第2膠體粒子（例如第1、 第2膠體矽石粒子）粒度分佈非常尖銳。 所含之膠體矽石粒子的平均粒徑係以5〜60nm爲佳， 5〜30nm更佳，20~50nm尤佳。爲達充分之硏磨加工速度， 以5nm以上之粒子爲佳。爲使硏磨加工中不產生過剩的摩 擦熱，粒徑以60nm以下爲佳。 於此，平均粒徑指硏磨液中以漿體狀配合之狀態下，使 用於硏磨前的粒子之平均粒徑。膠體矽石粒子之物性特性 上，因配合前之膠體矽石粒子的平均粒徑與存在於硏磨液 中之粒子的平均粒徑大約一致，可測定配合前之狀態下的 平均粒徑，做爲硏磨液中的粒子之平均粒徑。 此膠體矽石粒子之粒徑係以SEM(掃瞄電子顯微鏡）觀測 硏磨粒子時，構成1粒子的最小構成粒徑之測定値。 所用之膠體矽石粒子可係僅只1種，亦可倂用2種以 上。倂用時，從可達高硏磨速度之觀點，係以倂用粒徑或 形狀不同之2種以上的膠體粒子爲佳。 不同粒徑之組合者，例如平均粒徑30〜100nm之大粒徑 矽石與平均粒徑 20 ~60nm之小粒徑矽石，以質量比1 : 10〜10: 1倂用，即可提升對於各類膜之硏磨速度。 -10- 200915411 形狀不同之粒子，例如近乎真球之球形矽石，與長徑與 短徑的比（長徑/短徑）爲1.2~5.0之非真球形粒子、繭形矽石 粒子等，以質量比1 : 1 〇~ 10 : 1倂用，尤可提升對於絕緣 膜之硏磨速度。 具體而言，有例如，平均粒徑l〇~50nm左右之球形矽石 微粒子，與長徑爲50nm之長徑/短徑比=1~5之非真球形矽 石微粒子之組合等。 如此之非真球形膠體矽石粒子詳如特願2005- 3 667 1 2所 述，該記載亦適用於本案。 含膠體矽石粒子之硏磨粒子的濃度，係以使用時之硏磨 液總量的0.5〜15質量％爲佳，1〜10質量％更佳。在此範圍 則可達充分之硏磨加工速度，且硏磨加工中過剩摩擦熱之 產生可予抑制故較佳。 硏磨粒子（砥粒）亦可含膠體矽石粒子以外者，有例如煙 霧矽石、氧化鈽、氧化鋁、氧化鈦等。可是，此時全部砥 粒中（A)膠體矽石粒子之含有比率係50質量％以上，80質 量％以上更佳。所含之砥粒亦可全係（A)膠體矽石粒子。 <苯并***衍生物> 本發明中，（B)親水性苯并***衍生物與（C)疏水性苯并 ***衍生物係所謂腐蝕抑制劑，吸附於被硏磨表面形成皮 膜，控制金屬表面之腐蝕。 本發明中，尤因倂用（B)親水性苯并***衍生物與（C)疏 水性苯并***衍生物，可得良好之落差特性。其機制尙不 明確，但應係隨落差之進展因各苯并***之協同作用而該 -11 - 200915411 落差不再擴大；更具體而言，可預期親水性苯幷三@、疏 水性苯并***於落差凹凸部之吸附容易度、腐蝕抑制能力 各有不同。推測應係由於此機制，凹陷與侵蝕之發生受到 抑制。唯本發明不受限於該推測。 (B)親水性苯并***衍生物 本發明之（B)親水性苯并***衍生物若呈親水性即無其 它特殊限制，較佳者具有1以上之親水性基做爲取代基。 本發明之親水性苯并***係定義爲，在室溫（25 °C )下於 水100g中可溶解2g以上者。 親水性之苯并***衍生物之親水性基係以胺甲醯基、昨 唑基、羧基、草醯基、草醯胺醯基、氰基、伸亞胺醯基、 甲醯基、羥基、烷氧基、芳氧基、胺基、（烷基、芳基或雜 環）fee基、酿fee基、礦醯胺基 '脲基、.硫服基、酸亞胺基、 (烷氧或芳氧）羰胺基、胺磺醯胺基、半卡肼基、硫半卡肼 基、肼基、銨基、草醯胺醯胺基、硝基、含四級化氮原子 之雜環基（例如吡錠基、咪銼基、喹啉鑰基、異喹啉鑰基）、 異氰基、亞胺基、锍基、（烷基、芳基或雜環）硫基、（烷基、 方基或雜環）一硫基、（院基或芳基）擴驢基 '(院基或芳基） 亞擴醯基、礎酸基、胺磺酿基、膦基、滕醒基、膦醯氧基、 膦醯胺基、矽烷基等爲佳，羥基、胺基、羧基、磺酸基更 佳，羥基、胺基、羧基尤佳。 該親水性基之胺基可係一級、二級、三級中任一之胺 基，從可充分抑制能力之觀點，以一級或二級胺基爲佳， 一級者尤佳。 -12- 200915411 從可得充分抑制能力之觀點，親水性苯并***衍生物所 具之親水性基的數量係以1〜3個爲佳，1、2個更佳。 親水性之苯并***衍生物中以親水性基取代之位置不 特定，而當親水性基之個數爲3時，以1位、3位、4位係 親水性基爲佳，親水性基之個數爲2時，以1位及3位或3 位及4位係親水性基爲佳，親水性基之個數爲1時，以1 位或3位係親水性基爲佳。 以下具體例示（B)親水性之苯并***衍生物，而本發明不 限於這些。 B1 B2 B3 B4BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a honing liquid and a honing method for a process of a semiconductor integrated circuit, and more particularly to a planarization of a wiring step of a semiconductor integrated circuit. , honing liquid and honing method for chemical mechanical honing. [Prior Art] In the development of semiconductor devices typified by a semiconductor integrated circuit (hereinafter referred to as LSI), in order to achieve miniaturization and high speed, there is a need for higher density and higher integration. Therefore, in recent years, there has been an increasing demand for miniaturization and stratification of wiring. When a semiconductor integrated circuit such as an LSI is manufactured, a plurality of fine wirings are formed, and when metal wiring such as Cu is formed in each layer, barrier metals such as Ta, TaN, Ti, and Τι are generally formed in advance. The barrier layer is provided to prevent the wiring material from diffusing to the interlayer insulating film (hereinafter referred to as "insulating layer") or to improve the adhesion of the wiring material. Among the formation of the metal wiring, various techniques such as chemical mechanical polishing (hereinafter referred to as "CMP") are used. This CMP is a technique necessary for planarizing the surface of an insulating layer or the like, forming a plug, and forming a buried metal wiring. The smoothing of the substrate, the removal of excess metal film during wiring formation, and the removal of excess barrier layer are performed by C Μ P. The honing liquid for metal used in CMP generally contains cerium particles (e.g., alumina, vermiculite) and an oxidizing agent (e.g., hydrogen peroxide, persulfuric acid). Basically, the mechanism should be that the metal surface is oxidized by the oxidant. The oxidized film is removed by the granules for 200915411 honing. The general method of CMP is to attach a honing pad to the circular honing platform (piaten) to wet the surface of the honing pad with honing liquid, and press the surface of the substrate (wafer) against the honing pad to apply specificity from the back side. In the state of pressure (honing pressure), both the honing platform and the substrate are rotated, and the surface of the substrate is flattened by the mechanical friction generated. In order to form each wiring layer, honing is generally performed in two stages. The first stage of honing is to remove excess metal wiring material formed by plating or the like by CMP. Hereinafter, the metal film removing step of the excess metal wiring material is referred to as "metal film CMP". The metal film CMP is applied in one stage or in multiple stages. The honing of the second stage is to remove the barrier metal exposed by the first stage honing by CMP, and to planarize the surface of the insulating layer or the like. Hereinafter, the honing step is referred to as "barrier metal CMP". Barrier metal CMP is applied in 1 segment or in multiple segments. That is, the barrier metal C Μ P mainly hones the metal wiring material and the barrier metal at the same time to planarize the surface. At this time, when the barrier metal is used by using the honing liquid containing solid cerium particles, the wiring portion is quickly honed, and dents and fullness are generated. Therefore, in the barrier metal CMP, the honing speed of the metal wiring portion and the honing speed of the barrier metal portion are adjusted to finally form a wiring layer having a small drop such as a recess or uranium. That is, it is expected that the honing speed of the insulating layer can be increased without causing depression or erosion to approximately equal to the honing speed of the metal wiring member. In addition, there are other problems as follows: the use of honing 200915411 liquid containing solid cerium particles, after honing, in order to remove the honing liquid remaining on the semiconductor surface, the usual washing step is complicated, and, after processing the cleaning The liquid (waste liquid) must be separated and settled by solid granules, so the cost is high. As for such a honing liquid containing solid cerium particles, the following various investigations have been made. Each of the CMP honing agent and the honing method (for example, Patent Document 1) which has high-speed honing and has no honing damage, for example, a honing composition for improving the detergency of CMP and a honing method (refer to, for example, a patent) Document 2), and a proposal for preventing a honing composition for honing agglomerated granules (refer to, for example, Patent Document 3). However, in the current situation, although the honing liquid is as described above, the technique for sufficiently suppressing the occurrence of dents and erosion at the time of honing the barrier layer is not available. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2003-A No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. Publication No Semiconductor integrated circuit with barrier layer @ In the planarization step, the honing liquid containing solid cerium particles for chemical mechanical honing can suppress honing liquid and honing method for occurrence of dent and erosion. Means for Solving the Problems The present inventors conducted intensive studies and found that the following problems can be solved by using the following honing liquid. The honing fluid of the present invention is used in a chemical mechanical honing honing liquid in the planarization step of the semiconductor integrated body of each of the barrier layers, 200915411, characterized in that it contains (A) colloidal vermiculite particles, (B) a hydrophilic benzotriazole derivative, (C) a hydrophobic benzotriazole derivative, and (D) an oxidizing agent. The (B) hydrophilic benzotriazole derivative preferably has a hydroxyl group, an amine group, a carboxyl group or a sulfonic acid group. The (C) hydrophobic benzotriazole derivative is an carbonyl group having an unsubstituted alkyl group, an alkoxy group having 10 or more carbon atoms, an alkoxycarbonyl group having 15 or more carbon atoms, and 15 or more carbon atoms. An amine group or an amine carbonyl group having 15 or more carbon atoms is suitable. The honing liquid of the present invention preferably contains an amino acid, and a water-soluble polymer is also suitable. In the present invention, the total concentration of the (B) hydrophilic benzotriazole derivative and the (C) hydrophobic benzotriazole derivative is preferably 0.005% by mass or more and 5% by mass or less. (B) The content ratio of the hydrophilic benzotriazole derivative to the (C) hydrophobic benzotriazole derivative is suitably in a mass ratio of 2:1 to 1:5. The honing liquid of the present invention preferably has a pH of 2 to 5. The honing method of the present invention uses a crucible containing (A) colloidal vermiculite particles, (B) a hydrophilic benzotriazole derivative, (C) a hydrophobic benzotriazole derivative, and (D) an oxidizing agent. Grinding, chemical mechanical honing of a semiconductor integrated circuit with a barrier layer. The honing method of the present invention is applicable to the honing of any barrier layer, preferably the honing of the barrier layer formed of Mn, Ti, Ru or the like; in such a barrier layer, The invention can also work. 200915411 Effects of the Invention According to the present invention, in the planarization step of a semiconductor integrated circuit having a barrier layer, a honing liquid using solid cerium particles for chemical mechanical honing can suppress dents and erosive honing liquid and Honing method. [Embodiment] Hereinafter, specific aspects of the invention will be described. The honing fluid of the present invention is a honing fluid for chemically mechanically honing a barrier layer of a semiconductor integrated circuit, characterized by containing (A) colloidal vermiculite particles, and (B) hydrophilic benzotriazole derivative. The (C) hydrophobic benzotriazole derivative and (D) the oxidizing agent may optionally contain optional components. The components contained in the honing liquid of the present invention may be used alone or in combination of two or more. Hereinafter, (B) "hydrophilic benzotriazole derivative" is a "hydrophilic benzotriazole derivative" or a "hydrophilic B T A derivative". (C) "Hydrophobic benzotriazole derivative" is also called "hydrophobic benzotriazole derivative" or "hydrophobic BTA derivative". In the present invention, the "honing fluid" refers not only to the honing liquid used in the honing (i.e., the honing liquid which is diluted if necessary), but also to the concentrated liquid of the honing liquid. Concentrates or concentrated honing fluids are formulated to have a higher solute concentration than those used in honing; those used for honing are diluted with water or water solutions for use in honing. The dilution ratio is generally 1 to 20 times the volume. In the present specification, "concentration" and "concentrate" are used to refer to the "concentrated" and "concentrated liquid" in the use state, and their usage is different from the general term accompanying physical concentration operations such as evaporation. The components constituting the honing liquid of the present invention will be described in detail below. 200915411 (A) Colloidal vermiculite particles The honing liquid used in the present invention contains colloidal vermiculite particles as a constituent component. The colloidal vermiculite particles are used as honing particles (granules). The colloidal vermiculite particles can be produced by a sol-gel method such as Si(OC2H5)4, Si(sec-OC4H9)4, Si(OCH3)4, Si (hydrolysis of an alkoxylated alkoxide compound such as OC4H). The particle size distribution of the first and second colloidal particles (for example, the first and second colloidal vermiculite particles) is very sharp. The average particle diameter of the colloidal vermiculite particles is preferably 5 to 60 nm, more preferably 5 to 30 nm, and 20 It is preferable to use a particle of 5 nm or more in order to achieve a sufficient honing processing speed. In order to prevent excessive frictional heat during honing, the particle diameter is preferably 60 nm or less. The average particle size of the particles before honing in a state in which the honing liquid is in a slurry form. The physical properties of the colloidal vermiculite particles are due to the average particle size of the colloidal vermiculite particles before the mixing. The average particle diameter of the particles in the grinding liquid is approximately the same, and the average particle diameter in the state before the compounding can be determined as the average particle diameter of the particles in the honing liquid. The particle size of the colloidal vermiculite particles is SEM (scan) Measurement of the minimum constituent particle size of one particle when observing honing particles The colloidal vermiculite particles to be used may be used alone or in combination of two or more. When used, from the viewpoint of achieving high honing speed, two or more kinds of colloids having different particle diameters or shapes may be used. Particles are preferred. Combinations of different particle sizes, such as large particle size vermiculite with an average particle diameter of 30 to 100 nm and small particle size vermiculite with an average particle diameter of 20 to 60 nm, with a mass ratio of 1:10 to 10:1. , can improve the honing speed of various types of membranes. -10- 200915411 Particles with different shapes, such as spherical vermiculite near the true sphere, and the ratio of long diameter to short diameter (long diameter / short diameter) is 1.2~5.0 The non-true spherical particles, the samarium-shaped vermiculite particles, and the like are used in a mass ratio of 1: 1 〇 to 10:1 Å, and the honing speed for the insulating film can be particularly improved. Specifically, for example, the average particle diameter l〇 A combination of spherical vermiculite particles of about 50 nm and non-true spherical vermiculite particles having a long diameter/short diameter ratio of 50 nm of a long diameter of 50 nm, etc. Such a non-true spherical colloidal meteorite particle is detailed as a wish 2005 - 3 667 1 2, the description also applies to this case. The concentration of honing particles containing colloidal vermiculite particles is used The total amount of the honing liquid is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass. In this range, the honing processing speed can be sufficiently obtained, and the generation of excessive friction heat in the honing process can be suppressed. The honing particles (granules) may also contain colloidal vermiculite particles, such as smoky quartz, cerium oxide, aluminum oxide, titanium oxide, etc. However, at this time, all of the cerium particles (A) colloidal vermiculite particles The content ratio is preferably 50% by mass or more, more preferably 80% by mass or more, and the cerium particles contained therein may be all (A) colloidal vermiculite particles. <Benzenetriazole derivative> In the present invention, (B) The hydrophilic benzotriazole derivative and (C) a hydrophobic benzotriazole derivative are so-called corrosion inhibitors which are adsorbed on the surface to be honed to form a film to control corrosion of the metal surface. In the present invention, Ewing uses (B) a hydrophilic benzotriazole derivative and (C) a hydrophobic benzotriazole derivative to obtain a good drop characteristic. The mechanism is not clear, but it should be due to the synergy of each benzotriazole. The -11 - 200915411 gap will not expand; more specifically, hydrophilic benzoquinone @, hydrophobic benzene can be expected The ease of adsorption and corrosion inhibition ability of the triazole in the uneven portion are different. It is speculated that due to this mechanism, the occurrence of depressions and erosion is suppressed. The invention is not limited to this speculation. (B) Hydrophilic benzotriazole derivative The (B) hydrophilic benzotriazole derivative of the present invention is hydrophilic, that is, it is not particularly limited, and preferably has one or more hydrophilic groups as a substituent. The hydrophilic benzotriazole system of the present invention is defined as those which can dissolve 2 g or more in 100 g of water at room temperature (25 ° C). The hydrophilic group of the hydrophilic benzotriazole derivative is an amine methyl sulfonyl group, a oxazolyl group, a carboxyl group, a oxalyl group, a sulfhydryl sulfhydryl group, a cyano group, an imindolyl group, a decyl group, a hydroxy group. , alkoxy, aryloxy, amine, (alkyl, aryl or heterocyclic) feel, styrene, orthoamine, ureido, thiol, acid imine, (alkoxy) Or aryloxy)carbonylamino, amidoxime, hemocyanyl, thiosuccinyl, fluorenyl, ammonium, oxalylamine, nitro, heterocyclic ring containing a quaternary nitrogen atom Base (eg, pyridinyl, imidazolyl, quinoline, isoquinolyl), isocyano, imido, fluorenyl, (alkyl, aryl or heterocyclic)thio, (alkyl , aryl or heterocyclic) thiol, (hospital or aryl) thiol' (hospital or aryl) sub-alkyl, sulfhydryl, sulfonyl, phosphino, decyl, phosphine The oxy group, the phosphonium amino group, the decylalkyl group and the like are preferred, and the hydroxy group, the amine group, the carboxyl group and the sulfonic acid group are more preferred, and the hydroxyl group, the amine group and the carboxyl group are particularly preferred. The amine group of the hydrophilic group may be an amine group of any of the first, second or third stages, and a primary or secondary amine group is preferred from the viewpoint of sufficiently inhibiting the ability, and the first grade is particularly preferred. -12- 200915411 The hydrophilic benzotriazole derivative has a hydrophilic group of 1 to 3, preferably 1 or 2, from the viewpoint of sufficient suppression ability. The position of the hydrophilic benzotriazole derivative substituted with a hydrophilic group is not specific, and when the number of the hydrophilic groups is 3, the hydrophilic group at the 1st, 3rd, and 4th positions is preferred, and hydrophilicity is preferred. When the number of the base is 2, the hydrophilic group is preferably a 1-position or a 3-position or a 3-position or a 4-position. When the number of the hydrophilic groups is 1, the hydrophilic group at the 1-position or the 3-position is preferred. The (B) hydrophilic benzotriazole derivative is specifically exemplified below, and the present invention is not limited to these. B1 B2 B3 B4

