200826164 九、發明說明： 【發明所屬之技術領域】 本發明係關於用於例如在硏磨加工半導體裝置時，以 化學機械方式加以平坦化之硏磨方法及硏磨用組成物。 【先前技術】 在開發以半導體積體電路（在下文中則稱爲「LSI」） 所代表的半導體裝置方面，近年來爲了小型化•高速化而 要求藉由配線之微細化與積層化的高密度化•高積體化。 對於用於LSI的層間絶緣膜，則爲了 LSI之高速化而要求 配線間電容少的相對介電常數（relative dielectric constant )爲低之材料。 迄今爲止，半導體裝置之層間絶緣膜材料一向是使用 Si〇2，且其相對介電常數爲約3.8至4.2。然而，隨著線寬 演變成狹窄，層間絶緣膜材料之相對介電常數也必須予以 降低’例如線寬爲130奈米（nm )之元件，則需要相對介 電常數爲約2.5至3.0之材料。 可用於形成層間絶緣膜爲低相對介電常數之絶緣膜（ Low-k膜）所使用的材料，已知有SiOC系之材料（例如， 複數個Si— C、或包含Si— Η鍵之Si〇C)、MSQ等之有機_ 無機混成系材料。 具體而言，可用於形成低相對介電常數絶緣膜之材料 ’在SiOC系則有HSG-R7 (日立化成工業股份有限公司（ Hitachi Chemical Co· Ltd.))、黑鑽石（BLACKDIAMOND )(美商應用材料股份有限公司（Applied Materials，Inc. 200826164 ))等。 該等之Low-k膜，爲了 LSI之微細化則需要平坦化， 因此要求爲此所需要的技術。 將Low-k膜予以平坦化之方法，在專利文獻1中係揭 示一種使用CMP技術之平坦化方法，亦即，硏磨粒係使用 氧化鈽粒子來硏磨之方法。所謂的「CMP」是「化學機械 硏磨（Chemical Mechanical Polishing)」之縮寫語，一般 而言，其係在圓形的硏磨平台（platen )上貼附硏磨墊，以 硏磨液浸漬硏磨墊表面，將基板（晶圓）表面壓上於硏磨 墊，並在由其背面外加特定壓力（硏磨壓力）之狀態下， 使硏磨平台與基板之兩者相對旋轉，而以產生的機械性摩 擦來平坦化被硏磨面之表面者。 然而，硏磨粒使用氧化鈽粒子來硏磨之方法，其硏磨 速度緩慢，且容易造成金屬配線之間的絶緣膜受到過分硏 磨，而形成複數個配線金屬面表面呈碟狀凹部之現象（侵 蝕）。 (專利文獻1 )特開第2000-28625 5號公報 【發明内容】 〔所欲解決之技術問題〕 爲了高速化正在發展微細化的LSI之運作，藉由絶緣 膜之低介電常數化來降低配線間電容是有其必要。惟因低 相對介電常數之絶緣膜係機械強度比較低，以致欲在不至 於對此等絶緣膜造成刮傷等之缺陷下，提高硏磨速度則有 困難。 200826164 本發明係提供一種即使在硏磨使用低相對介電常數之 絶緣膜材料的被硏磨體之情形下，也可加快低相對介電常 數絶緣膜的硏磨速度之硏磨用組成物、及使用其之硏磨方 法爲其目的，且以達成該目的爲其課題。 〔解決問題之技術方法〕 爲解決上述課題之具體方法如下所述： (1) 一種硏磨用組成物，係在半導體裝置之製造方法中 ，用於以化學機械方式硏磨由具有有機矽氧烷結構 之相對介電常數爲3.0以下之絶緣膜隔著阻障金屬 層（barrier metal layer)而形成埋入配線所構成的 被硏磨體之該絶緣膜，該硏磨用組成物包含一次粒 徑（primary particle diameter)爲 10 至 80 奈米之二 氧化砂（silica)粒子、苯并三嗤（benzotriazole) 化合物、及1至10質量％之無機鹽，且pH爲在8 至1 1之範圍。 (2 ) 如第（1 )項所述之硏磨用組成物，其中該二氧化矽 粒子之濃度爲0.5至15質量％。 - (3 ) 如第（1 )或（2 )項所述之硏磨用組成物，其中該 苯并三唑化合物係選自1，2,3-苯并三唑（BTA)、5,6· 二甲基-1，2,3-苯并三唑（DBTA ) 、1-(1，2·二羧基 乙基）苯并三唑（DCEBTA ) 、1 -〔 N，N-雙（羥基乙 基）胺基甲基〕苯并三唑（HEABTA) 、1-(羥基甲 基）苯并三唑（HMBTA)中之至少一種。 (4 ) 如第（1 )至（3 )項中任一項所述之硏磨用組成物 200826164 ，其中該無機鹽係選自銨鹽、鈉鹽、鉀鹽中之至少 一種。 (5 ) 如第（1 )至（4 )項中任一項所述之硏磨用組成物 ，其係不含該苯并三唑化合物以外之芳香環化合物 〇 (6) 一種硏磨方法，係對硏磨平台上之硏磨墊供應硏磨 用組成物，邊使該硏磨墊與被硏磨體之絶緣膜接觸 ，邊旋轉該硏磨平台以使接觸面相對運動來進行硏 磨，其中該絶緣膜係在具有有機矽氧烷結構之相對 介電常數爲3.0以下之絶緣膜隔著阻障層而形成埋 入配線所構成的該被硏磨體之絶緣膜，且該硏磨用 組成物係如第（1 )至（5 )項中任一項所述之硏磨 用組成物。 (7 ) 如第（6 )項所述之硏磨方法，其中使硏磨墊接觸於 被硏磨體之絶緣膜時之負載（硏磨壓）爲0.69至21.6 KPa。 (8 ) 如第（6 )或（7 )項所述之硏磨方法，其中對硏磨 平台上之硏磨墊供應硏磨用組成物時之供應流量爲 0.035 至 0.60 ml/min · cm2 ° 〔發明之功效〕 根據本發明，即可提供一種即使在硏磨使用低相對介 電常數之絶緣膜材料的被硏磨體之情形下，也能加快低相 對介電常數絶緣膜的硏磨速度之硏磨用組成物、及使用其 之硏磨方法。 200826164 【實施方式】 〔本發明之最佳實施方式〕 本發明之硏磨用組成物係在半導體裝 ，用於以化學機械方式硏磨由具有有機形 介電常數爲3 · 0以下之絶緣膜隔著阻障層 所構成的被硏磨體之該絶緣膜，該硏磨用 粒徑爲1 0至8 0奈米之二氧化矽粒子、驾 及1至10質量％之無機鹽，且pH爲在8 以下，就本發明之具體方法加以說明 〔低相對介電常數絶緣膜〕 在本發明之絶緣膜（層間絶緣膜）係 結構之相對介電常數爲3.0以下之低相癸 膜（在下文中也稱爲「本發明之Low-k膜 可用於形成該低相對介電常數絶緣腠 只要其爲能形成具有有機矽氧烷結構之 3. 〇以下之絶緣膜時，則可在並無特殊限彳 較佳爲具有有機矽氧烷結構之SiOC ( —C、或包含Si— Η鍵之SiOC) 、MSQ等 成材料。 其中，較佳爲含有以下述通式（I )戶f 烷結構單元。 目置之製造方法中 7氧院結構之相對 ί而形成埋入配線 丨組成物包含一次 三并三唑化合物、 至1 1之範圍。 具有有機矽氧烷 ‘介電常數之絶緣 J ) ° 所使用的材料， 相對介電常數爲 訊下加以適用。 例如，複數個Si 之有機系-無機混 1代表之有機矽氧 200826164BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a honing method and a honing composition for planarizing chemically, for example, in honing a semiconductor device. [Prior Art] In recent years, in order to reduce the size and speed of semiconductor devices, the semiconductor devices represented by the semiconductor integrated circuits (hereinafter referred to as "LSI") have been required to have a high density and a high density of wiring. • High integration. In the interlayer insulating film used for LSI, in order to increase the speed of the LSI, a material having a low relative dielectric constant with a small inter-wiring capacitance is required. Heretofore, the interlayer insulating film material of a semiconductor device has conventionally used Si〇2, and its relative dielectric constant is about 3.8 to 4.2. However, as the line width evolves to be narrow, the relative dielectric constant of the interlayer insulating film material must also be lowered, for example, a component having a line width of 130 nm (nm), and a material having a relative dielectric constant of about 2.5 to 3.0 is required. . A material which can be used for forming an insulating film (Low-k film) in which an interlayer insulating film is a low relative dielectric constant, and a material of SiOC type (for example, a plurality of Si—C or Si containing a Si—Η bond is known.有机C), MSQ, etc. Organic _ Inorganic hybrid materials. Specifically, it can be used to form a material with a low relative dielectric constant insulating film. 'In the SiOC system, there are HSG-R7 (Hitachi Chemical Co. Ltd.) and BLACKDIAMOND (US). Applied Materials, Inc. (Applied Materials, Inc. 200826164)). These Low-k films require planarization in order to refine the LSI, and therefore a technique required for this is required. In the method of flattening the Low-k film, Patent Document 1 discloses a flattening method using a CMP technique, that is, a method in which the honing particles are honed using cerium oxide particles. The so-called "CMP" is the abbreviation of "Chemical Mechanical Polishing". Generally speaking, it is attached to a circular honing plate (platen) with a honing pad and impregnated with honing liquid. Grinding the surface of the substrate, pressing the surface of the substrate (wafer) against the honing pad, and rotating the honing platform and the substrate relative to each other with a specific pressure (honing pressure) applied thereto Mechanical friction to flatten the surface of the surface being honed. However, the honing grain is honed by cerium oxide particles, the honing speed is slow, and the insulating film between the metal wirings is easily excessively honed, and the surface of the plurality of wiring metal faces is formed into a dish-shaped concave portion. (erosion). [Patent Document 1] JP-A-2000-28625 5 SUMMARY OF INVENTION [Technical Problem to be Solved] In order to speed up the operation of the LSI which is being refined, the low dielectric constant of the insulating film is lowered. Wiring capacitance is necessary. However, the mechanical strength of the insulating film having a low relative dielectric constant is relatively low, so that it is difficult to increase the honing speed without causing scratches such as the insulating film. 200826164 The present invention provides a honing composition which can accelerate the honing speed of a low relative dielectric constant insulating film even in the case of honing a honed body using an insulating film material having a low relative dielectric constant, And the use of the honing