從良好控制凹陷、侵蝕之觀點’親水性之苯并***衍生物 之添加量係以相對於使用於硏磨之際的硏磨液質量0.0001 質量％以上且3質量％以下爲佳’0·005質量％以上且1質量 %以下更佳。 (C)疏水性苯幷***衍生物 疏水性苯幷***衍生物若呈疏水性即無其它特殊限 制，包含無取代基之苯并***，但以係具有下述取代基之 -13- 200915411 苯并***爲佳。 本發明之疏水性苯并***係定義爲在室溫（25 t：)下於水 100ml可溶解不到2g者。 疏水性苯并***衍生物中之取代基係以非取代之烷 基、碳原子數10以上之烷氧基、碳原子數15以上之烷氧 羰基、碳原子數15以上之羰醯胺基或碳原子數15以上之 胺羰基、烯基、環烷基、芳基爲佳，非取代之烷基、碳原 / 子數10以上之烷氧基、碳原子數15以上之烷氧羰基、碳 原子數15以上之羰醯胺基或碳原子數15以上之胺羰基、 環烷基、芳基更佳，非取代之烷基、碳原子數1 0以上之烷 氧基、碳原子數15以上之烷氧羰基、碳原子數15以上之 羰醯胺基或碳原子數15以上之胺羰基尤佳。 疏水性苯并***衍生物之非取代烷基可係直鏈、分枝、 環狀的任一，以直鏈烷基爲較佳。 非取代烷基係以碳原子數1~1〇之烷基爲佳，碳原子數 ί1~5之烷基更佳，碳原子數1~3之烷基尤佳。 疏水性苯并***衍生物之碳原子數丨〇以上的烷氧基係 以碳原子數10〜30之烷氧基爲佳’碳原子數10〜20之烷氧 基更佳。 疏水性苯并***衍生物的碳原子數1 5以上之烷氧羰基 係以碳原子數15~30之烷氧羰基爲佳’碳原子數15〜20之 烷氧羰基更佳。 疏水性苯并三哩衍生物的碳原子數1 5以上之羯酿目女基 係以碳原子數15〜30之羰醯胺基爲佳’碳原子數15~20之 -14- 200915411 羰醯胺基更佳。 疏水性苯并***衍生物的碳原子數1以上之胺羰基係以 碳原子數1~1〇之胺羰基爲佳，碳原子數1~5之胺羰基更佳。 這些取代基之中係以非取代之烷基爲佳。 從良好控制凹陷、侵蝕之觀點，疏水性苯并***衍生物 所具之取代基數量係以1〜3個爲佳，1、2個更佳。 疏水性苯并***衍生物中，由該取代基取代之位置不特 定，當取代基之個數爲3時，以1位、3位、4位係由取代 基取代爲佳，取代基之個數爲2時，以丨位及3位或3位 及4位係由取代基取代爲佳，取代基之個數爲1時，以^ 位或3位係由取代基取代爲佳。 以下具體例不（C)疏水性苯幷3唑衍生物，而本發明不限 於這些。 -15- 200915411The amount of the hydrophilic benzotriazole derivative added is preferably 0.0001% by mass or more and 3% by mass or less based on the mass of the honing liquid used for honing from the viewpoint of good control of the depression and erosion. More preferably, it is 005 mass% or more and 1 mass% or less. (C) Hydrophobic benzotriazole derivative The hydrophobic benzotriazole derivative is hydrophobic, that is, without any particular limitation, and contains an unsubstituted benzotriazole, but has a substituent of the following-13 - 200915411 Benzotriazole is preferred. The hydrophobic benzotriazole system of the present invention is defined as being soluble in water of 100 ml at room temperature (25 t:) in an amount of less than 2 g. The substituent in the hydrophobic benzotriazole derivative is an unsubstituted alkyl group, an alkoxy group having 10 or more carbon atoms, an alkoxycarbonyl group having 15 or more carbon atoms, and a carbonyl hydrazine group having 15 or more carbon atoms. Or an amine carbonyl group, an alkenyl group, a cycloalkyl group or an aryl group having 15 or more carbon atoms, preferably an unsubstituted alkyl group, an alkoxy group having a carbon number of 10 or more, an alkoxycarbonyl group having 15 or more carbon atoms, A carbonyl hydrazine group having 15 or more carbon atoms or an amine carbonyl group having 15 or more carbon atoms, a cycloalkyl group or an aryl group, an unsubstituted alkyl group, an alkoxy group having 1 or more carbon atoms, and 15 carbon atoms. The above alkoxycarbonyl group, a carbonyl hydrazine group having 15 or more carbon atoms or an amine carbonyl group having 15 or more carbon atoms is particularly preferable. The unsubstituted alkyl group of the hydrophobic benzotriazole derivative may be any of a straight chain, a branched chain, and a cyclic group, and a linear alkyl group is preferred. The unsubstituted alkyl group is preferably an alkyl group having 1 to 1 ring of carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. The alkoxy group having a carbon number of 丨〇 or more in the hydrophobic benzotriazole derivative is preferably an alkoxy group having 10 to 30 carbon atoms, and more preferably an alkoxy group having 10 to 20 carbon atoms. The alkoxycarbonyl group having a carbon number of 15 or more in the hydrophobic benzotriazole derivative is preferably an alkoxycarbonyl group having 15 to 30 carbon atoms, and more preferably an alkoxycarbonyl group having 15 to 20 carbon atoms. The hydrophobic benzotriazine derivative has a carbon number of 15 or more, and the fluorenylamine group having a carbon number of 15 to 30 is preferably a carbon atom number of 15 to 20-14-200915411 carbonyl hydrazine. The amine group is more preferred. The amine carbonyl group having 1 or more carbon atoms of the hydrophobic benzotriazole derivative is preferably an amine carbonyl group having 1 to 1 carbon atom, and more preferably an amine carbonyl group having 1 to 5 carbon atoms. Among these substituents, an unsubstituted alkyl group is preferred. From the viewpoint of good control of depression and erosion, the number of substituents of the hydrophobic benzotriazole derivative is preferably from 1 to 3, more preferably 1, two. In the hydrophobic benzotriazole derivative, the position substituted by the substituent is not specific, and when the number of the substituent is 3, it is preferably substituted with a substituent at the 1-, 3-, and 4-positions, and the substituent is preferably substituted. When the number of the substituents is 2, it is preferred that the substituents and the 3 or 3 and 4 positions are substituted by a substituent. When the number of the substituents is 1, it is preferred to substitute the substituents at the 3-position or the 3-position. The following specific examples are not (C) hydrophobic benzoquinone triazole derivatives, and the present invention is not limited to these. -15- 200915411

0C12H25 C9 C80C12H25 C9 C8

CibH31~~c~HN ° XX} —to C10CibH31~~c~HN ° XX} —to C10

C18H37一N一OC H 從良好控制凹陷、侵飩之觀點，疏水性苯并***衍生物 I 之添加量係以相對於使用於硏磨之際的硏磨液質量0.000 1 質量％以上且3質量％以下爲佳，0.005質量％以上且1質量 %以下更佳。 (B)親水性之苯并三哗衍生物與（c)疏水性苯并三哗衍生 物之合計濃度，係以相對於'使用於硏磨之際的硏磨液0.0 0 5 質量％以上且5質量％以下爲佳，0.01質量％以上且3質量 %以下更佳，0 · 0 3質量％以上且1質量％以下尤佳。 從良好控制凹陷、侵触之觀點，（B)親水性之苯并***衍 -16- 200915411 2: 1~1: 5爲佳，3: 2〜1: 5更佳，1: 1〜1: 5尤佳。 於本發明之硏磨液亦可倂用（B)親水性之苯并***衍生 物及（C)疏水性苯并***衍生物，並含有其它吡咯化合物。 相對於使用在硏磨之際的硏磨液中之全部苯并***，（B) 親水性之苯并***衍生物及（C)疏水性苯并***衍生物之 含有率可係50質量％ ~100質量％，60質量％〜90質量％較 佳，7 0質量％ ~ 9 0質量％更佳。 該其它吡咯衍生物可係甲苯***、1-(1,2-二羧乙基）甲苯 ***、1-[N，N-雙（羥乙基）胺甲基]甲苯***等***衍生物， 咪唑、1，2,3-***、1,2,4-***、四唑等母核大不相同之一 般習知腐蝕抑制劑及該等之衍生物，其中以1，2,3 -***、 1，2，4 -三哩、四α坐爲較佳。 (D)氧化劑 本發明之硏磨液含有可氧化硏磨對象金屬之氧化劑。 作爲氧化劑可舉出例如，過氧化氫、過氧化物、硝酸鹽、 碘酸鹽、過碘酸鹽、次亞氯酸鹽、亞氯酸鹽、氯酸鹽、過 氯酸鹽、過硫酸鹽、重鉻酸鹽、過錳酸鹽、臭氧水及銀（Π) 鹽、鐵（III)鹽。 作爲鐵（III)鹽適用者有例如硝酸鐵（III)、氯化鐵（III)、 硫酸鐵（111 )、溴化鐵（III)等無機鐵（πI)鹽，鐵（III)之有機錯 鹽。 使用鐵（III)之有機錯鹽時，構成鐵（III)錯鹽之配位化合 物者有例如乙酸、檸檬酸、草酸、柳酸、二乙二硫胺甲酸、 琥珀酸、酒石酸、二醇酸、甘胺酸、丙胺酸、天冬胺酸、 -17- 200915411 硫二醇酸、乙二胺、三亞甲二胺、二甘醇、三甘醇、1，2-乙二硫醇、丙二酸、戊二酸、3 -羥丁酸、丙酸、酞酸、異 酞酸、3 -羥柳酸、3 , 5 -二羥柳酸、沒食子酸、苯甲酸、順丁 烯二酸等、這些之鹽，胺基聚羧酸及其鹽。 胺基聚羧酸及其鹽有乙二胺-N，N，N’ ，N’ -四乙酸、二乙 三胺五乙酸、1，3-二胺丙烷- N，N，N’ ，N’ -四乙酸、1,2-二胺 丙烷- N，N，N，，N’ -四乙酸、乙二胺-N，N’ -二琥珀酸（消旋 體）、乙二胺二琥珀酸（SS體）、N-(2-甲酸根乙基）-L-天冬胺 酸、N-(羧甲基）-L -天冬胺酸、/3-丙胺酸二乙酸、甲亞胺二 乙酸、氮三乙酸、環己二胺四乙酸、亞胺二乙酸、二醇醚 二胺四乙酸、乙二胺-1-N，N’ -二乙酸、乙二胺鄰羥苯乙酸、 N，N -雙（2 -羥苯甲基）乙二胺-N，N -二乙酸等及其鹽。相對鹽 之種類係以鹼金屬鹽及銨鹽爲佳’銨鹽尤佳。 這些氧化劑之中係以過氧化氫、碘酸鹽、次氯酸鹽、氯 酸鹽、過硫酸鹽、鐵（III)之有機錯鹽爲佳，使用鐵（ΠΙ)之 有機錯鹽時較佳之配位化合物可舉出有檸檬酸、酒石酸、 胺基聚羧酸（具體而言，乙二胺- N，N，N’ ，N’ -四乙酸、二乙 三胺五乙酸、1,3-二胺丙烷-N，N，N’ ，N’ -四乙酸、乙二胺 -N，N’ -二琥珀酸（消旋體）、乙二胺二琥珀酸（SS體）、N-(2- 甲酸根乙基）-L-天冬胺酸、N-(羧甲基）-L-天冬胺酸、/3 -丙 胺酸二乙酸、甲亞胺二乙酸、氮三乙酸、亞胺二乙酸）。 氧化劑更以過氧化氫、過硫酸鹽以及鐵（111)之乙二胺 -N，N，N’ ，N’ -四乙酸、1,3-二胺丙烷-N.，N，N’ ，N’ -四乙酸 及乙二胺二琥珀酸（S S體）之錯合物爲尤佳。 -18- 200915411 氧化劑係以在使用硏磨液進行硏磨之際，混合於含氧化 劑以外之其它成分的組成物使用爲佳。混合氧化劑之時機 係以剛要使用硏磨液前之1小時以內爲佳，5分鐘以內更 佳；尤佳者爲在剛要供給硏磨液於硏磨裝置前設置混合 器’剛要往被硏磨面供給前之5秒以內混合。 氧化劑之添加量係以使用於硏磨之際的金屬用硏磨液 每1L 0.001質量％以上且5質量％以下爲佳，0.003質量％ 以上且3質量％以下更佳。亦即，基於金屬之充分氧化而確 保高CMP速度，氧化劑之添加量係以0.001質量％以上爲 佳，基於防止硏磨面之粗糙，以5質量％以下爲佳。 (E)有機酸 本發明中，硏磨液可更含有機酸。此所謂有機酸係用以 促進氧化，調整pH，當作緩衝劑。本發明中所謂有機酸係 構造與用以氧化金屬之氧化劑不同的化合物，不包含前述 具氧化劑功能之酸。 本發明中之有機酸係以選自以下之群者爲佳。 亦即，甲酸、乙酸、丙酸、丁酸、戊酸、2 -甲基丁酸、 正己酸、3，3-二甲基丁酸、2 -乙基丁酸、4 -甲基戊酸、正庚 酸、2 -甲基己酸、正辛酸' 2 -乙基己酸、苯甲酸、二醇酸、 柳酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、 庚二酸、順丁烯二酸、酞酸、蘋果酸、酒石酸、檸檬酸' 乳酸及該等之銨鹽、鹼金屬鹽等鹽，硫酸、硝酸、氨、銨 鹽類或該等之混合物等。 這些之中’甲酸、丙二酸、蘋果酸、酒石酸、檸檬酸適 -19- 200915411 合於含選自銅 '銅合金及銅或銅合金之氧化物的至少丨種 金屬層之積層膜。 本發明中之有機酸’合適者可舉出有胺基酸等。 此胺基酸等係以水溶性者爲佳，選自以下之群者更合 適。 亦即宜含例如甘胺酸、L -丙胺酸、沒-丙胺酸、l - 2 -胺基 丁酸、L -正纈胺酸、L -纈胺酸、l -白胺酸、L -正白胺酸、 L -異白胺酸、L -別異白胺酸、L -***酸、L -脯胺酸、肌 胺酸、L -鳥胺酸、L -離胺酸、牛磺酸、l -絲胺酸、L -酥胺 酸、L -別酥胺酸、L -高絲胺酸、L -酪胺酸、3 , 5 -二碘-L -酪 胺酸、/5 -(3,4-二羥苯基）-L-丙胺酸' L-甲狀腺素' 4-羥-L-脯胺酸、L-硫胱酸、L-甲硫胺酸、L-乙硫胺酸、L-羊毛硫 胺酸、L-胱硫醚、L-胱胺酸、L-半胱胺酸、L-天冬胺酸、 L-麩胺酸、S-(羧甲基）-L-硫胱酸、4-胺基丁酸、L-天冬醯胺 酸、L -麩醯胺酸、氮絲胺酸、L -精胺酸、L -刀豆胺酸、L -瓜胺酸、（5 -羥-L-離胺酸、肌酸、L-犬尿素、L-組胺酸、1-甲基-L-組胺酸、3-甲基-L-組胺酸、麥角硫鹼、L-色胺酸、 放線菌素C1、阿帕明（Apamin)、升壓素I、升壓素II及抗 痛素（Antipain)等胺基酸中之至少1種。 這些之中尤以蘋果酸、酒石酸、檸檬酸、甘胺酸、二醇 酸因可維持實用之CMP速度，並有效抑制蝕刻速度而較佳。 有機酸之添加量係以使用於硏磨之際的硏磨液1 L中 0.0005~0.5mol 爲佳，0.005~0.3mol 更佳，0.01~0.1mol 尤佳 ° 亦即，基於侵蝕之抑制，有機酸之添加量係以0.5 mol以下 -20- 200915411 爲佳，爲得充分效果則以0.0005 mol以上爲佳。 (F)水溶性高分子 本發明之硏磨液可含有水溶性高分子做爲較佳倂用成 分。 (F)水溶性高分子者可舉出有多糖類（例如褐藻酸、果膠 酸、羧甲纖維素、洋菜、三仙膠、聚葡萄胺糖、甲基二醇 聚葡萄胺糖、甲基纖維素、乙基纖維素、羥甲基纖維素、 ,, 羥乙基纖維素、羥丙基纖維素、羥丙基甲基纖維素、羧甲 基纖維素、羧乙基纖維素、聚三葡萄糖）' 聚羧酸及其衍生 物（例如，聚丙烯酸、聚甲基丙烯酸、聚天冬胺酸 '聚麩胺 酸、聚離胺酸、聚蘋果酸、聚順丁烯二酸、聚伊康酸、聚 延胡索酸、聚（對苯乙烯甲酸）、聚乙烯硫酸、聚胺基丙烯 醯胺、聚醯胺酸、聚乙醛酸）、聚乙烯亞胺、乙烯基系聚合 物（例如聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯醛）、聚二醇 類（例如聚乙二醇、聚丙二醇、聚四亞甲二醇）等；較佳者 ί 可舉出有多糖類（例如褐藻酸、果膠酸、羧甲基纖維素、洋 菜、三仙膠、聚葡萄胺糖、甲基二醇聚葡萄胺糖、甲基纖 維素、乙基纖維素、羥甲基纖維素、羥乙基纖維素、羥丙 基纖維素、羥丙基甲基纖維素、羧甲基纖維素、羧乙基纖 維素、聚三葡萄糖）、聚羧酸及其衍生物（例如’聚丙烯酸、 聚甲基丙烯酸、聚天冬胺酸、聚麩胺酸、聚離胺酸、聚蘋 果酸、聚順丁烯二酸、聚伊康酸、聚延胡索酸、聚（對苯乙 烯甲酸）、聚乙烯硫酸、聚胺基丙烯醯胺、聚醯胺酸、聚乙 醛酸）、聚乙烯亞胺、乙烯基系聚合物（例如聚乙燒醇、聚 -21 - 200915411 乙烯吡咯烷酮、聚丙烯醛）。 唯因適用之被硏磨體係半導體積體電路用矽基板等 時，期無鹼金屬、鹼土金屬、鹵化物等之污染，故水溶性 高分子係酸時’宜直接以酸或其銨鹽之狀態使用。 (F)水溶性高分子之添加量係以使用於硏磨之際的硏磨 液總量每1L中，〇.〇〇l~l〇g爲佳’ 〇.〇1〜5g更佳，0.1~3g尤 佳。亦即，爲得充分效果’水溶性高分子之添加量係以 O.OOlg以上爲佳，基於防止CMP速度低落則以l〇g以下爲 佳。 (F)水溶性高分子之重量平均分子量係以500〜100,000爲 佳，2000~50000 尤佳。 本發明有關之（F)水溶性高分子可係僅只1種，亦可倂用 不同的2種以上。 (F)水溶性高分子與（A)膠體矽石粒子之含有質量比係以 0.0001 ： 1〜1 : 0.001 爲佳，0.001 ： 1~1: 0.01 更佳，0.005 ： 1〜1 : 0.1尤佳。 [其它成分] 本發明之硏磨液除該必要成分（A)成分〜（D)成分及較佳倂 用成分該（E)成分、（F)成分以外，在無損於本發明效果之範 圍內亦可倂用其它習知成分。 (G)四級銨陽離子 本發明之硏磨液可含有（G)分子中具有1以上四級氮原 子之四級銨陽離子（以下或簡稱「特定陽離子」或「四級銨 陽離子」）做爲較佳倂用成分。 -22- 200915411 四級銨陽離子之作用雖不明確，但推測係如下。 亦即應係’硏磨液中之四級銨陽離子吸附於硏磨粒子表 面’硏磨粒子與被硏磨面間之相互作用增強。更具體而言 應係’表面帶負電之硏磨粒子、表面帶負電的被硏磨面間 之排斥力爲四級銨陽離子所緩和。結果，硏磨粒子-被硏磨 面間之物理作用（物理刮除作用）增強，對於各膜種之硏磨 速度提升。 本發明中’四級銨陽離子若係於分子構造中含1以上四 級氮之構造即無特殊限制。其中，從充分提升硏磨速度之 觀點’以係下述一般式（1)或—般式（2)之陽離子爲佳。 R3 R4—N+ -R2 一般式（1 ) R1 R1 R4 一 2+ R2—N—-X R3 -N R6 一 R5 一般式（2) 該一般式（1) 般式（2)中，R|〜R6各自獨立表碳原子數 -23- 200915411 1~20之烷基、烯基、環烷基、芳基或芳烷基，亦可R1〜R6 之中有2互相結合形成環狀構造。 做爲R1〜R6的碳原子數1〜20之烷基具體可舉出有甲基、 乙基、丙基、丁基、戊基 '己基 '庚基、辛基等，其中以 甲基、乙基、丙基、丁基爲佳。 做爲該R1〜R6的烯基以碳原子數2〜10者爲佳，具體而言 可舉出有乙烯基、丙烯基等。 做爲該R1〜R6的環烷基具體可舉出有環己基、環戊基 等，其中以環己基爲佳。 做爲該R1〜R6的芳基具體可舉出有苯基、萘基等，其中 以苯基爲佳。 做爲該R1〜R6的芳烷基具體可舉出有苯甲基，其中以苯 甲基爲佳。 該Ri~R6的各基可更具有取代基，可導入之取代基可舉 出有羥基、胺基、羧基、雜環基、吡錠基、胺烷基、磷酸 基、亞胺基、硫醇基、擴酸基、硝基等。 該一般式（2)中，X表碳原子數1〜1〇之伸烷基、伸烯基、 伸環烷基、伸芳基或2以上的這些基組合成之基。 而X所表之連結基除該有機連結基以外，亦可於其鏈中 含-S-、-S( = 〇)2_、.〇_、-C( = 〇）-。 該碳原子數idO之伸烷基具體有亞甲基、伸烯基、伸 丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基等，其 中以伸乙基、伸戊基爲佳。 該伸烯基具體可舉出有伸乙烯基、伸丙烯基等，其中以 -24- 200915411 伸丙烯基爲佳。 該伸環院基具體可舉出有伸環己基、伸環庚基等’其中 以伸環己基爲佳。 該伸芳基具體可舉出有伸苯基、伸萘基’其中以伸苯基 爲佳。 該各連結基可更有取代基，可導入之取代基可舉出有經 基、胺基、磺醯基、羧基、雜環基、吡錠基、胺烷基、磷 酸基、亞胺基、硫醇基、磺酸基、硝基等。 以下具體例示本發明中之四級銨陽離子（特定陽離 子）[例示化合物（A1)〜（A46)]，但本發明不限於這些。 -25- 200915411 A2 A1 ch3 ch3 H3G—l|>J+—(CH2)2—N·5—CH3 ch3 ch3 CH3 ch3 H3G—N+—(CH2)6—N~CH3 ch3 A3 A4 CH3 CH3 ch3 H3G—l|J+ (CH2)8~ CH3 ch3 CH3 CH3 H3C-[Jj+—(CH2)10-^CHcC18H37-N-OC H The hydrophobic benzotriazole derivative I is added in an amount of 0.000 1% by mass or more based on the mass of the honing liquid used for honing from the viewpoint of good control of depression and erosion. The mass% or less is preferably at least 0.005 mass% and more preferably 1 mass% or less. (B) the total concentration of the hydrophilic benzotriazine derivative and (c) the hydrophobic benzotriazine derivative is 0.02 mass% or more with respect to the honing liquid used for honing 5 mass% or less is preferable, 0.01 mass% or more and 3% mass% or less are more preferable, and 0. 03 mass% or more and 1 mass% or less are especially preferable. From the viewpoint of good control of depression and invasion, (B) hydrophilic benzotriazole derivative-16- 200915411 2: 1~1: 5 is better, 3: 2~1: 5 is better, 1: 1~1: 5 is especially good. The honing liquid of the present invention may also be used (B) a hydrophilic benzotriazole derivative and (C) a hydrophobic benzotriazole derivative, and contain other azole compounds. The content of (B) the hydrophilic benzotriazole derivative and (C) the hydrophobic benzotriazole derivative may be 50 relative to the total benzotriazole used in the honing liquid at the time of honing. The mass % to 100% by mass, preferably 60% by mass to 90% by mass, more preferably 70% by mass to 90% by mass. The other pyrrole derivatives may be triazoles such as tolutriazole, 1-(1,2-dicarboxyethyl)toluenetriazole, 1-[N,N-bis(hydroxyethyl)aminemethyl]tolutriazole Derivatives, general known corrosion inhibitors such as imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, etc., and derivatives thereof, of which 1,2 3 - triazole, 1, 2, 4 - triterpene, and tetra-α are preferred. (D) Oxidizing agent The honing liquid of the present invention contains an oxidizing agent which can oxidize the metal to be honed. Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, and persulfate. , dichromate, permanganate, ozone water and silver (Π) salt, iron (III) salt. As the iron (III) salt, there are inorganic iron (πI) salts such as iron (III) nitrate, iron (III) chloride, iron (111) sulfate and iron (III), and iron (III). salt. When an organic salt of iron (III) is used, the complex compound constituting the iron (III) salt is, for example, acetic acid, citric acid, oxalic acid, salicylic acid, diethylenedithiocarbamic acid, succinic acid, tartaric acid, glycolic acid. , glycine, alanine, aspartic acid, -17- 200915411 thioglycolic acid, ethylenediamine, trimethylenediamine, diethylene glycol, triethylene glycol, 1,2-ethanedithiol, propylene Acid, glutaric acid, 3-hydroxybutyric acid, propionic acid, citric acid, isodecanoic acid, 3-hydroxysulphonic acid, 3,5-dihydroxysalic acid, gallic acid, benzoic acid, maleic acid Etc., these salts, amine polycarboxylic acids and their salts. Amine polycarboxylic acids and salts thereof are ethylenediamine-N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminepropane-N,N,N',N' -tetraacetic acid, 1,2-diamine propane - N,N,N,,N'-tetraacetic acid, ethylenediamine-N,N'-disuccinic acid (racemic), ethylenediamine disuccinic acid ( SS body), N-(2-formateethyl)-L-aspartic acid, N-(carboxymethyl)-L-aspartic acid, /3-alanine diacetic acid, methylimine diacetic acid , nitrogen triacetic acid, cyclohexanediaminetetraacetic acid, imine diacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine-1-N, N'-diacetic acid, ethylenediamine o-hydroxyphenylacetic acid, N, N - bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid and the like and salts thereof. The type of the relative salt is preferably an alkali metal salt or an ammonium salt. Among these oxidizing agents, organic acid salts of hydrogen peroxide, iodate, hypochlorite, chlorate, persulfate and iron (III) are preferred, and it is preferred to use an organic salt of iron. The coordination compound may, for example, be citric acid, tartaric acid or an amine polycarboxylic acid (specifically, ethylenediamine-N,N,N', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, 1,3- Diamine propane-N,N,N',N'-tetraacetic acid, ethylenediamine-N,N'-disuccinic acid (racemic), ethylenediamine disuccinic acid (SS body), N-(2 - formate ethyl)-L-aspartic acid, N-(carboxymethyl)-L-aspartic acid, /3-alanine diacetic acid, methylimine diacetic acid, nitrogen triacetic acid, imine Acetic acid). The oxidant is further hydrogen peroxide, persulfate and iron (111) ethylenediamine-N,N,N',N'-tetraacetic acid, 1,3-diaminepropane-N.,N,N',N A complex of -tetraacetic acid and ethylenediamine disuccinic acid (SS body) is preferred. -18- 200915411 The oxidizing agent is preferably a composition which is mixed with a component other than the oxidizing agent when honing using a honing liquid. The timing of mixing the oxidant is preferably within 1 hour before the honing liquid is used, and preferably within 5 minutes; especially when the honing liquid is just supplied to the honing device, the mixer is just ready to be Mix the honing surface within 5 seconds before the supply. The amount of the oxidizing agent to be added is preferably 0.001% by mass or more and 5% by mass or less per liter of the honing liquid for the honing, and more