method for its purpose, and to achieve this purpose as its subject. [Technical method for solving the problem] The specific method for solving the above problems is as follows: (1) A composition for honing, which is used in a method of manufacturing a semiconductor device, for chemical mechanical honing by having organic oxime An insulating film having a relative dielectric constant of an alkyl structure of 3.0 or less forms a barrier film of a honed body formed by embedding a wiring via a barrier metal layer, and the honing composition contains primary particles. The primary particle diameter is 10 to 80 nm of silica particles, benzotriazole compounds, and 1 to 10% by mass of inorganic salts, and the pH is in the range of 8 to 11. . (2) The honing composition according to Item (1), wherein the concentration of the cerium oxide particles is from 0.5 to 15% by mass. The honing composition according to the item (1) or (2), wherein the benzotriazole compound is selected from the group consisting of 1,2,3-benzotriazole (BTA), 5, 6 · Dimethyl-1,2,3-benzotriazole (DBTA), 1-(1,2·dicarboxyethyl)benzotriazole (DCEBTA), 1-[N,N-double (hydroxyl) At least one of amino)methyl]benzotriazole (HEABTA) and 1-(hydroxymethyl)benzotriazole (HMBTA). The honing composition 200826164 according to any one of the items (1) to (3), wherein the inorganic salt is at least one selected from the group consisting of an ammonium salt, a sodium salt and a potassium salt. (5) The honing composition according to any one of the items (1) to (4), which does not contain an aromatic ring compound other than the benzotriazole compound (6), a honing method, Providing a honing composition to the honing pad on the honing platform, and causing the honing pad to contact the insulating film of the honing body, and rotating the honing platform to make the contact surface move relative to each other to perform honing, The insulating film is an insulating film of the object to be honed, which is formed by embedding a wiring layer, with an insulating film having a relative dielectric constant of 3.0 or less of an organic siloxane structure, and is used for the honing. The honing composition according to any one of the items (1) to (5). (7) The honing method according to the item (6), wherein a load (honing pressure) when the honing pad is brought into contact with the insulating film of the honed body is 0.69 to 21.6 KPa. (8) The honing method according to item (6) or (7), wherein the supply flow rate for supplying the honing composition to the honing pad on the honing table is 0.035 to 0.60 ml/min · cm2 ° [Effect of the Invention] According to the present invention, it is possible to provide a honing speed of a low relative dielectric constant insulating film even in the case where a honed body of an insulating film material having a low relative dielectric constant is used for honing The honing composition and the honing method using the same. [Embodiment] The preferred embodiment of the present invention is a semiconductor package for chemically mechanically honing an insulating film having an organic dielectric constant of 3.0 or less. The insulating film of the honed body formed by the barrier layer, the cerium oxide particle having a particle diameter of 10 to 80 nm, and 1 to 10% by mass of an inorganic salt, and pH In the following, a specific method of the present invention will be described. [Low Relative Dielectric Constant Insulating Film] A low phase tantalum film having a relative dielectric constant of 3.0 or less in the insulating film (interlayer insulating film) structure of the present invention (below Also referred to herein as "the Low-k film of the present invention can be used to form the low relative dielectric constant insulating material, as long as it is capable of forming an insulating film having an organic germanium oxyalkylene structure of 3. 〇 or less, The material is preferably a material having an organic siloxane structure of SiOC (-C, or SiOC containing a ytterbium bond), MSQ or the like. Among them, it preferably contains a unit of the following formula (I) The relative structure of the 7 oxygen institute structure in the manufacturing method of the eye The composition for forming the buried wiring 包含 includes a primary tris-triazole compound and a range of 11. The insulating material having the dielectric constant of the organic siloxane is J). The material used has a relative dielectric constant. For example, a plurality of Si organic-inorganic mixed 1 represents organic oxime 200826164
通式（I) 通式（I)中，R1係代表氫原子、烴基或〇R3，R2係代 表烴基或OR4。R3、R4係分別獨立地代表烴基。 通式（Π中’以R1至R4所代表之烴基係包括脂肪族 烴基或芳香族烴基。 可用於形成如上所述之低相對介電常數絶緣膜之材料 係例如：「SiOC系」係包括·· HSG-R7 (日立化成工業股份 有限公司製造：相對介電常數爲2.8)、黑鑽石（ BLACKDIAMOND )(美商應用材料股份有限公司製造：相 對介電常數爲2.4至3.0)、Coral (香港商諾發系統有限公 司（Novellus Systems，Inc.)製造··相對介電常數爲2.4至 2.7) 、Aurora (日本EMS股份有限公司（EMS·，Inc.)製 造：相對介電常數爲2·7 );另外，「MSQ系」係包括： 0CDT-9C東京應化工業股份有限公司（Tokyo 〇hka Co. Ltd. )製造：相對介電常數爲2.7)、LKD-T200(JSR公司（JSR Corp.)製造：相對介電常數爲2.5至2.7) 、H0SP (霍尼 -10- 200826164 韋爾電子材料公司（Honeywell Electronic Materials)製造 :相對介電常數爲2.5 ) 、HSG-RZ25 (日立化成工業股份 有限公司製造：相對介電常數爲2.5) 、OCLT-31 (東京應 化工業股份有限公司製造：相對介電常數爲2 3 )、LKI^T4〇〇 (JSR公司製造：相對介電常數爲2.0至2.2)、HSG-6211X (日化成工業股份有限公司製造：相對介電常數爲2.1 )、ALCAP-S (旭化成工業股份有限公司（Asahi Kasei Chemicals)製造：相對介電常數爲ι·8至2.3) 、OCLT-77 (東京應化工業股份有限公司製造：相對介電常數爲1.9 至2.2) 、HSG-6211X(曰立化成工業股份有限公司製造： 相對介電常數爲2.4·) 、silica aerogel (神戸製鋼有限公司 (Kobe Steel·，Ltd.)製造：相對介電常數爲^丨至L4)等 ，但是並不受限於此等。 可用於形成低相對介電常數絶緣膜之材料可單獨使用 一種、或其數種組合倂用。並且，經由該等材料所形成之 絶緣膜也可具有微小空孔。 在本發明之絶緣膜之形成方法，也可爲電漿CVD法或 旋轉式塗佈法。 在本發明之絶緣膜之相對介電常數係必須爲3.0以下 ，但是較佳爲更低者，特佳爲1.8至2.8。 在本發明之相對介電常數，關於全面性膜則可以使用 水銀探針之測定方法，另外，關於經設置配線之絶緣膜的 相對介電常數則可以Presision 4284A LCR Meter(安捷倫科 技（Agilent Technologies)公司製造）來加以測定。例如 -11- 200826164 ，在線寬爲9 0奈米以下之元件，較佳爲相 於 2.4。 〔硏磨用組成物〕 本發明之硏磨用組成物，其特徵爲包 粒子、（b)苯并三嗤化合物、及（c)無 〔（a )二氧化矽粒子〕 本發明之硏磨用組成物係含有一次粒 米之二氧化矽粒子作爲構成成份。該二氧 爲硏磨粒。在本發明之「二氧化矽粒子」 澱二氧化矽、氣相法二氧化矽（白碳黑） 、膠態二氧化矽（colloidal silica )、合成 ，從硏磨速度的觀點來看，則較佳爲膠態 相法二氧化矽（白碳黑），更佳爲膠態二 膠態二氧化矽粒子之製造方法，例如 Si(sec-〇C4H9)4、Si(〇CH3)4、Si(〇C4H9)4 之 以溶膠-凝膠法加以水解即可製得。此種膠 其粒度分佈將呈非常陡峻者。 氣相法二氧化矽粒子之製造方法係包 矽之酸氫焰中之高溫水解法。 在本發明所謂的二氧化矽粒子之一次 示二氧化矽粒子之粒徑與具有其粒徑的粒 獲得的累積度數之關係的粒度累積曲線， 累積度數爲5 0 %之點的粒徑。該二氧化矽 示在由動態光散射法所測得之粒度分佈所 對介電常數爲低 含（a )二氧化矽 機鹽。 徑爲10至80奈 化矽粒子係用作 係包括例如=沉 (fumed silica ) 二氧化矽。其中 二氧化政、或氣 氧化砂。 將 Si(〇C2H5)4、 烷氧化矽化合物 態二氧化矽粒子 括例如在四氯化 粒徑係先求得表 子數予以積算所 而意謂該曲線之 粒子之粒徑係表 計算得之平均粒 -12- 200826164 徑。