preferably 0.003% by mass or more and 3% by mass or less. In other words, the CMP is preferably 0.001% by mass or more based on the sufficient oxidation of the metal, and the amount of the oxidizing agent is preferably 0.001% by mass or more, and more preferably 5% by mass or less based on the roughness of the honing surface. (E) Organic acid In the present invention, the honing liquid may further contain organic acid. This so-called organic acid is used to promote oxidation, adjust pH, and act as a buffer. The compound having an organic acid-based structure different from the oxidizing agent for oxidizing a metal in the present invention does not include the above-mentioned acid having an oxidizing agent function. The organic acid in the present invention is preferably selected from the group consisting of the following. That is, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, Orthoheptanoic acid, 2-methylhexanoic acid, n-octanoic acid '2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , pimelic acid, maleic acid, citric acid, malic acid, tartaric acid, citric acid 'lactic acid and salts of such ammonium salts, alkali metal salts, sulfuric acid, nitric acid, ammonia, ammonium salts or mixtures thereof Wait. Among these, 'formic acid, malonic acid, malic acid, tartaric acid, and citric acid -19-200915411 are laminated to a laminated film containing at least a metal layer selected from the group consisting of copper 'copper alloys and oxides of copper or copper alloys. The organic acid in the present invention is preferably an amino acid or the like. The amino acid or the like is preferably water-soluble, and is preferably selected from the group consisting of the following. That is, it is preferable to contain, for example, glycine, L-alanine, no-alanine, l-2-aminobutyric acid, L-nuronic acid, L-proline, l-leucine, L-positive Aleucine, L-isoleucine, L-isoisoleucine, L-phenylalanine, L-proline, sarcosine, L-ornithine, L-lysine, taurine, l -serine, L-chymidine, L-Burric acid, L-homoserine, L-tyrosine, 3,5-diiodo-L-tyrosine, /5-(3, 4-dihydroxyphenyl)-L-alanine 'L-thyroxine' 4-hydroxy-L-proline, L-thiocysteine, L-methionine, L-ethylthioacetate, L- Worm thiamine, L-cystathion, L-cystine, L-cysteine, L-aspartic acid, L-glutamic acid, S-(carboxymethyl)-L-thiocyanate , 4-aminobutyric acid, L-aspartic acid, L-glutamic acid, nitrogen serine, L-arginine, L-cutosin, L-citrulline, (5 - Hydroxy-L-lysine, creatine, L-canine urea, L-histidine, 1-methyl-L-histidine, 3-methyl-L-histidine, ergot sulfate, L - Amino acids such as tryptophan, actinomycin C1, Apamin, vasopressin I, vasopressin II and antipain At least one of these. In particular, malic acid, tartaric acid, citric acid, glycine, and glycolic acid are preferred because they maintain a practical CMP rate and effectively suppress the etching rate. The amount of organic acid added is used. In the case of honing, the honing liquid 1 L is preferably 0.0005 to 0.5 mol, more preferably 0.005 to 0.3 mol, and more preferably 0.01 to 0.1 mol. That is, the amount of the organic acid added is 0.5 mol or less or less based on the inhibition of the erosion. -20- 200915411 is preferable, and it is preferably 0.0005 mol or more for sufficient effect. (F) Water-soluble polymer The honing liquid of the present invention may contain a water-soluble polymer as a preferred ingredient. (F) Water-soluble The polymer may be exemplified by polysaccharides (for example, alginic acid, pectic acid, carboxymethylcellulose, acacia, sinosaur, polyglucosamine, methyl glycol polyglucosamine, methylcellulose, Ethylcellulose, hydroxymethylcellulose, ,, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, polytriglucose) Polycarboxylic acids and their derivatives (for example, polyacrylic acid, polymethacrylic acid, polyaspartic acid' Aminic acid, polylysine, polymalic acid, polymaleic acid, polyisic acid, polyfumaric acid, poly(p-styrenecarboxylic acid), polyvinylsulfuric acid, polyaminoacrylamide, polylysine , polyglyoxylic acid), polyethyleneimine, vinyl polymer (such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylaldehyde), polyglycols (such as polyethylene glycol, polypropylene glycol, polytetramethylene Glycol), etc.; preferably, ί may include polysaccharides (for example, alginic acid, pectic acid, carboxymethyl cellulose, agar, trisin, polyglucosamine, methyl glycol polyglucosamine) , methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, poly Triglucose), polycarboxylic acids and derivatives thereof (eg 'polyacrylic acid, polymethacrylic acid, polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymaleic acid, poly Itaconic acid, polyfumaric acid, poly(p-styrenecarboxylic acid), polyvinylsulfate, polyaminoacrylamide Polyamide acid, polyethylene uronic acid), polyethylene imine, vinyl polymers (e.g. polyethylene burning alcohol, polyethylene -21--200915411 vinyl pyrrolidone, polyacrolein). Only when it is applied to a ruthenium system semiconductor integrated circuit for a substrate or the like, it is not contaminated with alkali metals, alkaline earth metals, halides, etc., so when the water-soluble polymer is acid, it is preferable to directly use an acid or an ammonium salt thereof. Status is used. (F) The amount of the water-soluble polymer added is preferably 1 to 5 g per liter of the total amount of the honing liquid used for honing. 〇. 〇 1 to 5 g is more preferable, 0.1 ~3g is especially good. That is, in order to obtain a sufficient effect, the amount of the water-soluble polymer added is preferably O.Olg or more, and it is preferably 10 g or less based on the prevention of a decrease in the CMP rate. (F) The weight average molecular weight of the water-soluble polymer is preferably from 500 to 100,000, more preferably from 2,000 to 50,000. The (F) water-soluble polymer according to the present invention may be used alone or in combination of two or more. (F) The mass ratio of the water-soluble polymer to the (A) colloidal vermiculite particles is preferably 0.0001:1 to 1:0.001, 0.001:1 to 1:0.01, more preferably 0.005:1 to 1:0.1. . [Other components] The honing liquid of the present invention is not detrimental to the effects of the present invention, except for the essential component (A) component (D) component and the preferred component (E) component and (F) component. Other conventional ingredients can also be used. (G) quaternary ammonium cation The honing liquid of the present invention may contain a quaternary ammonium cation having 1 or more quaternary nitrogen atoms in the molecule (hereinafter referred to as "specific cation" or "quaternary ammonium cation") as It is preferred to use ingredients. -22- 200915411 Although the role of the quaternary ammonium cation is not clear, it is estimated to be as follows. That is, the quaternary ammonium cation in the honing liquid is adsorbed on the surface of the honing particle, and the interaction between the honing particle and the surface to be honed is enhanced. More specifically, it should be such that the repulsive force between the surface of the negatively charged honing particles and the negatively charged surface of the surface is moderated by the quaternary ammonium cation. As a result, the honing particles - the physical interaction between the honing surfaces (physical scraping action) is enhanced, and the honing speed is increased for each film type. In the present invention, the "quaternary ammonium cation" is not particularly limited as long as it has a structure containing 1 or more nitrogens in the molecular structure. Among them, from the viewpoint of sufficiently increasing the honing speed, it is preferable to use a cation of the following general formula (1) or the general formula (2). R3 R4—N+ -R2 General formula (1) R1 R1 R4 2+ R2—N—-X R3 -N R6 A R5 General formula (2) The general formula (1) In the general formula (2), R|~ R6 each independently has a carbon number of from -23 to 200915411, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and two of R1 to R6 may be bonded to each other to form a cyclic structure. Specific examples of the alkyl group having 1 to 20 carbon atoms of R1 to R6 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl 'hexyl'heptyl group, an octyl group and the like. Base, propyl, butyl are preferred. The alkenyl group of R1 to R6 is preferably a carbon number of 2 to 10, and specific examples thereof include a vinyl group and a propenyl group. Specific examples of the cycloalkyl group of R1 to R6 include a cyclohexyl group and a cyclopentyl group, and among them, a cyclohexyl group is preferred. Specific examples of the aryl group of R1 to R6 include a phenyl group and a naphthyl group, and among them, a phenyl group is preferred. Specific examples of the aralkyl group as the R1 to R6 include a benzyl group, and a benzyl group is preferred. Each of the groups of Ri~R6 may have a substituent, and examples of the substituent which may be introduced include a hydroxyl group, an amine group, a carboxyl group, a heterocyclic group, a pyridyl group, an amine alkyl group, a phosphoric acid group, an imido group, and a mercaptan. Base, acid extension, nitro, and the like. In the general formula (2), an alkyl group, an alkenyl group, a cycloalkyl group, an extended aryl group or a group of 2 or more having a carbon number of 1 to 1 Å in the X group is combined. The linking group represented by X may contain -S-, -S(= 〇)2_, .〇_, -C( = 〇)- in the chain in addition to the organic linking group. The alkylene group having a carbon atom number iDO specifically has a methylene group, an alkenyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a octyl group, and the like. Amyl is preferred. Specific examples of the alkenyl group include a vinyl group, a propylene group and the like, and a propylene group is preferably used in the range of -24 to 200915411. Specific examples of the extensible ring base include a stretched cyclohexyl group, a cyclopentene group, and the like. Specifically, the aryl group may be a phenyl group or a naphthyl group, and a phenyl group is preferred. Each of the linking groups may have a more substituent, and examples of the substituent which may be introduced include a trans group, an amine group, a sulfonyl group, a carboxyl group, a heterocyclic group, a pyridyl group, an amine alkyl group, a phosphoric acid group, an imido group, A thiol group, a sulfonic acid group, a nitro group or the like. The quaternary ammonium cation (specific cation) in the present invention [exemplary compounds (A1) to (A46)] is specifically exemplified below, but the present invention is not limited thereto. -25- 200915411 A2 A1 ch3 ch3 H3G—l|>J+—(CH2)2—N·5—CH3 ch3 ch3 CH3 ch3 H3G—N+—(CH2)6—N~CH3 ch3 A3 A4 CH3 CH3 ch3 H3G— l|J+ (CH2)8~ CH3 ch3 CH3 CH3 H3C-[Jj+—(CH2)10-^CHc