用於求出粒度分佈之測定裝置係使用例如LB·500 (堀 場製作所（Horiba, Ltd.)製造）等。 在本發明中，所包含的二氧化矽粒子之一次粒徑係需 要爲10至80奈米，但是較佳爲10至60奈米’更佳爲 至30奈米。從爲達成足夠的硏磨加工速度目的的觀點而言 ，較佳爲10奈米以上之粒子。另外，就在硏磨加工中不至 於造成過量摩擦熱之目的而言，粒徑較佳爲80奈米以下° 在本發明中，二氧化矽粒子係可單獨使用一種、或其 兩種以上組合倂用。 在本發明中，所包含的二氧化矽粒子之濃度，在使用 於硏磨時的硏磨用組成物中，較佳爲含有〇. 5至1 5質量％ 之比率，更佳爲1至10質量％。就爲達成足夠的硏磨加工 速度的觀點而言，濃度較佳爲0.5質量％以上。另外’從抑 制在硏磨加工中產生過量摩擦熱的觀點來看，則濃度較佳 爲15質量％以下。所謂的在硏磨用組成物中含有0.5至15 質量％之比率係意謂在硏磨用組成物每1公升中含有5至 150 克。 另外，本發明之硏磨用組成物雖然可以其狀態直接使 用，並且也可以經稀釋之形態來使用，但是即使爲稀釋硏 磨用組成物後使用之情形，使用時之硏磨用組成物稀釋液 中的濃度係仍與硏磨用組成物之濃度範圍相同，且較佳的 範圍也相同。 〔（b )苯并三唑化合物〕 本發明之硏磨液係含有苯并三唑化合物。 -13- 200826164 在本發明中，苯并三唑化合物較佳爲包含 苯并三唑（ΒΤΑ) 、5,6-二甲基-1，2,3-苯并三唑 1-(1,2-二羧基乙基）苯并三唑（DCEBTA)、 (羥基乙基）胺基甲基〕苯并三唑（HEABTA) 甲基）苯并三唑（HMBTA)中之至少一種。 苯并三唑化合物經使用特定的化合物，即 的低相對介電常數之絶緣膜與埋入配線的硏磨 擇比）之値。 在本發明使用之苯并三唑化合物可單獨使 其兩種以上組合倂用。 另一方面，該苯并三唑化合物之濃度，雖 限制，但是在使用於硏磨時的硏磨用組成物中 質量％以上、0.2質量％以下，更佳爲0.05質量 質量％以下。 在本發明之硏磨用組成物中，較佳爲不含 唑化合物以外之芳香環化合物。在本發明中， 合物以外之芳香環化合物係例如包括三唑、四 不含苯并三唑化合物以外之芳香環化合物，可 埋入配線之硏磨速度比（選擇比）之値。 〔（c )無機鹽〕 本發明之硏磨用組成物係在使用硏磨時之 物中含有1至10質量％之無機鹽。該添加量係 1公升之在使用於硏磨時之硏磨用組成物中爲1 100克之無機鹽。由於含有該範圍之無機鹽，可 選自1，2,3-(DBTA)、 1- 〔 N，N-雙 、1 -(羥基 可獲得適當 速度比（選 用一種、或 然並無特殊 較佳爲0 . 〇 1 %以上、0.2 上述苯并三 苯并三唑化 唑等。由於 獲得適當的 硏磨用組成 意謂相對於 I有10克至 提高低相對 • 14- 200826164 介電常數之絶緣膜的硏磨速度。 在本發明中，無機鹽之含量較佳爲丨至5質量％，更佳 爲2至3質量％。 可使用於本發明之無機鹽，雖然並無特殊限制，但是 從洗淨性的觀點來看，則較佳爲選自銨鹽、鈉鹽、鉀鹽中 之至少一種。其中，較佳爲銨鹽、鉀鹽，更佳爲錢鹽。 可使用於本發明的無機鹽之陰離子，並無特殊限制， 可使用例如：氯化物離子、硝酸離子、硫酸離子、磷酸離 子等。 可使用於本發明之無機鹽之具體實例係包括··硝酸錢 、硫酸銨、磷酸銨、氯化銨、硝酸鈉、硫酸鈉、氯化鈉、 硝酸鉀、硫酸鉀、氯化鉀等。 該等之中，從抑制隨著CMP的各種缺陷的觀點來看， 則較佳爲硝酸銨。 在本發明之上述無機鹽可單獨使用一種、或其兩種以 上組合倂用。 〔pH〕 本發明之硏磨用組成物，使用於硏磨時之硏磨用組成 物中的pH必須爲在8至1 1之範圍，但是PH較佳爲9至 1 1，更佳爲9.5至1 0.5。 爲調整pH爲較佳範圍，可使用鹼/酸或緩衝劑。本發 明之硏磨用組成物，使用於硏磨時的硏磨用組成物之pH在 該範圍時，則其係可發揮提高硏磨速度之功效。 「鹼/酸或緩衝劑」較佳爲氨、氫氧化銨及氫氧化四甲 -15- 200826164 基銨等之「有機氫氧化銨」：二乙醇胺、三乙醇胺、三 丙醇胺等「烷醇胺類」等之「非金屬鹼性劑」；氫氧化 、氫氧化鉀、氫氧化鋰等之「鹼金屬氫氧化物」：硝酸 硫酸、磷酸等之「無機酸」；碳酸鈉等之「碳酸鹽」； 酸三鈉等之「磷酸鹽」；硼酸鹽、四硼酸鹽、羥基安息 酸鹽等。特佳的鹼性劑是氫氧化銨、氫氧化鉀、氫氧化 及氫氧化四甲基銨。 鹼/酸或緩衝劑之添加量，只要其爲能維持pH於適 範圍之量即可，較佳爲使用於硏磨時之硏磨用組成物每 公升中設定在0.0001克至1克，更佳爲設定在0.001克 0.1 克。 〔氧化劑〕 在本發明之硏磨用組成物中，較佳爲含有可將硏磨 象之金屬加以氧化之化合物（氧化劑）。 「氧化劑」係包括例如：過氧化氫、過氧化物、硝 鹽、碘酸鹽、過碘酸鹽、次氯酸鹽、亞氯酸鹽、氯酸鹽 過氣酸鹽、過硫酸鹽、重絡酸鹽、過鍾酸鹽、臭氧水、 銀（II )鹽、鐵（III )鹽，其中適合使用過氧化氫。 「鐵（III )鹽」係包括例如：硝酸鐵（III )、氯化 (III )、硫酸鐵（III)、溴化鐵（III)等無機之鐵（ )鹽以外，適合使用鐵（III )之有機錯合鹽。 氧化劑之添加量，較佳爲每1公升使用於硏磨時之 磨液中，設定在0.01莫耳至1莫耳，特佳爲設定在0.05 耳至0.6莫耳。 異 鈉 Λ 磷 香 鋰 合 1 至 對 酸 及 鐵 III 硏 莫 -16- 200826164 〔螯合劑〕 在本發明之硏磨用組成物中，爲降低混入的多價金屬 離子等之不良影響，視需要可含有螯合劑。 「螯合劑」係包括例如：屬鈣或鎂之抗沉澱劑的通用 之硬水軟化劑或其類似化合物，例如氮基三醋酸、二伸乙 三胺五醋酸、伸乙二胺四醋酸、Ν,Ν,Ν-三亞甲基膦酸、伸 乙二胺-Ν，Ν，Ν’ ，Ν’ -四亞甲基磺酸、反式環己烷二胺四醋 酸、1，2-二胺基丙烷四醋酸、乙二醇醚二胺四醋酸、伸乙二 胺鄰羥基苯基醋酸、伸乙二胺二琥珀酸（SS體）、Ν- ( 2-羧酸根合乙基）-L-天冬胺酸、^ -丙胺酸二醋酸、2-膦酸丁 烷-1，2,4-三羧酸、卜羥基亞乙基-1,1-二膦酸、Ν，Ν’ -雙（2-羥基苯甲基）伸乙二胺- Ν，Ν’ -二醋酸、1，2-二羥基苯- 4,6-二磺酸等。 〔有機酸〕 在本發明之硏磨液可進一步含有有機酸。 所謂的有機酸係結構與用於氧化金屬之氧化劑不同的 化合物’並非爲包含作爲如上所述之氧化劑而發生作用的 酸。在此所謂酸係具有作爲促進氧化、調整pH、緩衝劑之 作用。 在本發明中之有機酸較佳爲選自由下列所組成之族群 者。 亦即，包括：甲酸、醋酸、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 -17- 200826164 酸、乙醇酸、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、鄰苯二甲酸、蘋果 酸、酒石酸、檸檬酸、乳酸、及其等之銨鹽或鹼金屬鹽等 之鹽、硫酸、硝酸、氨、銨鹽類、或其等之混合物等。 該等之中，甲酸、丙二酸、蘋果酸、酒石酸、檸檬酸 係對於含有選自銅、銅合金及銅或銅合金之氧化物中之至 少一種金屬層之積層膜是適合使用。 在本發明中之有機酸係適合使用胺基酸等。 該胺基酸等較佳爲具有水溶性者，更佳爲選自由下列 所組成之族群者。 亦即，較佳爲選自例如甘胺酸、L-丙胺酸、Θ -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-合金型異白胺酸、L-苯基丙胺 酸、L-脯胺酸、肌胺酸、L-鳥胺酸、L·離胺酸、牛磺酸、 L-絲胺酸、L-蘇胺酸、L-別蘇胺酸、L-高絲胺酸、L-酪胺酸 、3,5-二碘-L-酪胺酸、/3-(3,4-二羥基苯基）-L-丙胺酸、 L-甲狀腺素' 4-羥基-L-脯胺酸、L-半胱胺酸、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-磺基丙胺酸、L-天冬胺酸、L-麩胺酸、S-(羧基甲基）-L-半胱胺酸、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 -羥基-L-離胺酸、肌酸、L-犬尿胺酸、L·組胺酸、1-甲基-L-組胺酸 、3-甲基-L-組胺酸、麥角硫醇、L-色胺酸、放線菌素C1、 蜂母明（Apamin)、血管收縮素i(angi〇tensin I)、血管收 -18- 200826164 縮素II、及抗木瓜酶等之胺基酸等中之至少一種。 該等之中，特別是對於蘋果酸、酒石酸、檸檬酸、甘 胺酸、乙醇酸而言，由於可在維持實用性的CMP速度下有 效率地抑制触刻速度，因此爲較佳。 有機酸之添加量，在每1公升之使用於硏磨時的硏磨 液中，較佳爲設定在0.0 00 5莫耳至0.5莫耳，更佳爲設定 在0.005莫耳至0.3莫耳，特佳爲設定在〇.〇1莫耳至〇.1 莫耳。亦即，有機酸之添加量，從抑制鈾刻的觀點來看， 則較佳爲0.5莫耳以下，從獲得足夠的功效的觀點來看， 則較佳爲0.0005莫耳以上。 〔其他添加劑〕 在本發明之硏磨用組成物中，視需要可含有界面活性 劑等之傳統添加劑。 〔硏磨方法〕 本發明之硏磨方法係對硏磨平台上之硏磨墊供應硏磨 用組成物，邊使該硏磨墊與被硏磨體之絶緣膜接觸，邊旋 轉該硏磨平台以使接觸面相對運動來進行硏磨，其特徵爲 該絶緣膜係在具有有機矽氧烷結構之相對介電常數爲3.0 以下之絶緣膜隔著阻障層而形成埋入配線所構成的該被硏 磨體之絶緣膜，且該硏磨用組成物係由本發明之硏磨用組 成物所構成。藉此，即使在硏磨低相對介電常數之絶緣膜 的情形下，可在不至於對絶緣膜造成刮傷等之缺陷下，提 高硏磨速度。 在本發明之硏磨方法中，關於具有如上所述之有機矽 -19- 200826164 氧烷結構的相對介電常數爲3.0以下之絶緣膜，係與揭示 於上述本發明之硏磨用組成物項中者相同，且較佳實例也 是相同。 另外，在本發明之硏磨方法使用之硏磨用組成物係與 上述本發明之硏磨用組成物相同，且較佳實例也是相同。 本發明之硏磨用組成物，在使用時之形態則有如下述 三種：1 )作成爲濃縮液，而在使用時以水或水溶液加以稀 釋作爲使用液之情形；2 )各成份係準備成爲次項所述之水 溶液形態，而在使用時混合該等，且視需要而加水稀釋作 爲使用液之情形；及3)己調製成使用液之情形。 對於使用本發明硏磨用組成物之硏磨方法，上述任何 硏磨用組成物（硏磨液）形態皆可適用。 用於硏磨之裝置係可使用具備：具有用於保持被硏磨 面的被硏磨體（例如，形成導電性材料膜之晶圓等）之保 持器、與貼附硏磨墊之（經搭配可變更旋轉數之馬達等） 硏磨平台的一般硏磨裝置。 該硏磨裝置之具體實例係包括：Mirra Mesa CMP、 Reflexion CMP (美商應用材料股份有限公司製造）； FREX2 00、FREX3 00 (莲原製作所(ERABA Corp.)製造） ;NPS 3 3 0 1、NPS 230 1 (尼康公司（Nikon Corp.)製造）； 八-叩-310人、人-??-210八（東京精密（丁〇]^〇361111士11〇〇.,1^(1· )製造）；2300 TERES( Lam Research 公司製造）；Momentum (Speedfam IPEC股份有限公司製造）等。 硏磨墊可使用一般性的不織布、發泡聚胺基甲酸酯、 -20- 200826164 多孔性氟樹脂等，且並無特殊限制。詳細容後說明。 另外’硏磨條件雖然並無特殊限制，但是硏磨平台之 旋轉速度較佳爲200 rpm以下之低旋轉以防止被硏磨體被 甩出。具有被硏磨面（被硏磨膜）之被硏磨體對於硏磨墊 的按壓壓力，較佳爲0.68至34.5 KPa，更佳爲0.69至21.6 KPa，且爲符合硏磨速度在被硏磨體面內之均勻性及圖案平 坦性之條件，更佳爲3.40至20.7 KPa。 在進行硏磨期間，可以泵等來對硏磨墊連續供應硏磨 用組成物。硏磨結束後之被硏磨體，可經在流水中充分地 加以洗滌後，使用旋轉式乾燥機等來甩落附著在被硏磨體 上的水滴後加以乾燥。 在本發明中，如上所述之第1項之方法，稀釋濃縮液 時可使用下述水溶液。水溶液係預先使其含有氧化劑、有 機酸、添加劑、界面活性劑中之至少一種之水，且必須使 全部包含在該水溶液中之成份，與包含在經稀釋的濃縮液 中之成份的成份能一致於硏磨時所使用的硏磨用組成物（ 使用液）之成份。 如上所述，在用水溶液稀釋濃縮液來使用之情形時， 則由於可將難溶成份以水溶液之形態加以後混合，因此可 調製得更濃縮的濃縮液。 另外，在濃縮液加入水或水溶液以稀釋之方法，則有 將用於供應經加以濃縮的組成之濃縮液之配管與供應水或 水溶液之配管在途中使其合流而混合，然後，供應經混合 並稀釋之硏磨用組成物使用液於硏磨墊之方法。濃縮液與 -21-In the formula (I), R1 represents a hydrogen atom, a hydrocarbon group or hydrazine R3, and R2 represents a hydrocarbon group or OR4. R3 and R4 each independently represent a hydrocarbon group. The hydrocarbon group represented by the formula "R1 to R4" includes an aliphatic hydrocarbon group or an aromatic hydrocarbon group. A material which can be used to form the low relative dielectric constant insulating film as described above, for example, "SiOC system" includes · HSG-R7 (manufactured by Hitachi Chemical Co., Ltd.: relative dielectric constant: 2.8), black diamond (BLACKDIAMOND) (manufactured by American Applied Materials Co., Ltd.: relative dielectric constant: 2.4 to 3.0), Coral (Hong Kong business) Manufactured by Novellus Systems, Inc., with a relative dielectric constant of 2.4 to 2.7), Aurora (manufactured by EMS, Inc., Japan: relative dielectric constant of 2·7) In addition, the "MSQ system" includes: 0CDT-9C manufactured by Tokyo 化hka Co. Ltd.: relative dielectric constant is 2.7), LKD-T200 (JSR Corp.) Manufacturing: relative dielectric constant of 2.5 to 2.7), H0SP (Honey-10-200826164 manufactured by Honeywell Electronic Materials: relative dielectric constant of 2.5), HSG-RZ25 (Hitachi Chemical Industry Co., Ltd. Manufacturing: Relative The constant is 2.5), OCLT-31 (manufactured by Tokyo Ohka Kogyo Co., Ltd.: relative dielectric constant is 2 3 ), LKI^T4〇〇 (manufactured by JSR: relative dielectric constant: 2.0 to 2.2), HSG-6211X (Manufactured by Nippon Kasei Kogyo Co., Ltd.: relative dielectric constant is 2.1), ALCAP-S (made by Asahi Kasei Chemicals Co., Ltd.: relative dielectric constant is ι·8 to 2.3), OCLT-77 (Tokyo Manufactured by Yinghua Industrial Co., Ltd.: relative dielectric constant is 1.9 to 2.2), HSG-6211X (manufactured by Shengli Chemical Industry Co., Ltd.: relative dielectric constant is 2.4·), silica aerogel (Kobe Steel) ·, Ltd.) Manufacture: relative dielectric constant is from 丨 to L4), etc., but is not limited thereto. The material which can be used for forming the low relative dielectric constant insulating film can be used alone or in combination of several kinds thereof. Further, the insulating film formed through the materials may have minute voids. The method of forming the insulating film of the present invention may be a plasma CVD method or a rotary coating method. The relative dielectric constant of the insulating film of the present invention must be 3.0 or less, but is preferably lower, and particularly preferably 1.8 to 2.8. In the relative dielectric constant of the present invention, a measurement method of a mercury probe can be used for a comprehensive film, and a relative dielectric constant of an insulating film provided with a wiring can be a Presision 4284A LCR Meter (Agilent Technologies). The company manufactures) to determine. For example, -11-200826164, the line width is below 90 nm, preferably about 2.4. [The composition for honing] The composition for honing of the present invention is characterized by comprising particles, (b) a benzotriazine compound, and (c) no [(a) cerium oxide particles] The composition contains a primary particle of cerium oxide as a constituent component. The dioxane is a honing grain. In the "cerium oxide particles" of the present invention, cerium oxide, gas phase cerium oxide (white carbon black), colloidal silica, and synthesis, from the viewpoint of honing speed, Preferably, the colloidal phase method is cerium oxide (white carbon black), more preferably a method for producing colloidal dicolloid cerium oxide particles, such as Si (sec-〇C4H9)4, Si(〇CH3)4, Si ( 〇C4H9)4 can be obtained by hydrolysis by a sol-gel method. The particle size distribution of this glue will be very steep. The method for producing a vapor phase cerium oxide particle is a high temperature hydrolysis method in a hydrogen hydride flame. In the so-called cerium oxide particles of the present invention, the particle size cumulative curve showing the relationship between the particle diameter of the cerium oxide particles and the cumulative degree of the particles having the particle diameter is a particle diameter at a point of cumulative value of 50%. The cerium oxide is shown in the particle size distribution measured by the dynamic light scattering method and has a low dielectric constant (a) cerium oxide machine salt. The cerium particle system having a diameter of 10 to 80 is used as a system including, for example, fumed silica. Among them, dioxide, or gas oxidized sand. The Si (〇C2H5)4, alkoxylated ruthenium compound-state cerium oxide particles include, for example, a four-chlorinated particle size system to obtain a table number to be integrated, meaning that the particle size of the curve is calculated. Average grain-12- 200826164 Trail. For the measurement device for determining the particle size distribution, for example, LB·500 (manufactured by Horiba, Ltd.) or the like is used. In the present invention, the primary particle diameter of the cerium oxide particles to be contained needs to be 10 to 80 nm, but preferably 10 to 60 nm' or more preferably 30 nm. From the viewpoint of achieving a sufficient honing processing speed, particles of 10 nm or more are preferable. Further, the particle diameter is preferably 80 nm or less for the purpose of not causing excessive frictional heat in the honing processing. In the present invention, the cerium oxide particles may be used singly or in combination of two or more thereof. Use. In the present invention, the concentration of the cerium oxide particles contained in the honing composition used in the honing preferably contains a ratio of 〇 5 to 15% by mass, more preferably 1 to 10%. quality%. The concentration is preferably 0.5% by mass or more from the viewpoint of achieving a sufficient honing speed. Further, from the viewpoint of suppressing excessive frictional heat generated in the honing process, the concentration is preferably 15% by mass or less. The so-called ratio of 0.5 to 15% by mass in the honing composition means that the composition for honing contains 5 to 150 g per 1 liter. Further, the composition for honing of the present invention may be used as it is, and may be used in a diluted form. However, even if it is used after diluting the composition for honing, the composition for honing is diluted at the time of use. The concentration in the liquid is still the same as the concentration range of the honing composition, and the preferred range is also the same. [(b) benzotriazole compound] The honing liquid of the present invention contains a benzotriazole compound. -13- 200826164 In the present invention, the benzotriazole compound preferably comprises benzotriazole (oxime), 5,6-dimethyl-1,2,3-benzotriazole 1-(1,2 At least one of -dicarboxyethyl)benzotriazole (DCEBTA), (hydroxyethyl)aminomethyl]benzotriazole (HEABTA) methyl)benzotriazole (HMBTA). The benzotriazole compound is subjected to a specific compound, i.e., a low relative dielectric constant insulating film and a buried wiring. The benzotriazole compound used in the present invention may be used alone or in combination of two or more. On the other hand, the concentration of the benzotriazole compound is not less than or equal to 0.2% by mass, more preferably 0.05% by mass or less, based on the honing composition used for honing. In the honing composition of the present invention, an aromatic ring compound other than the azole compound is preferred. In the present invention, the aromatic ring compound other than the compound is, for example, an aromatic ring compound other than the triazole or tetra-free benzotriazole compound, and the honing speed ratio (selection ratio) of the wiring can be buried. [(c) Inorganic salt] The honing composition of the present invention contains 1 to 10% by mass of an inorganic salt in the case of using honing. The addition amount is 1 liter of an inorganic salt of 1 100 g in the honing composition used for honing. Due to the inclusion of inorganic salts in this range, it may be selected from 1,2,3-(DBTA), 1-[N,N-bis, 1 - (hydroxyl to obtain a suitable speed ratio (option of one, or no particular preference) 0. 〇1% or more, 0.2 benzotribenzotriazole, etc. Since the composition obtained by appropriate honing means that there is 10 gram relative to I to improve the low relative insulation of 14-200826164 dielectric constant In the present invention, the content of the inorganic salt is preferably from 丨 to 5% by mass, more preferably from 2 to 3% by mass. The inorganic salt which can be used in the present invention, although not particularly limited, From the viewpoint of detergency, it is preferably at least one selected from the group consisting of an ammonium salt, a sodium salt, and a potassium salt. Among them, an ammonium salt, a potassium salt, and more preferably a money salt are preferred. The anion of the inorganic salt is not particularly limited, and for example, chloride ion, nitrate ion, sulfate ion, phosphate ion, etc. may be used. Specific examples of the inorganic salt which can be used in the present invention include nitric acid, ammonium sulfate, and phosphoric acid. Ammonium, ammonium chloride, sodium nitrate, sodium sulfate, sodium chloride, nitric acid And potassium sulphate, potassium chloride, etc. Among these, it is preferable to use ammonium nitrate from the viewpoint of suppressing various defects of CMP. The above-mentioned inorganic salt of the present invention may be used alone or in combination of two or more. The above composition is used in combination. [pH] The composition for honing of the present invention, the pH used in the honing composition for honing must be in the range of 8 to 11, but the pH is preferably 9 to 1 1 More preferably, it is 9.5 to 1 0.5. In order to adjust the pH to a preferred range, a base/acid or a buffer may be used. The honing composition of the present invention is used for the pH of the honing composition at the time of honing. In the range, it can improve the speed of honing. The "alkali/acid or buffer" is preferably "organic ammonium hydroxide" such as ammonia, ammonium hydroxide and tetramethyl-15-200826164 ammonium. "Non-metal alkaline agent" such as "alkanolamines" such as diethanolamine, triethanolamine or tripropanolamine; "alkali metal hydroxide" such as hydrogen hydroxide, potassium hydroxide or lithium hydroxide: nitric acid sulfate "Inorganic acid" such as phosphoric acid; "carbonate" such as sodium carbonate; "phosphate" such as trisodium acid Borate, tetraborate, hydroxybenzoate, etc. Particularly preferred alkaline agents are ammonium hydroxide, potassium hydroxide, hydrogen hydroxide and tetramethylammonium hydroxide. The amount of alkali/acid or buffer added is as long as It is preferable to maintain the pH in an appropriate range, and it is preferable to set the honing composition used for honing to 0.0001 g to 1 g per liter, more preferably 0.001 g to 0.1 g. In the honing composition of the present invention, it is preferred to contain a compound (oxidizing agent) which can oxidize the metal of the honing image. The "oxidizing agent" includes, for example, hydrogen peroxide, peroxide, nitrate salt, and iodine. Acid salt, periodate, hypochlorite, chlorite, chlorate peroxy acid salt, persulfate, heavy complex salt, perchlorate, ozone water, silver (II) salt, iron (III) a salt in which hydrogen peroxide is suitably used. The "iron (III) salt" includes, for example, iron (III) nitrate, chlorinated (III), iron (III) sulfate, iron (III) iron or the like, and iron (III). Organically mixed salt. The amount of the oxidizing agent to be added is preferably from 0.01 mol to 1 mol, and particularly preferably from 0.05 to 0.6 mol, per 1 liter of the grinding liquid used in the honing. Isocyanine Phosphate Lithium Complex 1 to Acid and Iron III 硏 Mo-16- 200826164 [Chelating Agent] In the honing composition of the present invention, in order to reduce the adverse effects of mixed polyvalent metal ions, etc., It may contain a chelating agent. The "chelating agent" includes, for example, a general hard water softening agent or the like which is an anti-precipitating agent of calcium or magnesium, such as nitrogen triacetic acid, diethylene glycol triacetic acid, ethylenediamine tetraacetic acid, hydrazine, Ν,Ν-trimethylenephosphonic acid, ethylenediamine-oxime, oxime, Ν', Ν'-tetramethylenesulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropane Tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS body), bismuth-(2-carboxylateethyl)-L-aspartate Amino acid, ^-alanine diacetic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, hydroxyethylidene-1,1-diphosphonic acid, hydrazine, Ν'-double (2- Hydroxybenzyl) ethylenediamine-oxime, Ν'-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and the like. [Organic Acid] The honing liquid of the present invention may further contain an organic acid. The compound 'that is different from the oxidizing agent for oxidizing a metal' is not an acid which acts as an oxidizing agent as described above. Here, the acid system functions to promote oxidation, adjust pH, and buffer. The organic acid in the present invention is preferably selected from the group consisting of the following. That is, including: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methyl Valeric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benz-17-200826164 acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, Salts of succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, and the like, ammonium salts or alkali metal salts thereof, A mixture of sulfuric acid, nitric acid, ammonia, ammonium salts, or the like, and the like. Among these, formic acid, malonic acid, malic acid, tartaric acid, and citric acid are suitably used for a laminated film containing at least one metal layer selected from the group consisting of copper, a copper alloy, and an oxide of copper or a copper alloy. 