ChU A5 c2h5 c2h5 C2H5—N+—(CH2)2— C2H5 C2H5 A6 C2H5 C2H5—I^T (CH2)5 ^2h5ChU A5 c2h5 c2h5 C2H5—N+—(CH2)2—C2H5 C2H5 A6 C2H5 C2H5—I^T (CH2)5 ^2h5

c2h5 —N—C 2H5 A7C2h5 —N—C 2H5 A7

ch3 c6h13-t|j+—(ch2)5 ch3 A8 C4H9 A10 C4H9 i4H9 C4H9 '(CH2)5~I>1—C4H9 〒H3 5—N—C4 C4H9 ch3 i—rjj—c CH, ch3 OH^ A13Ch3 c6h13-t|j+—(ch2)5 ch3 A8 C4H9 A10 C4H9 i4H9 C4H9 '(CH2)5~I>1—C4H9 〒H3 5—N—C4 C4H9 ch3 i—rjj—c CH, ch3 OH^ A13

A15 CH3 ch3 (+ ~~(CH2)5- ch3A15 CH3 ch3 (+ ~~(CH2)5- ch3

C4H9—N (CH2)5—rjJ—C4H9 CH3 A12 ch3 ch3 CsH 17-f|J+ (CH2)s—N—CgH^ CH3 ch3 A14 ch3 ch3 H〇-C2H5-f|j+—(CH2)2H\l:L-C2H5-〇H ch3 ch3 ch3 ch3 ^C4H9—N (CH2)5—rjJ—C4H9 CH3 A12 ch3 ch3 CsH 17-f|J+ (CH2)s—N—CgH^ CH3 ch3 A14 ch3 ch3 H〇-C2H5-f|j+—(CH2)2H\l :L-C2H5-〇H ch3 ch3 ch3 ch3 ^

H〇-C2H5—N+—(〇曰2)5~^^~〇2闪5—OH ch3 ch3 -26- 200915411 A16 ch3 ch3 \_/~CH2—(CH2)5-|||—CH — CH^ CH-, ch3H〇-C2H5—N+—(〇曰2)5~^^~〇2flash 5—OH ch3 ch3 -26- 200915411 A16 ch3 ch3 \_/~CH2—(CH2)5-|||—CH — CH ^ CH-, ch3

广U A17 CH2—i^l+—(CH2)2—s—(CH2)； ch3 A18 A19Wide U A17 CH2—i^l+—(CH2)2—s—(CH2); ch3 A18 A19

CH 3 CH ‘CH 3 CH ‘

H3G—N^/^N—CHa C2H5— A20 ^N-CH.H3G—N^/^N—CHa C2H5— A20 ^N-CH.

ch2- A21Ch2- A21

OrOr

ch3 CH2~N+~(CH2)2 ch3 ch3 (CH2)2—ch2-ch3Ch3 CH2~N+~(CH2)2 ch3 ch3 (CH2)2—ch2-ch3

V A22V A22

-27- 200915411 A25 CH3 o CH3 H3C-^+—(〇Η2)2-έ-(〇Η2)2-Ν±--〇Η3 CH3 ώ CH3 A26-27- 200915411 A25 CH3 o CH3 H3C-^+—(〇Η2)2-έ-(〇Η2)2-Ν±--〇Η3 CH3 ώ CH3 A26

N—(CH2)5_~N+N—(CH2)5_~N+

A28 νΝ^Η2〇〇0(ΟΗ2)4〇〇〇〇Η2A28 νΝ^Η2〇〇0(ΟΗ2)4〇〇〇〇Η2

A30A30

A29A29

VCH3 C4H9 ^^ 亡4H9VCH3 C4H9 ^^ 死4H9

A33 04A33 04

\ CH3 /—N—CH3 ihu -28- 200915411 4 A3\ CH3 /—N—CH3 ihu -28- 200915411 4 A3

n3c H3+H3 C——N——C A3 5 5 2 HsIH5o)—N-—o A3 cN3c H3+H3 C——N——C A3 5 5 2 HsIH5o)—N-—o A3 c

3 CIN -7 3 7 9 7 H.l Η3 CIN -7 3 7 9 7 H.l Η

A - 9 4hcA - 9 4hc

H 88 cA3 -9 H9—CH9 4+一 4 C——N——CH 88 cA3 -9 H9—CH9 4+ a 4 C——N——C

H 8 17-C17 8H+I8h C——N——C A3 H21 o c1 OH H21fH21 10+10 o.—-N—o H3 5 1C1 A4 5 2 2 5 15 H2-CH2 2 2 1+1 1o—N-—o 5 2 2 0C1 A4H 8 17-C17 8H+I8h C——N——C A3 H21 o c1 OH H21fH21 10+10 o.—N—o H3 5 1C1 A4 5 2 2 5 15 H2-CH2 2 2 1+1 1o— N--o 5 2 2 0C1 A4

C——N——C 5 oC——N——C 5 o

Ho H31-C1H2 2 A4Ho H31-C1H2 2 A4

% A4 3 H h ^ h H3C(H3(c+l(c c——N—c I )3C -3 (c A44 A45% A4 3 H h ^ h H3C(H3(c+l(c c——N-c I )3C -3 (c A44 A45

CH 2' CH2—N—CH: HOC2H4-CH 2' CH2—N—CH: HOC2H4-

CHCH

C2H4OHl + -N—C2H4OH C2H4OHC2H4OHl + -N-C2H4OH C2H4OH

A46 c5Hu 1 + C5Hh—-N—C5H11 C5HH 從在硏磨液中之分散安定性的觀點，如上述之（G)四級 -29- 200915411 銨陽離子（特定陽離子）中’以A8、A10、All、A12、A36、 A37、A46 爲佳。 本發明中之（G)四級銨陽離子（特定陽離子）可例如以 氨、各種胺等用作求核劑經取代反應合成。 亦可購用一般市售試劑。 本發明中（G)四級銨陽離子（特定陽離子）之添加量係以 相對於使用於硏磨之際的硏磨液（亦即，以水或水溶液稀釋 時爲稀釋後之硏磨液。此後之「使用於硏磨之際的硏磨液」 亦同）0.000 1質量％以上且1質量％以下爲佳，〇·〇01質量％ 以上且0.3質量％以下更佳。亦即，如此的陽離子之添加 量，從充分提升硏磨速度之觀點係以0.000 1質量％以上爲 佳，從充分的漿體安定性之觀點，以1質量％以下爲佳。 本發明有關之（G)四級銨陽離子（特定陽離子）可僅只1種 亦可倂用不同的2種以上。 (Η)界面活性劑 本發明之硏磨液可倂用界面活性劑。可倂用之界面活性 劑可舉出有陰離子界面活性劑、陽離子界面活性劑。 陰離子界面活性劑具體可舉出有例如癸苯磺酸、十二苯 磺酸 '十四苯磺酸、十六苯磺酸、十二萘磺酸、十四萘磺 酸等化合物。 陽離子界面活性劑具體有例如月桂基三甲銨、月桂基三 乙銨、硬脂基三甲銨、棕櫚基三甲銨、辛基三甲銨、十二 基吡錠、癸基吡錠、辛基吡錠等化合物。 可用於本發明之陰離子界面活性劑除該磺酸鹽以外，較 -30- 200915411 佳者尙可舉出有羧酸鹽、硫酸酯鹽、磷酸酯鹽。 更具體而言，適用之羧酸鹽有肥皂、N -醯基胺酸鹽、聚 氧乙烯或聚氧丙烯烷基醚羧酸鹽、醯化肽； 硫酸酯鹽有硫酸化油、烷基硫酸鹽、烷基醚硫酸鹽、聚 氧乙烯或聚氧丙烯烷基醚硫酸鹽、烷基醯胺硫酸鹽； 磷酸酯鹽有烷基磷酸鹽、聚氧乙烯或聚氧丙烯烷基醚磷 酸鹽。 界面活性劑之添加量係以使用於硏磨之際的硏磨液總 量每1L中0.001~10g爲佳，0.01~5g更佳，0.01〜lg尤佳。 亦即，界面活性劑之添加量，爲得充分之效果係以0.0 1 g 以上爲佳，爲防CMP速度低落則以1 g以下爲佳。 界面活性劑可單獨使用1種，亦可倂用2種以上。 (I)pH調整劑 本發明之硏磨液係以PH2〜5爲佳，PH2~4更佳’ ΡΗ2·5~4 尤佳。如上控制硏磨液之pH即可更有效調整層間絕緣膜之 硏磨速度。 本發明之金屬用硏磨液爲達特定pH，係以添加鹼/酸或 緩衝劑爲佳。 鹼/酸或緩衝劑較佳可舉出有氫氧化錢及氫氧化四甲錢 等有機氫氧化銨，如二乙醇胺、三乙醇胺、三異丙醇胺等 之烷醇胺類等非金屬鹼劑，氫氧化鈉、氫氧化鉀、氫氧化 鋰等鹼金屬氫氧化物，硝酸、硫酸、磷酸等之無機酸’碳 酸鈉等碳酸鹽，磷酸三鈉等之磷酸鹽，硼酸鹽，四硼酸鹽’ 羥基苯甲酸鹽等。尤佳之鹼劑係氫氧化銨、氫氧化鉀、氫 -31 - 200915411 氧化鋰及氫氧化四甲銨。 鹼或緩衝劑較佳可舉出有氨、氫氧化銨、氫氧化四甲銨 等有機氫氧化銨，二乙醇胺、三乙醇胺、三異丙醇胺等之 烷醇胺類等非金屬鹼劑，氫氧化鈉、氫氧化鉀、氫氧化鋰 等鹼金屬氫氧化物。 尤佳之鹼劑係氫氧化銨、氫氧化鉀、氫氧化鋰及氫氧化 四甲錢。 f 鹼或緩衝劑之添加量若能維持pH於良好範圍即可，以 使其爲使用於硏磨之際的硏磨液1 L中0.0 0 0 1 m ο 1 ~ 1. 0 m ο 1爲 佳，0.003mol~0.5mol 更佳。 (J)螯合劑 本發明之硏磨液爲降低混入之多價金屬離子等之不良 影響，必要時以含有螯合劑（亦即硬水軟化劑）爲佳。 螯合劑乃泛用之硬水軟化劑（鈣、鎂之沈澱防止劑）、其 相關化合物，可舉出例如氮三乙酸：二乙三胺五乙酸、乙 ^ >； 二胺四乙酸、N，N，N-三亞甲磺酸、乙二胺- N，N，N’ ，N’ 四 亞甲磺酸、反式環己二胺四乙酸、1,2 -二胺丙烷四乙酸、二 醇醚二胺四乙酸、乙二胺鄰羥苯乙酸、乙二胺二琥珀酸（SS 體）、N-(2 -甲酸根乙基）-L -天冬胺酸、/3 -丙胺酸二乙酸、2-磷丁烷-1,2,4-三甲酸、1-羥伸乙烯-1，卜二磺酸、Ν,Ν’ -雙（2-羥苯甲基）乙二胺-Ν，Ν’ -二乙酸、1,2-二羥苯-4,6-二磺酸 等。 螯合劑在必要時亦可倂用2種以上。 螯合劑之添加量若能充分封鎖混入的多價金屬離子等 -32- 200915411 金屬離子即佳’可例如添加至使用於硏磨之際的硏磨液1 L 中達 0.0003mol〜0.07mol。 [硏磨液之用途] 一般而言’本發明之硏磨液適用於硏磨防止存在於銅金 屬及/或銅合金構成的配線與層間絕緣膜間之銅的擴散之 阻障層。 於阻障層CMP ’當以一階段一倂進行阻障層硏磨及絕緣 層硏磨時’本發明之硏磨液亦適用，故本發明之硏磨液亦 適用於絕緣層之硏磨。 [阻障層金屬材料] 構成阻障層之材料者’ 一般低電阻金屬材料即可，TiN、 TiW、Ta、TaN、W、WN、Ru 等較適用，其中以 Ta、TaN 爲佳。這些Ta系金屬材料以外，由Μη、Ti、Ru或該等之 衍生物形成的阻障層者，本發明之硏磨液亦適用。 [層間絕緣膜] 層間絕緣膜（絕緣層）除TEOS等常用層間絕緣膜以外， 可舉出例如含相對電容率3 · 5〜2.0左右之低電容率材料（例 如有機聚合物系、Si OC系、SiOF系等，通常簡稱爲Low-k 膜）的層間絕緣膜。 具體而言’用於形成低電容率層間絕緣膜之材料，有 SiOC 系的 HSG-R7 (日立化成工業）、BLACKDIAMOND (Applied Materials, Inc)等。A46 c5Hu 1 + C5Hh--N-C5H11 C5HH From the viewpoint of dispersion stability in honing liquid, as in the above (G) quaternary -29-200915411 ammonium cation (specific cation) 'with A8, A10, All A12, A36, A37, A46 are preferred. The (G) quaternary ammonium cation (specific cation) in the present invention can be synthesized, for example, by a substitution reaction using ammonia, various amines or the like as a nucleating agent. General commercially available reagents can also be purchased. In the present invention, the (G) quaternary ammonium cation (specific cation) is added in an amount relative to the honing liquid used for honing (that is, the honing liquid diluted after dilution with water or an aqueous solution. Thereafter) The same applies to 0.000 1% by mass or more and 1% by mass or less, and more preferably 质量·〇01% by mass or more and 0.3% by mass or less. In other words, the amount of the cation added is preferably 0.0001% by mass or more from the viewpoint of sufficiently increasing the honing speed, and is preferably 1% by mass or less from the viewpoint of sufficient slurry stability. The (G) quaternary ammonium cation (specific cation) according to the present invention may be used alone or in combination of two or more. (Η) Surfactant The honing fluid of the present invention can be used as a surfactant. Examples of the surfactant which can be used include an anionic surfactant and a cationic surfactant. Specific examples of the anionic surfactant include compounds such as toluenesulfonic acid, dodecylsulfonic acid 'tetradecenesulfonic acid, cetylsulfonic acid, dodecanesulfonic acid, and tetradecylsulfonic acid. The cationic surfactants are specifically, for example, lauryl trimethylammonium, lauryl triethylammonium, stearyl trimethylammonium, palmityl trimethylammonium, octyltrimethylammonium, dodecylpyridinium, decylpyridinium, octylpyridinium, etc. Compound. The anionic surfactant which can be used in the present invention has, in addition to the sulfonate, a carboxylate, a sulfate salt or a phosphate salt as compared with -30 to 200915411. More specifically, suitable carboxylates are soaps, N-mercaptoamines, polyoxyethylene or polyoxypropylene alkyl ether carboxylates, deuterated peptides; sulfates are sulfated oils, alkyl sulfates Salt, alkyl ether sulfate, polyoxyethylene or polyoxypropylene alkyl ether sulfate, alkyl decylamine sulfate; phosphate salt is alkyl phosphate, polyoxyethylene or polyoxypropylene alkyl ether phosphate. The amount of the surfactant added is preferably 0.001 to 10 g per 1 L of the honing liquid used in the honing, more preferably 0.01 to 5 g, and particularly preferably 0.01 to lg. That is, the amount of the surfactant to be added is preferably 0.01 g or more for the sufficient effect, and preferably 1 g or less for preventing the CMP from being lowered. The surfactant may be used singly or in combination of two or more. (I) pH adjuster The honing liquid of the present invention is preferably pH 2 to 5, and more preferably PH 2 to 4 is more preferably ΡΗ 2·5 to 4 . By controlling the pH of the honing liquid as above, the honing speed of the interlayer insulating film can be more effectively adjusted. The metal honing liquid of the present invention is preferably at a specific pH, and is preferably added with a base/acid or a buffer. The alkali/acid or the buffering agent is preferably an organic ammonium hydroxide such as a hydrogen peroxide or a tetramethylammonium hydroxide, or a non-metal alkaline agent such as an alkanolamine such as diethanolamine, triethanolamine or triisopropanolamine. An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide, a mineral acid such as nitric acid, sulfuric acid or phosphoric acid, a carbonate such as sodium carbonate, a phosphate such as trisodium phosphate, a borate or a tetraborate. Hydroxybenzoate and the like. A particularly good base is ammonium hydroxide, potassium hydroxide, hydrogen -31 - 200915411 lithium oxide and tetramethylammonium hydroxide. The alkali or the buffering agent is preferably a non-metal alkaline agent such as an organic ammonium hydroxide such as ammonia, ammonium hydroxide or tetramethylammonium hydroxide, or an alkanolamine such as diethanolamine, triethanolamine or triisopropanolamine. An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide. The base agent is preferably ammonium hydroxide, potassium hydroxide, lithium hydroxide and tetramethyl hydride. f If the amount of alkali or buffer added can maintain the pH in a good range, so that it is used in the honing of the honing liquid 1 L 0.00 0 1 m ο 1 ~ 1. 0 m ο 1 Preferably, 0.003 mol to 0.5 mol is more preferred. (J) Chelating agent The honing liquid of the present invention is preferably a chelating agent (i.e., a hard water softening agent) if it is used to reduce the adverse effects of the mixed polyvalent metal ions and the like. The chelating agent is a hard water softening agent (precipitation preventing agent for calcium and magnesium), and a related compound thereof, for example, nitrogen triacetic acid: diethylenetriaminepentaacetic acid, ethylene > diamine tetraacetic acid, N, N,N-trimethanesulfonic acid, ethylenediamine-N,N,N',N' tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminepropane tetraacetic acid, glycol ether Diaminetetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS body), N-(2-formateethyl)-L-aspartic acid, /3-alanine diacetic acid, 2-Phosphetane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1, bis disulfonic acid, hydrazine, Ν'-bis(2-hydroxybenzyl)ethylenediamine-hydrazine, Ν' - diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and the like. The chelating agent may be used in combination of two or more kinds as necessary. If the amount of the chelating agent added is sufficient to block the polyvalent metal ion to be mixed, etc. -32-200915411, the metal ion is preferably added to the honing liquid 1 L used for honing to 0.0003 mol to 0.07 mol. [Use of honing liquid] Generally, the honing liquid of the present invention is suitable for damaging a barrier layer which prevents the diffusion of copper existing between a wiring composed of a copper metal and/or a copper alloy and an interlayer insulating film. In the barrier layer CMP', when the barrier layer honing and the insulating layer honing are performed in one stage, the honing liquid of the present invention is also applicable, and the honing liquid of the present invention is also suitable for honing of the insulating layer. [Mesible material for barrier layer] The material constituting the barrier layer is generally a low-resistance metal material. TiN, TiW, Ta, TaN, W, WN, Ru, etc. are suitable, and Ta and TaN are preferred. The honing liquid of the present invention is also applicable to a barrier layer formed of Μη, Ti, Ru or such derivatives other than these Ta-based metal materials. [Interlayer insulating film] The interlayer insulating film (insulating layer) may be, for example, a low-permittivity material having a relative permittivity of about 3·5 to 2.0, in addition to a common interlayer insulating film such as TEOS (for example, an organic polymer system or a Si OC system). An interlayer insulating film of an OOF type or the like, which is usually simply referred to as a Low-k film. Specifically, materials for forming a low-resistivity interlayer insulating film include SiOC-based HSG-R7 (Hitachi Chemical Industry Co., Ltd.) and BLACKDIAMOND (Applied Materials, Inc.).