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 more preferably selected from the group consisting of the following. That is, it is preferably selected from, for example, glycine, L-alanine, Θ-alanine, L-2-aminobutyric acid, L-nuronic acid, L-proline, L-leucine , L-positive leucine, L-isoleucine, L-alloy, isoleucine, L-phenylalanine, L-proline, sarcosine, L-ornithine, L·ion Aminic acid, taurine, L-serine, L-threonine, L-bethionine, L-homoserine, L-tyramine, 3,5-diiodo-L-tyrosine , /3-(3,4-dihydroxyphenyl)-L-alanine, L-thyroxin' 4-hydroxy-L-proline, L-cysteine, L-methionine, L - Ethionine, L-lanine thiol, L-cystathion, L-cystamine, L-sulfoalanine, L-aspartic acid, L-glutamic acid, S-(carboxyl -L-cysteine, 4-aminobutyric acid, L-aspartic acid, L-glutamic acid, nitrogen serine, L-arginine, L-cutosin, L-citrulline, 5-hydroxy-L-lysine, creatine, L-kynurenine, L-histamine, 1-methyl-L-histidine, 3-methyl-L- Histamine, ergothiol, L-tryptophan, actinomycin C1, Amamin, vasopressin i, vasoconstriction - 18- 200826164 At least one of the condensed protein II, and an amino acid such as an anti-papaya enzyme. Among these, in particular, malic acid, tartaric acid, citric acid, glycine acid, and glycolic acid are preferred because the etch rate can be effectively suppressed while maintaining a practical CMP rate. The amount of the organic acid added is preferably set to 0.000 m to 0.5 m, and more preferably 0.005 m to 0.3 m, per 1 liter of the honing liquid used for honing. Very good for setting in 〇.〇1莫耳至〇.1 Moer. In other words, the amount of the organic acid to be added is preferably 0.5 mol or less from the viewpoint of suppressing uranium engraving, and is preferably 0.0005 mol or more from the viewpoint of obtaining sufficient efficacy. [Other Additives] The honing composition of the present invention may contain a conventional additive such as a surfactant as needed. [honing method] The honing method of the present invention supplies a honing composition to the honing pad on the honing platform, and rotates the honing platform while contacting the honing pad with the insulating film of the honing body. The honing is performed by moving the contact surface relative to each other, and the insulating film is formed by forming an embedded wiring having an organic dielectric structure having a relative dielectric constant of 3.0 or less across the barrier layer. The insulating film is honed, and the honing composition is composed of the honing composition of the present invention. Thereby, even in the case of honing the insulating film having a low relative dielectric constant, the honing speed can be improved without causing scratches or the like on the insulating film. In the honing method of the present invention, the insulating film having a relative dielectric constant of 3.0 or less having the organic hydrazine-19-200826164 oxyalkylene structure as described above is the honing composition item disclosed in the above-mentioned present invention. The same is true, and the preferred examples are the same. Further, the honing composition used in the honing method of the present invention is the same as the above-described honing composition of the present invention, and preferred examples are also the same. The composition for honing of the present invention may be in the following three forms when used: 1) as a concentrate, and diluted with water or an aqueous solution as a use liquid at the time of use; 2) each component is prepared to be The form of the aqueous solution described in the above paragraph, which is mixed at the time of use, and diluted with water as a use liquid as needed; and 3) has been prepared into a use liquid. For the honing method using the honing composition of the present invention, any of the above honing compositions (honing liquid) forms can be applied. The apparatus for honing can be used with a holder having a honed body for holding a honed surface (for example, a wafer forming a film of a conductive material, etc.) and a honing pad attached thereto With a motor that can change the number of rotations, etc.) A general honing device for honing platforms. Specific examples of the honing device include: Mirra Mesa CMP, Reflexion CMP (manufactured by American Applied Materials Co., Ltd.); FREX 2 00, FREX3 00 (manufactured by ERABA Corp.); NPS 3 3 0 1, NPS 230 1 (manufactured by Nikon Corp.); eight-叩-310 people, person-??-210 eight (Tokyo Precision (丁〇)^〇361111士11〇〇.,1^(1·) Manufactured; 2300 TERES (manufactured by Lam Research); Momentum (manufactured by Speedfam IPEC Co., Ltd.), etc. General non-woven fabric, foamed polyurethane, -20- 200826164 porous fluororesin Etc., and there are no special restrictions. For details, please refer to the following. In addition, the honing condition is not particularly limited, but the rotation speed of the honing platform is preferably a low rotation of 200 rpm or less to prevent the honed body from being thrown out. The pressing force of the honed body having the honed surface (the honed film) for the honing pad is preferably 0.68 to 34.5 KPa, more preferably 0.69 to 21.6 KPa, and is honed to meet the honing speed. The condition of uniformity in the body surface and the flatness of the pattern is more preferably 3.40 to 20.7 KPa. During the honing, the honing pad can be continuously supplied to the honing pad by pumping, etc. The honed body after the honing can be thoroughly washed in the running water, and the rotary dryer is used. In the present invention, the method of the first aspect described above, when diluting the concentrate, may use the following aqueous solution. The aqueous solution is previously prepared to contain an oxidizing agent. a water of at least one of an organic acid, an additive, and a surfactant, and it is necessary to make all the components contained in the aqueous solution consistent with the components contained in the diluted concentrate to be used in the honing As a component of the grinding composition (use liquid), as described above, when the concentrate is diluted with an aqueous solution, the insoluble component can be mixed and mixed in the form of an aqueous solution, so that a more concentrated concentration can be prepared. In addition, when the concentrate is added with water or an aqueous solution to be diluted, there is a piping for supplying a concentrated liquid of the concentrated composition with a supply water or an aqueous solution. On the way it merged and mixed, and then, supply of the mixed and diluted WH grinding liquid composition for use in the method of the sanding pad of WH Concentrate and -21-
200826164 水或水溶液之混合’可採用以外加壓力 窄通路以使液彼此予以衝突混合之方法 璃管等之塡充物以使液體流反復進行分 法，以及在配管中設置藉由動力旋轉的 採用之方法。 硏磨用組成物之供應速度較佳爲1 〇 3 ，若欲滿足硏磨速度之被硏磨面內均勻性 條件，則更佳爲170至800毫升/分鐘。 另外，硏磨用組成物之供應流量爲S 墊）供應的硏磨組成物之每分鐘流量，若 硏磨加工的被硏磨體上之被硏磨面面積（ 量時，則硏磨用組成物之供應流量較佳j ml/min · cm2。藉此即可滿足硏磨速度之補 及圖案之平坦性條件。 此外，以水或水溶液等邊使濃縮液更 方法’則有一種分開獨立設置用於供應濃 於供應水或水溶液之配管，並由各自對研 之液’以硏磨墊與被硏磨面之相對運動 法。另外，也可使用在一容器中裝入特 或水溶液並加以混合後，對硏磨墊供應 成物以進行硏磨之方法。 另外’其他硏磨方法，則有將硏磨 成份至少分成兩種構成成份，然後，在 入水或水溶液以稀釋而供應至硏磨平台 狀態使其通過狹 在配管中裝入玻 分離、合流之方 片之法等通常被 1，000毫升/分鐘 及圖案之平坦性 被硏磨體（硏磨 假設相對於在被 晶圓面積）之流 ^ 0.035 至 0.60 硏磨面內均勻性 加稀釋邊硏磨之 縮液之配管與用 磨墊供應特定量 混合邊硏磨之方 量之濃縮液與水 混合的硏磨用組 組成物應含有之 用其等時，則加 之硏磨墊，使其 -22- 200826164 與被硏磨面接觸並使被硏磨面與硏磨墊相對運動以進行硏 磨之方法。 例如，可以氧化劑爲構成成份（A ) ’以有機酸、添加 劑、界面活性劑、及水爲構成成份（B )，在使用其等時， 則以水或水溶液稀釋構成成份（A )及構成成份（B )來使 用。 另外，將溶解度低之添加劑分成兩種構成成份（A )與 (B )，例如將氧化劑、添加劑、及界面活性劑作爲構成成 份（A)，將有機酸、添加劑、界面活性劑、及水作爲構成 成份（B )，在使用其等時，則加入水或水溶液，以稀釋構 成成份（A )及構成成份（B )來使用。在此等情況下，本 發明之二氧化矽粒子（硏磨粒）較佳爲使其包含在構成成 份（A )中。 在如上所述方法實例之情形時，則需要三種用於分別 供應構成成份（A )與構成成份（B )與水或水溶液之配管 ，稀釋混合則將三種配管結合於對硏磨墊供應的一配管， 而在其配管內進行混合之方法，此種情形下，也可爲先結 合二種配管後再結合其他之一配管。具體而言，其係先混 合含有不易溶解的添加劑之構成成份與其他構成成份，使 混合路徑拉長以確保足夠的溶解時間後，再結合水或水溶 液的配管之方法。 其他混合方法，則有如上所述，直接將三種配管分別 引導至硏磨墊’以藉硏磨墊與被硏磨面之相對運動來混合 之方法’或在一個容器中混合三種構成成份，然後，由其 -23- 200826164 對硏磨墊供應經稀釋的硏磨用組成物之方法。 在如上所述之硏磨方法中，可採取：設定含有氧化劑 之一構成成份爲40°C以下，其他構成成份則加溫至在室溫 至1 0 0 °c之範圍，然後，在混合一構成成份與其他構成成份 時，或加入水或水溶液以稀釋時，則將液溫設定在40 °c以 下之方法。該方法係利用溫度高時，則溶解度將增高之現 象，是一種對於提高硏磨用組成物之低溶解度原料的溶解 度上是適合使用之方法。 如上所述之經藉由在室溫至1 00 °c之範圍的加溫來溶 解其他構成成份所獲得之原料，由於溫度一旦降低則將析 出於溶液中，因此使用低溫狀態的其他構成成份時，則必 須預先加溫以溶解所析出的原料。其可採用予以加溫，然 後送液原料已溶解的其他構成成份之方法，與預先攪拌含 有析出物之液，然後送液並加溫配管以使其溶解之方法。 經加溫之其他構成成份，若使得含有氧化劑的一構成成份 之溫度升高至40 °C以上時，則有導致氧化劑分解之顧慮， 在混合該經加溫之其他構成成份與含有氧化劑的一構成成 份之情形時，則較佳爲設定在40°C以下。 如上所述，在本發明中，也可將硏磨用組成物之成份 分割成二分割以上來以供應至被硏磨面。此種情形下，較 佳爲分割成含氧化物成份與含有機酸子成份來供應。另外 ，也可爲以硏磨用組成物爲濃縮液，稀釋水則分開供應至 被硏磨面。 在本發明中，在適用分割硏磨用組成物成份爲二分割 -24- 200826164 以上來供應至被硏磨面之方法時，則其供應量係表示來自 各配管之全部供應量。 〔墊〕 可適用於本發明之硏磨方法之硏磨用硏磨墊係可爲無 發泡結構之墊或發泡結構之墊。前者係使用例如塑膠板之 硬質合成樹脂鬆散（bulk )材料爲墊者。另外，後者係又 有獨立發泡體（乾式發泡系）、連續發泡體（濕式發泡系 )、二層複合體（積層系）之三種，特佳的是二層複合體 (積層系）。發泡可爲均勻或不均勻。 並且，也可爲含有一般使用於硏磨之硏磨粒（例如二 氧化鈽、二氧化矽、氧化鋁、樹脂等）者。另外，硬度係 各自皆有軟質與硬質者，惟任一者皆可使用，在積層系， 較佳爲分別在各層使用不同硬度者。材質較佳爲不織布、 人工皮革、聚醯胺、聚胺基甲酸酯、聚酯、聚碳酸酯等。 另外，對於與被硏磨面相接觸之面，也可施加格子溝/穴/ 同心溝/螺旋狀溝等之加工。 〔晶圓〕 以本發明之硏磨用組成物施加CMP之對象的被硏磨體 之晶圓係直徑較佳爲2Ό0 mm以上，特佳爲3 00 mm以上。 若其爲3 00 mm以上時，則將顯著地發揮本發明之功效。 《實施例》 以下，以實施例具體說明本發明，但是本發明並不受 限於此等實施例。 〔實施例1〕 -25- 200826164 (硏磨用組成物之調製） 10克/公升 10克/公升 0.5克/公升 100克/公升 (粉體換算） 1，〇〇〇毫升 9.5 混合下述組成以調製硏磨用組成物。 過氧化氫（氧化劑） 硝酸銨（無機鹽，和光純藥工業公司（ Wako Pure Chemical Industries, Ltd.)製 造）200826164 Mixing of water or aqueous solution can be carried out by applying a narrow pressure path to make the liquids conflict with each other. The filling of the glass tube or the like is repeated for the liquid flow, and the rotation by the power is set in the piping. The method. The supply speed of the honing composition is preferably 1 〇 3 , and more preferably 170 to 800 ml/min if the honing speed of the honing speed is satisfied. In addition, the supply flow rate of the honing composition is the flow rate per minute of the honing composition supplied by the S pad), and if the honed surface area of the honed body is honed (the amount is honed) The supply flow rate of the material is preferably j ml/min · cm2, thereby satisfying the honing speed compensation and the flatness condition of the pattern. In addition, the method of making the concentrated liquid by water or aqueous solution is a separate method. For the supply of pipes rich in water or aqueous solution, and the relative motion of the honing pad and the honed surface by the respective liquids. Alternatively, it is also possible to use a special or aqueous solution in a container and apply After mixing, the honing pad is supplied with a product for honing. In addition, 'other honing methods have at least two components into the honing component, and then supplied to the honing water in the water or the aqueous solution. The state of the platform is such that the method of loading the glass into the glass in the narrow tube, the method of joining the square sheets, etc., is usually honed by the flatness of 1,000 ml/min and the pattern (the assumption is relative to the area of the wafer) Stream ^ 0.035 0.60 honing surface uniformity plus dilution side honing liquid shrinkage piping and grinding pad supply a certain amount of mixing side honing amount of concentrated liquid and water mixing honing group composition should be used In addition, the honing pad is added so that -22-200826164 is in contact with the honed surface and the honing surface is moved relative to the honing pad to perform honing. For example, the oxidizing agent can be used as a constituent (A). The organic acid, the additive, the surfactant, and water are used as the component (B), and when it is used, the component (A) and the component (B) are diluted with water or an aqueous solution. In addition, the solubility is low. The additive is divided into two components (A) and (B), for example, an oxidizing agent, an additive, and a surfactant are used as a constituent component (A), and an organic acid, an additive, a surfactant, and water are used as a constituent component (B). When it is used, water or an aqueous solution is added to dilute the constituent (A) and the constituent (B). In these cases, the cerium oxide particles (honing particles) of the present invention are preferably Make it contain In the case of the component (A), in the case of the method example as described above, three kinds of pipes for separately supplying the component (A) and the component (B) with water or an aqueous solution are required, and the three types of pipes are bonded to the pair by dilution and mixing. A method of mixing the piping supplied by the honing pad and mixing it in the piping. In this case, it is also possible to combine the two types of piping and then combine the other piping. Specifically, the first mixing is difficult to dissolve. The composition of the additive and other constituent components, the mixing path is elongated to ensure sufficient dissolution time, and then the method of combining the water or the aqueous solution is combined. Other mixing methods, as described above, directly direct the three types of piping to the respective The honing pad 'mixes the lining pad with the relative movement of the honed surface' or mixes the three components in a container, and then supplies the diluted honing pad to the honing pad from -23-200826164 The method of using the composition. In the honing method as described above, it may be adopted that: one of the constituents containing the oxidizing agent is 40 ° C or less, and the other constituents are heated to a temperature ranging from room temperature to 100 ° C, and then, in the mixing one When the constituents and other constituent components are added, or water or an aqueous solution is added for dilution, the liquid temperature is set to 40 ° C or less. This method is a method in which the solubility is increased when the temperature is high, and it is a method suitable for improving the solubility of the low-solubility raw material of the honing composition. The raw material obtained by dissolving other constituent components by heating at a temperature ranging from room temperature to 100 ° C as described above will precipitate in the solution as the temperature is lowered, so that when other components in a low temperature state are used, , it must be preheated to dissolve the precipitated raw materials. It may be a method of heating, and then the other constituent components in which the liquid feed material has been dissolved, and a method of previously stirring the liquid containing the precipitate, and then feeding the liquid and heating the tube to dissolve it. When the temperature of a constituent component containing the oxidizing agent is raised to 40 ° C or higher, there is a concern that the oxidizing agent is decomposed, and the other components which are heated and the oxidizing agent are mixed. In the case of a component, it is preferably set to 40 ° C or lower. As described above, in the present invention, the components of the honing composition may be divided into two or more portions to be supplied to the honed surface. In this case, it is preferably supplied as an oxide-containing component and an organic acid-containing component. Alternatively, the composition for honing may be used as a concentrate, and the diluted water may be supplied separately to the surface to be honed. In the present invention, when the method of supplying the components for the split honing is divided into two parts -24-200826164 or more and supplied to the surface to be honed, the supply amount means the total supply amount from each of the pipes. [Cushion] The honing pad for honing which can be applied to the honing method of the present invention may be a mat of a non-foamed structure or a mat of a foamed structure. The former uses a hard synthetic resin bulk material such as a plastic plate as a cushion. In addition, the latter has three types of independent foam (dry foaming), continuous foam (wet foaming), and two-layer composite (layered), and particularly preferred is a two-layer composite (layered) system). Foaming can be uniform or non-uniform. Further, it may be one containing cerium abrasive grains (for example, cerium oxide, cerium oxide, aluminum oxide, resin, etc.) which are generally used for honing. Further, each of the hardness systems may be soft or hard, and any one may be used. In the laminated system, it is preferred to use different hardnesses in each layer. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate, or the like. Further, for the surface in contact with the surface to be honed, processing such as lattice grooves/holes/concentric grooves/spiral grooves may be applied. [Wafer] The diameter of the wafer to be honed body to which the CMP is applied by the honing composition of the present invention is preferably 2 Ό 0 mm or more, and particularly preferably 300 Å or more. If it is 300 mm or more, the effects of the present invention will be remarkably exerted. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. [Example 1] -25- 200826164 (Preparation of composition for honing) 10 g / liter 10 g / liter 0.5 g / liter 100 g / liter (powder conversion) 1, 〇〇〇 ml 9.5 The following composition was mixed To modulate the composition for honing. Hydrogen peroxide (oxidizing agent) Ammonium nitrate (inorganic salt, manufactured by Wako Pure Chemical Industries, Ltd.)
ί 1，2,3-苯并三唑（BTA:芳香環化合物） 膠體二氧化矽粒子（PL-3 ) 加入純水後之總量 pH (以氨水與硫酸加以調整） 〔實施例2至18及比較例1至5〕 除在實施例1之硏磨用組成物之調製中，變更硏磨粒 (二氧化矽粒子）、無機鹽、及pH爲如表1所示以外，其 餘則以與實施例1相同的方式調製得硏磨用組成物。 (硏磨試驗及評估） 硏磨裝置係使用Lapmaster SFT公司所製造之裝置「 LGP-612」，並以下述條件，邊供應藉由如上所述所製得之 硏磨用組成物（漿體），邊硏磨設置在晶圚上之絶緣膜， 並測定其時之硏磨速度。 具體而言，在硏磨裝置之硏磨平台之硏磨墊邊供應硏 磨用組成物，邊在將基板（被硏磨體）按壓於硏磨墊之狀 態下，使硏磨平台與基板相對運動，以進行硏磨絶緣膜（ BDI )。 -26- 200826164 一被硏磨體一 絶緣膜材料使用黑鑽石（blackdiam〇nd)(讀、 美商應用材料股份有限公司製造），並以CVD法在8英吋 晶圓上形成絶緣膜。 一硏磨條件一 • 轉盤旋轉數：64 rpm •硏磨頭旋轉數：65 rpm (加工線速度=丨.0公尺/秒鐘 ) • 硏磨壓力：6.89kPa •硏磨墊：羅門哈斯公司（Rohm andHaasCo.)製造之 型號 IC-1400 (K— XY — grv) +(A21) • 漿體供應速度：200毫升/分鐘· 一評估方法一 (1 )絶緣膜硏磨速度 硏磨速度係由電阻値換算在CMP前後的絶緣膜（BDI )之fe厚差’而以下式計算得。測定膜厚差係使用Matrix (股）公司製造之F20來實施。 BDI硏磨速度（奈米/分鐘）=(硏磨前之BDI厚度― 硏磨後之BDI厚度）/硏磨時間 -27- 200826164 表1 硏磨粒（粒徑 (奈米）；克/公升） i機鹽 (質量％) pH BDI硏磨速度 (奈米/分鐘） 實施例1 膠體二氧化矽（40奈米、100克/公升） 硝酸銨（1.0%) 9.5 72 實施例2 氣相法二氧化矽（20奈米、100克/公升） 硝酸鉀（1.0%) 9.5 35 實施例3 膠體二氧化矽（60奈米、80克/公升） 硫酸銨（1.0%) 9.5 76 實施例4 氣相法二氧化矽（30奈米、150克/公升） 硫酸銨（3.0%) 9.5 95 實施例5 膠體二氧化矽（40奈米、200克/公升） 氯化鈉（1.0%) 9 68 實施例6 氣相法二氧化矽（15奈米、150克/公升） 硝酸鉀（1.0%) 9 20 實施例7 膠體二氧化矽（80奈米、50克/公升） 氯化銨（1.5%) 9.5 60 實施例8 膠體二氧化矽（20奈米、200克/公升） 硝酸鉀（1.0%) 10.5 55 實施例9 氣相法二氧化矽（20奈米、100克/公升） 硝酸鈉（1.0%) 10.5 65 實施例10 膠體二氧化矽（20奈米、80克/公升） 硫酸銨（1.0%) 9.5 60 實施例11 氣相法二氧化矽（60奈米、100克/公升） 硝酸銨（4.0%) 10 90 實施例12 膠體二氧化砂（80奈米、150克/公升） 氯化銨（1.0%) 9.5 70 實施例13 氣相法二氧化矽（40奈米、100克/公升） 氣相法二氧化矽（30奈米、150克/公升） 硝酸銨（1.0%) 8.5 51 實施例14 氣相法二氧化矽（20奈米、100克/公升） 膠體二氧化矽（40奈米、100克/公升） 硝酸銨（1.0%) 9.5 71 實施例15 膠體二氧化矽（10奈米、10克/公升） 膠體二氧化矽（40奈米、100克/公升） 硝酸銨（1.0%) 9.5 68 實施例16 膠體二氧化矽（20奈米、80克/公升） 膠體二氧化矽（60奈米、100克/公升） 硝酸銨（1.0%) 9.5 75 實施例17 氣相法二氧化矽（10奈米、40克/公升） 氣相法二氧化砂（15奈米、50克/公升） 氣相法二氧化矽（30奈米、100克/公升） 硝酸銨（1.0%) 10.5 105 實施例18 氣相法二氧化矽（10奈米、40克/公升） 氣相法二氧化砂（15奈米、50克/公升） 膠體二氧化矽（80奈米、150克/公升） 硝酸銨（3.0%) 9.5 110 比較例1 膠體二氧化矽（40奈米、100克/公升） 硝酸銨（1.0%) 2 16 比較例2 膠體二氧化矽（40奈米、100克/公升） 硝酸銨（0.1%) 2 14 比較例3 膠體二氧化矽（40奈米