如此之Low-k膜通常係位於TEOS絕緣膜下，並於TEOS 絕緣膜上形成阻障層及金屬配線。 -33- 200915411 [金屬配線原材料] 本發明中’被硏磨體（硏磨對象）係以例如具有適 LSI等之半導體積體電路，由銅金屬及/或銅合金構 線爲佳。此配線之原材料係以銅合金爲尤佳。銅合. 係以含有銀之銅合金爲更佳。 銅合金之銀含量係以40質量％以下爲佳，1〇質量 更佳，1質量％以下尤佳；於0.0 000 1〜0」質量％範圍 金可發揮最佳效果。 [配線粗細] 本發明中’被硏磨體（硏磨對象）係以例如採用於 兀件系時’具有半間距0. 1 5 /z m以下的配線爲佳，〇 以下者更佳，0.08# m以下者尤佳。 另一方面’被硏磨體係以例如採用於MPU元件系 有〇.12#m以下之配線者爲佳，〇.〇9#ιη以下者更佳 μ m以下者尤佳。 對於具有如此之配線的被硏磨體，上述本發明之 尤可發揮優異效果。 [硏磨方法] 本發明之硏磨液有（1)係爲濃縮液，使用之際加水 液稀釋成使用液者，（2)以下述之水溶液形態準備各 將這些混合，必要時加水稀釋成使用液者，（3 )調製 液者。 使用本發明之硏磨液的硏磨方法可採用任一者 液。 於如 成之配 金之中 %以下 之銅合 dram .1 0 // m 時，具 '0.07 硏磨液 或水溶 成分， 爲使用 之硏磨 -34- 200915411 此硏磨方法係供給硏磨液於硏磨平台上之硏磨墊，使與 被硏磨體之被硏磨面接觸’使被硏磨面與硏磨墊相對運動 之方法。 用於硏磨之裝置可使用一般硏磨裝置，其具備，保持具 有被硏磨面之被硏磨體（例如’形成有導電性材料膜的晶圓 等）之支架’與貼附有硏磨墊之（裝有轉數可變的馬達等之） 硏磨平台。硏磨墊者可以使用一般的不織布、發泡聚氨酯、 / 多孔質氟樹脂等，無特殊限制。 硏磨條件亦無特殊限制，硏磨平台之旋轉速度係以不使 被硏磨體飛出的200rpm以下之低轉數爲佳。往硏磨墊按押 具有被硏磨面（被硏磨膜）的被硏磨體之壓力以係 0.68~34.5KPa爲佳’爲得硏磨速度下被硏磨體之面內均勻 性及圖案之平坦性，以3.40〜20.7KPa爲更佳。 硏磨期間，以泵等連續供給硏磨液於硏磨墊。 硏磨結束後，被硏磨體於流水中充分洗淨後，使用旋乾 機等去除附著在被硏磨體上之水滴使乾燥。 本發明中，如該（1)之方法，將濃縮液稀釋之際，可使用 下示之水溶液。水溶液係已含有（A)膠體矽石粒子、（B)親 水性之苯并***衍生物、（C)疏水性之苯并***衍生物及（D) 氧化劑中之至少1種以上的水；此水溶液中含之成分，與 將予稀釋之濃縮液中含之成分的合計成分係使之成爲使用 於硏磨之際的硏磨液（使用液）之成分。 如此，濃縮液以水溶液稀釋使用時，可將難以溶解之成 分製成水溶液之形態後配合，故可調製更爲濃縮之濃縮液。 -35- 200915411 又，於濃縮液加水或水溶液而稀釋之方法，有使供給經 濃縮之硏磨液的配管與供給水或水溶液之配管於途中合流 而混合，供給經混合稀釋之硏磨液使用液於硏磨墊之方 法。濃縮液與水或水溶液之混合可採用，施壓狀態下通過 狹窄通路使液體互相衝擊混合之方法，於配管中設置動力 旋轉葉片的方法等通常採行之方法。 硏磨液之供給速度係以1 0 ~ 1 〇 〇 〇 m 1 / m i η爲佳，爲滿足硏 磨速度下被硏磨面內之均勻性及圖案平坦性，以係 170 〜800ml/min 爲更佳。 進一步，濃縮液經以水或水溶液等稀釋且一邊硏磨之方 法有獨立設置供給硏磨液之配管與供給水或水溶液之配 管，各供給特定量液體於硏磨墊，藉硏磨墊與被硏磨面之 相對運動混合且一邊硏磨之方法。再者，亦可採用於丨容 器放入特定量之濃縮液與水或水溶液並混合，供給該經混 合之硏磨液於硏磨墊而硏磨之方法。 其它硏磨方法有將硏磨液應含之成分分成至少2構成成 分’使用之際對其加水或水溶液稀釋，供給於硏磨平台上 之硏磨墊，使與被硏磨面接觸，使被硏磨面與硏磨墊相對 運動而硏磨之方法。 例如’可以氧化劑爲構成成分（A)，其它添加劑及水爲 構成成分（B)，使用之際以水或水溶液稀釋構成成分（幻及 構成成分（B)而使用。 亦可將溶解度低之添加劑分成構成成分（A)與（B)，使用 之際於該等加水或水溶液稀釋構成成分（A)及構成成分（B) -36- 200915411 而使用。 如上之例者，乃必須有各供給構成成分（A )、構成成分（B) 與水或水溶液的3配管，稀釋混合係將3配管結合成供給 於硏磨墊的1配管’於該配管內混合之方法，此時，亦可 結合2配管後結合另1配管。具體而言乃混合含不易溶解 之添加劑的構成成分與其它構成成分，延長混合路徑確保 溶解時間’再結合水或水溶液之配管的方法。 f , 其它混合方法有，如上直接將3配管各導至硏磨墊，藉 硏磨墊與被硏磨面之相對運動混合之方法，或於1容器混 合3構成成分，之後於硏磨墊供給經稀釋之硏磨液的方法。 上述方法中，可保持含氧化劑的第1構成成分於40°C以 下，以室溫至1 00 °C之範圍加溫其它構成成分，混合第1 構成成分與其它構成成分之際，或加水或水溶液稀釋之 際’使液溫爲4 0 °C以下。此方法係利用溫度高則溶解度高 之現象’以提高硏磨液中的低溶解度原料之溶解度的較佳 ί」 方法。 以室溫至100°c之範圍加溫該其它構成成分而溶解之原 料，溫度下降即自溶液中析出，故使用低溫狀態之其它構 成成分時，必須先予加溫，使析出之原料溶解。於此可採 用加溫並輸液作爲原料之已溶解之其它構成成分的手段， 與先攙拌含析出物之液體，輸液，將配管加溫以使溶解的 手段。經加溫之其它構成成分若使含氧化劑之第1構成成 分的溫度高於40°c以上，則氧化劑有分解之虞，故混合此 經加溫之其它構成成分與含氧化劑之第1構成成分時，較 -37- 200915411 佳者係使其在40°C以下。 如此，本發明中，亦可將硏磨液之成分分成二部分以 上，供給於被硏磨面。此時，以分成含氧化劑之成分與含 有機酸之成分而供給爲佳。亦可使硏磨液爲濃縮液，另供 給稀釋水於被硏磨面。 本發明中，採用將硏磨液之成分分成二部分以上，供給 於被硏磨面之方法時，其供給量代表來自各配管之供給量 的合計。 〔墊〕 適用於本發明之硏磨方法的硏磨墊可爲非發泡構造 墊、發泡構造墊。前者之墊使用如塑膠板之硬質合成樹脂 塊狀材。後者更有獨立發泡體（乾式發泡系）、連續發泡體（濕 式發泡系）、2層複合體（積層系）3類，2層複合體（積層系） 尤佳。發泡可係均勻或非均勻。 ϋ 一步·’尙可係含有一般使用於硏磨之砥粒（例如氧化 鈽、砂石、氧化鋁、樹脂等）者。而硬度方面則可爲軟質或 硬質之任一 ’於積層系則以使用各層硬度不同者爲佳。材 質則以不織布、人造皮、聚醯胺、聚氨酯、聚酯、聚碳酸 酉旨等爲佳。亦可於與被硏磨面接觸之面施以格子溝紋/洞穴 /同心溝紋/螺旋溝紋等之加工。 [晶圓] 本發明中以硏磨液進行CMP之對象，做爲被硏磨體之晶 圓’係以直徑200mm以上者爲佳，3 00mm以上尤佳。3 00mm 以上者本發明之效果顯著。 -38- 200915411 [硏磨裝置] 可使用本發明之硏磨液實施硏磨的裝置無特殊限制，有 Mirra Mesa CMP ' Reflexion CMP(Applied Materials) ' FREX200 、 FREX300(荏原製作所）、NPS 3 30 1 、 NPS 230 1 (Nikon)、A-FP-310A、A-FP-210A(東京精密）、2300 TERES(Lam Research)、Momentum(Speedfam IPEC)等。 實施例 以下舉實施例更詳細說明本發明，但本發明不限於該 等。 [實施例1 ] 調製下示組成之硏磨液，進行硏磨實驗。 <組成（1) >Such a Low-k film is usually under the TEOS insulating film, and a barrier layer and a metal wiring are formed on the TEOS insulating film. -33-200915411 [Metal wiring material] In the present invention, the honed body (honing target) is preferably a semiconductor integrated circuit having an appropriate LSI or the like, and is preferably composed of a copper metal and/or a copper alloy. The raw material of this wiring is preferably copper alloy. Copper. It is more preferable to use a copper alloy containing silver. The silver content of the copper alloy is preferably 40% by mass or less, more preferably 1% by mass, more preferably 1% by mass or less, and most preferably in the range of 0.0 000 1 to 0% by mass. [Wiring thickness] In the present invention, the honed body (honing object) is preferably used in the case of a 系 系 ' 具有 具有 0 0 0 0 0 0 0 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有The following are preferred. On the other hand, the honing system is preferably used for, for example, a wiring harness having an MPU component of 12.12#m or less, and 〇.〇9#ιη is preferably better than μm. The above-described present invention particularly exerts an excellent effect on the honed body having such wiring. [Horse method] The honing liquid of the present invention has (1) a concentrated liquid, and is diluted with a water solution to be used as a use liquid, and (2) prepared in the form of the following aqueous solution, and if necessary, diluted with water. Use liquid, (3) modulate. Any of the honing methods using the honing liquid of the present invention may be employed.铜 0.0 之 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 The honing pad on the honing platform is in contact with the honed surface of the honed body to make the honed surface and the honing pad relatively move. A device for honing can use a general honing device having a holder for holding a honed body having a honed surface (for example, a wafer on which a film of a conductive material is formed, etc.) and attaching a honing Pad (with a variable number of motors, etc.) honing platform. As the honing pad, a general non-woven fabric, a foamed urethane, a porous fluororesin, or the like can be used without particular limitation. The honing condition is also not particularly limited, and the rotational speed of the honing platform is preferably a low number of revolutions of 200 rpm or less which does not cause the honing body to fly out. Pressing the honing pad to press the pressure of the honed body with the honed surface (the honing film) is preferably 0.68~34.5KPa' for the in-plane uniformity and pattern of the honed body at the honing speed The flatness is preferably 3.40 to 20.7 KPa. During the honing, the honing liquid is continuously supplied to the honing pad by a pump or the like. After the completion of the honing, the honed body is sufficiently washed in the running water, and then the water droplets adhering to the honed body are removed by a spin dryer or the like to be dried. In the present invention, as the method (1), when the concentrate is diluted, the aqueous solution shown below can be used. The aqueous solution already contains at least one of (A) colloidal vermiculite particles, (B) a hydrophilic benzotriazole derivative, (C) a hydrophobic benzotriazole derivative, and (D) an oxidizing agent. The components contained in the aqueous solution and the components contained in the concentrated liquid to be diluted are used as components of the honing liquid (use liquid) used in the honing. Thus, when the concentrate is diluted with an aqueous solution, the component which is difficult to dissolve can be prepared in the form of an aqueous solution, and a more concentrated concentrate can be prepared. -35- 200915411 Further, in the method of diluting the concentrated liquid with water or an aqueous solution, the piping for supplying the concentrated honing liquid and the piping for supplying the water or the aqueous solution are mixed and mixed in the middle, and are supplied to the mixed dilution honing liquid. Liquid in the method of honing the mat. The mixing of the concentrated liquid with water or an aqueous solution may be carried out by a method in which a liquid is mutually impact-mixed by a narrow passage under a pressurized state, a method of providing a rotating blade in a pipe, and the like. The supply rate of the honing liquid is preferably 10 to 1 〇〇〇m 1 / mi η, in order to satisfy the uniformity and pattern flatness in the honing surface under the honing speed, and the ratio is 170 to 800 ml/min. Better. Further, the concentrate is diluted with water or an aqueous solution and honed, and a pipe for supplying the honing liquid and a pipe for supplying water or an aqueous solution are separately provided, and each of the liquid is supplied to the honing pad, and the lap pad and the quilt are supplied. The method of mixing the relative motion of the honing surface and honing it. Further, a method in which a specific amount of the concentrate is mixed with water or an aqueous solution and mixed with the mixed honing liquid on the honing pad may be used. Other honing methods include dividing the components contained in the honing liquid into at least two constituent components. When used, it is diluted with water or an aqueous solution, and is supplied to the honing pad on the honing platform to make contact with the surface to be honed. The method of honing the surface and the honing pad to move relative to each other. For example, the oxidizing agent may be the component (A), and the other additives and water may be the component (B). When used, the component (the phantom and the component (B) may be diluted with water or an aqueous solution. The additive having a low solubility may also be used. It is divided into the constituent components (A) and (B), and is used by diluting the constituent component (A) and the constituent component (B) -36-200915411 in the water or aqueous solution. In the above case, it is necessary to have a supply composition. a component (A), a component (B), a pipe for water or an aqueous solution, and a method of mixing the three pipes into a pipe of one pipe supplied to the honing pad, and mixing the same in the pipe. After the piping, the other piping is combined. Specifically, a method of mixing the constituent components and the other constituent components containing the insoluble additive, and prolonging the mixing path to ensure the dissolution time 'recombination with the water or the aqueous solution is obtained. f. Other mixing methods are as above. Directly transfer the 3 pipes to the honing pad, mix the lap pad with the relative movement of the honed surface, or mix the 3 components in a container, and then supply the diluted 硏 to the honing pad. In the above method, the first constituent component containing the oxidizing agent may be kept at 40 ° C or lower, and the other constituent components may be heated from room temperature to 100 ° C to mix the first constituent component with other constituent components. Or when adding water or an aqueous solution to dilute the liquid temperature to 40 ° C or less. This method is a method of increasing the solubility of a low solubility raw material in the honing liquid by using a phenomenon in which the temperature is high and the solubility is high. The raw material which is dissolved by heating the other constituent components in the range of room temperature to 100 ° C is precipitated from the solution when the temperature is lowered. Therefore, when other components in a low temperature state are used, it is necessary to warm the mixture to dissolve the precipitated raw material. Here, a means for heating and infusion as a raw material to dissolve other constituent components, a method of mixing the liquid containing the precipitate with the liquid, and injecting the liquid to heat the tube to dissolve the mixture may be employed. When the temperature of the first constituent component containing the oxidizing agent is higher than 40° C., the oxidizing agent is decomposed. Therefore, when the other constituent component heated and the first constituent component containing the oxidizing agent are mixed, -37- 200915411 The temperature is preferably 40 ° C or less. In the present invention, the composition of the honing liquid may be divided into two or more parts and supplied to the surface to be honed. It is preferable to supply the component containing the organic acid, and the honing liquid may be a concentrated liquid, and the dilution water may be supplied to the surface to be honed. In the present invention, the component of the honing liquid is divided into two or more parts and supplied to the quilt. In the method of honing the surface, the supply amount represents the total amount of supply from each pipe. [Mat] The honing pad which is suitable for the honing method of the present invention may be a non-foamed structural mat or a foamed structural mat. The mat uses a hard synthetic resin block such as a plastic sheet, and the latter has three types of independent foam (dry foaming), continuous foam (wet foaming), and two-layer composite (layered). A two-layer composite (layered system) is especially preferred. Foaming can be uniform or non-uniform. ϋ One step can be used to contain granules (such as cerium oxide, sand, alumina, resin, etc.) that are generally used in honing. In terms of hardness, it may be either soft or hard. In the case of the laminated layer, it is preferred to use the hardness of each layer. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate or the like. It is also possible to apply lattice grooves/cavities/concentric grooves/spiral grooves to the surface that is in contact with the honed surface. [Wafer] In the present invention, the object of CMP by the honing liquid is preferably a crystal diameter of the honed body of 200 mm or more, more preferably 300 mm or more. The effect of the present invention is remarkable in the case of 3 00 mm or more. -38- 200915411 [Horry Device] There are no special restrictions on the device that can be used for honing using the honing fluid of the present invention, and there are Mirra Mesa CMP 'Reflexion CMP (Applied Materials) 'FREX200, FREX300 (荏原制所), NPS 3 30 1 NPS 230 1 (Nikon), A-FP-310A, A-FP-210A (Tokyo Precision), 2300 TERES (Lam Research), Momentum (Speedfam IPEC), and the like. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto. [Example 1] A honing liquid having the composition shown below was prepared, and a honing experiment was performed. <Composition (1) >

(A)硏磨粒子：膠體矽石粒子A-1 粉體換算l〇〇g/L(A) Honing particles: colloidal vermiculite particles A-1 powder conversion l〇〇g/L

(B )親水性B T A衍生物：具體例化合物B 1 0.2 g/L(B) Hydrophilic B T A derivative: specific example compound B 1 0.2 g/L

(C) 疏水性BTA衍生物：具體例化合物Cl 0.8 g/L(C) Hydrophobic BTA derivative: specific example compound Cl 0.8 g/L

(D) 氧化劑：過氧化氫 5g/L (F)水溶性高分子：重量平均分子量15 000之聚乙嫌醇(D) Oxidizing agent: hydrogen peroxide 5g/L (F) water-soluble polymer: polyethylene glycol with a weight average molecular weight of 15 000

1 .Og/L1 .Og/L

•加純水至總量 1 0 0 0 m L • pH(以氨水與硝酸調整） 3 〇 <評估方法> 硏磨裝置係使用MUSASIN◦電子公司製裝置MA_3〇〇D 依下述條件，一邊供給漿體一邊硏磨下述之晶圓。 -39- 200915411 •台轉數： 112rpm •頭轉數： 1 1 3rpm •硏磨壓力： 9. 19kPa •硏磨墊：Rodel Nitta(股）製 IC1400 XY-K-Pad •硏磨液供給速度： 5 0 m 1 / m 1 η <硏磨對象> 凹陷及侵蝕評估之晶圓係如下準備。 首先，經光微影步驟與反應性離子蝕刻步驟將Si基盤上 之氧化矽膜圖案化，形成寬度0.09~100 // m，深度600nm 之配線用溝與連接孔。其次，以濺鍍法形成厚度20nm之 Ta膜，繼之以濺鍍法形成厚度50nm之銅膜。然後以鍍敷 法形成合計厚度lOOOnm之銅膜。將此晶圓（通稱8 54PTN晶 圓）切成6x6cm，爲硏磨對象晶圓。 <凹陷及侵蝕評估> 首先，將該硏磨對象晶圓使用Cu-CMP漿體以恰相當於 Ο P + 3 0 %之時間硏磨。其次，使用該組成（1)之硏磨液硏磨該 晶圓 45秒，處理後之晶圓使用觸針式落差測定計 DektakV 320Si(Veeco公司製）測定9^111/1# m的線條/間隔 部之落差，爲侵蝕量。得到之各結果如表1。 [實施例2~7及比較例1~4] 變更實施例1中之組成，改依下述表1所述之組成調製 硏磨液使用，以如同實施例1之硏磨條件進行硏磨實驗。 結果如表1。 -40- 200915411 侵蝕 (nm) 〇 CnI 〇 τ~~Η 〇 S 〇 〇 凹陷 (nm) CO ON ON V〇 o OO CZ) ρ S 运_ {A3<rn 1 TBAN (〇.5g/L) TBAN (〇.5g/L) DBSA (l.Og/L) 1 DBSA (l.Og/L) TMAN (〇.5g/L) DBSA (l.Og/L) J 1 1 有機酸 (含量） 1 氍G 耍S 氍Θ E： 〇 1 經G E〇 天冬胺酸 (〇.5g/L) 1 氍G 舆 ίπ 〇 1 1 1 水溶性高分子 (含量） (MW15000)聚乙烯醇 (l.〇g/L) (MW30000)羧甲纖維素 (l.Og/L) (MW8000)聚乙烯醇 (l.Og/L) (MW10000)羧甲纖維素 (l.Og/L) (MW8000)聚乙烯醇 (l.Og/L) (MW15000)聚乙烯醇 (l.Og/L) (MW30000)羧甲纖維素 (l.Og/L) 1 (MW15000)聚乙烯醇 (l.Og/L) 1 (MW15000)聚乙烯醇 (l.Og/L) BTA衍生物 (含量） Bl(0.2g/L) Cl(0.8g/L) B2(0.2g/L) C4(0.8g/L) s /—S OJQ bi} c〇 oo 〇 〇 CO m U —S bjo c〇 oo O CD r- cn m U © S § Bl(0.2g/L) C4(0.4g/L) BB2(0.4g/L) ^ td td OX) &/) txo »—H r-H OO o 〇 o __^ '--- y—i t—H PQ PQ CJ BTA( l.Og/L) BTA( l.Og/L) BTA( l.Og/L) BTA( l.Og/L) 硏磨粒子 (含量） A-l(100g/L) A-3(100g/L) A-l(100g/L) A-2(20g/L) A-l(100g/L) A-l(100g/L) A-2(150g/L) 1 A-l(50g/L) A-3(50g/L) A-4(100g/L) A-5(100g/L) A-4(100g/L) A-l(100g/L) 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 比較例1 比較例2 比較例3 比較例4 200915411 該表1所列之（B)親水性之苯并***衍生物B 1、2、4、5、 7及（C)疏水性苯并***衍生物C 1〜C4指前述例示化合物。 倂用之苯并***B B 1、B B 2係以下之化合物。• Add pure water to a total of 1 0 0 m L • pH (adjusted with ammonia and nitric acid) 3 〇<Evaluation method> The honing device uses the MA_3〇〇D manufactured by MUSASIN◦Electronics Co., Ltd. according to the following conditions, The following wafers are honed while supplying the slurry. -39- 200915411 • Number of revolutions: 112 rpm • Number of revolutions: 1 1 3 rpm • Honing pressure: 9. 19 kPa • Honing pad: Rodel Nitta IC1400 XY-K-Pad • Honing fluid supply speed: 5 0 m 1 / m 1 η <honing objects> The wafers for dent and erosion evaluation are prepared as follows. First, the ruthenium oxide film on the Si substrate is patterned by a photolithography step and a reactive ion etching step to form a wiring trench and a connection hole having a width of 0.09 to 100 // m and a depth of 600 nm. Next, a Ta film having a thickness of 20 nm was formed by sputtering, followed by sputtering to form a copper film having a thickness of 50 nm. Then, a copper film having a total thickness of 100 nm was formed by plating. This wafer (commonly known as 8 54 PTN crystal) was cut into 6 x 6 cm to honing the target wafer. <Indentation and erosion evaluation> First, the honing target wafer was honed using a Cu-CMP slurry at a time equivalent to Ο P + 30%. Next, the wafer was honed using the honing liquid of the composition (1) for 45 seconds, and the processed wafer was measured for a line of 9^111/1# m using a stylus type drop meter Dektak V 320Si (manufactured by Veeco). The difference in the spacing is the amount of erosion. The results obtained are shown in Table 1. [Examples 2 to 7 and Comparative Examples 1 to 4] The composition in Example 1 was changed, and the composition honing liquid described in Table 1 below was used, and the honing experiment was carried out in the same manner as the honing condition of Example 1. . The results are shown in Table 1. -40- 200915411 Erosion (nm) 〇CnI 〇τ~~Η 〇S 〇〇 sag (nm) CO ON ON V〇o OO CZ) ρ S _ _ {A3<rn 1 TBAN (〇.5g/L) TBAN (〇.5g/L) DBSA (l.Og/L) 1 DBSA (l.Og/L) TMAN (〇.5g/L) DBSA (l.Og/L) J 1 1 Organic acid (content) 1 氍G S S 氍Θ E: 〇1 by GE 〇 aspartic acid (〇.5g / L) 1 氍G 舆ίπ 〇 1 1 1 Water-soluble polymer (content) (MW15000) polyvinyl alcohol (l.〇g /L) (MW30000) carboxymethylcellulose (1.0 g/L) (MW 8000) polyvinyl alcohol (1.0 g / L) (MW 10000) carboxymethyl cellulose (1.0 g / L) (MW 8000) polyvinyl alcohol (l.Og/L) (MW15000) polyvinyl alcohol (1.0 g/L) (MW30000) carboxymethylcellulose (1.0 g/L) 1 (MW15000) polyvinyl alcohol (1.0 g/L) 1 ( MW15000) polyvinyl alcohol (1.0 g/L) BTA derivative (content) Bl (0.2 g / L) Cl (0.8 g / L) B2 (0.2 g / L) C4 (0.8 g / L) s / - S OJQ bi} c〇oo 〇〇CO m U —S bjo c〇oo O CD r- cn m U © S § Bl(0.2g/L) C4(0.4g/L) BB2(0.4g/L) ^ td Td OX) &/) txo »—H rH OO o 〇o __^ '--- y—it—H PQ PQ CJ BTA( l.Og/L) BTA( l.Og/L) BTA( l. Og/L) BTA ( l.Og/L) honing particles (content Al(100g/L) A-3(100g/L) Al(100g/L) A-2(20g/L) Al(100g/L) Al(100g/L) A-2(150g/L) 1 Al (50 g/L) A-3 (50 g/L) A-4 (100 g/L) A-5 (100 g/L) A-4 (100 g/L) Al (100 g/L) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 200915411 (B) Hydrophilic benzotriazole derivatives B 1 and 2 listed in Table 1 4, 5, 7 and (C) Hydrophobic benzotriazole derivatives C 1 to C4 refer to the aforementioned exemplified compounds. A compound of the following benzotriazole B B 1 or B B 2 is used.

BB1BB1

NN

NN

I ch2cooh ch2ococh2ch2coch3 該表1中簡稱之化合物詳細如下。 TBAN :硝酸四丁錶[陽離子性四級銨鹽化合物] T M A N :硝酸四甲錢[陽離子性四級錢鹽化合物] DBSA:十二苯磺酸[界面活性劑] B T A : 1，2,3 -苯并***[腐蝕抑制劑] 該表1中““意指該項目不添加該化合物。 該表1中所列之硏磨粒子詳如下述表2。又’硏磨粒子 之平均粒徑係以SEM(掃猫電子顯微鏡）觀測硏磨粒子時， 構成1粒子的最小構成粒子徑之測定値 表 2 _ _______ 硏磨粒子種類 粒徑 (nm) A-1 膠體矽石 PL3 繭形 35 A-2 膠體矽石 PL3L 球狀 35 A-3 膠體矽石 PL3H 凝集塊 35 A-4 氧化鋁 氧化鋁C 凝集塊 100 A-5 煙霧矽石 AEROSDL50 凝集塊 50 -42 - 200915411 表2中Α-1~Α-3之膠體矽石係扶桑化學公司製之膠體矽 石。此外，A-4之氧化鋁係日本AEROSIL公司製，A-5之 煙霧矽石係日本AEROSIL公司製。 依表1，與比較例1 ~ 4比較，使用實施例卜7之硏磨液 時’凹陷及侵蝕之抑制效果高。 另一方面，比較例1〜4之硏磨液則凹陷及侵蝕任一的抑 制效果皆劣於實施例之硏磨液。 基於以上可知，本發明之硏磨液能抑制凹陷及侵蝕之發 /生’達成良好之平坦性。 【圖式簡單說明】 ftE 〇 /\\\ 【主要元件符號說明】 無。 -43-I ch2cooh ch2ococh2ch2coch3 The compounds referred to in Table 1 are detailed below. TBAN: tetrabutyl nitrate [cationic quaternary ammonium compound] TMAN: tetramethyl nitrate [cationic quaternary salt compound] DBSA: dodecylsulfonic acid [surfactant] BTA : 1,2,3 - Benzotriazole [Corrosion Inhibitor] In Table 1, "" means that the compound is not added to the project. The honing particles listed in Table 1 are detailed in Table 2 below. Further, when the average particle diameter of the honing particles is observed by SEM (sweeping cat electron microscope), the measurement of the minimum constituent particle diameter of the first particle is shown in Table 2 _ _______ honing particle type particle size (nm) A- 1 colloidal vermiculite PL3 茧 shape 35 A-2 colloidal vermiculite PL3L spherical 35 A-3 colloidal vermiculite PL3H agglomerate 35 A-4 alumina alumina C agglomerate 100 A-5 smog meteorite AEROSDL50 agglomerate 50 - 42 - 200915411 The colloidal vermiculite of Α-1~Α-3 in Table 2 is a colloidal vermiculite made by Fusang Chemical Co., Ltd. Further, the alumina of A-4 is manufactured by AEROSIL Co., Ltd. of Japan, and the smogstone of A-5 is manufactured by AEROSIL Co., Ltd. of Japan. According to Table 1, in comparison with Comparative Examples 1 to 4, when the honing liquid of Example 7 was used, the effect of suppressing depression and erosion was high. On the other hand, the honing liquids of Comparative Examples 1 to 4 were inferior to the honing liquid of the examples in terms of the suppression effect of the sag and the etch. Based on the above, it is understood that the honing liquid of the present invention can suppress the occurrence of dents and erosions to achieve good flatness. [Simple description] ftE 〇 /\\\ [Main component symbol description] None. -43-

Claims (1)

200915411 十、申請專利範圍： 1.—種硏磨液，係具有阻障層之半導體積體電路的平坦化 步驟中，用於化學機械硏磨之硏磨液，其特徵爲 含有（A)膠體矽石粒子、（B)親水性之苯并***衍生物、 (C)疏水性之苯并***衍生物及（D)氧化劑。 2 .如申請專利範圍第1項之硏磨液，其中該（B )親水性之苯 并***衍生物具有羥基、胺基、羧基或磺酸基。 3. 如申請專利範圍第1或2項之硏磨液，其中該（C)疏水性 之苯并***衍生物具有非取代之烷基、碳原子數1 0以上 之烷氧基、碳原子數15以上之烷氧羰基、碳原子數15 以上之羰醯胺基或碳原子數15以上之胺羰基。 4. 如申請專利範圍第1或2項之硏磨液，其中更含有胺基 酸。 5 ·如申請專利範圍第1或2項之硏磨液，其中更含有水溶 性高分子。 6.如申請專利範圍第1或2項之硏磨液，其中該（B)親水性 之苯并***衍生物與該（C)疏水性之苯并***衍生物之合 計濃度係0.005質量％以上且5質量％以下。 7 ·如申請專利範圍第1或2項之硏磨液，其中該（B)親水性 之苯并***衍生物與該（C)疏水性之苯并***衍生物之含 有比率係質量比2 : ~丨：5。 8. 如申請專利範圍第丨或2項之硏磨液，其中pH係2〜5。 9. 一種硏磨方法，其特徵爲使用含有（A)膠體矽石粒子、（B) -44 - 200915411 親水性之苯并***衍生物、（C)疏水性之苯并 及（D)氧化劑之硏磨液，化學機械硏磨具備阻 體積體電路。 1 0 .如申請專利範圍第9項之硏磨方法，其中5 ΊΊ、Ru或該等之衍生物形成之上述阻障層。 ***衍生物 障層之半導 f磨以Μη、 -45- 200915411 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明: 〇 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：200915411 X. Patent application scope: 1. A honing fluid, a honing fluid for chemical mechanical honing in a planarization step of a semiconductor integrated circuit having a barrier layer, characterized in that it contains (A) colloid Vermiculite particles, (B) a hydrophilic benzotriazole derivative, (C) a hydrophobic benzotriazole derivative, and (D) an oxidizing agent. 2. The honing fluid according to claim 1, wherein the (B) hydrophilic benzotriazole derivative has a hydroxyl group, an amine group, a carboxyl group or a sulfonic acid group. 3. The honing liquid according to claim 1 or 2, wherein the (C) hydrophobic benzotriazole derivative has an unsubstituted alkyl group, an alkoxy group having 10 or more carbon atoms, and a carbon atom. The alkoxycarbonyl group having 15 or more, the carbonyl hydrazine group having 15 or more carbon atoms or the amine carbonyl group having 15 or more carbon atoms. 4. For the honing fluid of claim 1 or 2, which further contains an amino acid. 5 · The honing liquid of claim 1 or 2, which further contains a water-soluble polymer. 6. The honing liquid according to claim 1 or 2, wherein the total concentration of the (B) hydrophilic benzotriazole derivative and the (C) hydrophobic benzotriazole derivative is 0.005 mass % or more and 5% by mass or less. 7. The honing liquid according to claim 1 or 2, wherein the content ratio of the (B) hydrophilic benzotriazole derivative to the (C) hydrophobic benzotriazole derivative is mass ratio 2 : ~丨: 5. 8. For example, the honing fluid of the second or second patent application, wherein the pH system is 2 to 5. A honing method characterized by using (A) colloidal vermiculite particles, (B) -44 - 200915411 hydrophilic benzotriazole derivative, (C) hydrophobic benzo and (D) oxidizing agent The honing fluid, chemical mechanical honing has a resistance volume circuit. 10. The honing method of claim 9, wherein the barrier layer is formed of 5 Å, Ru or a derivative thereof. Triazole derivatives The semi-conductivity of the barrier layer f is milled to Μη, -45- 200915411 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 八 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: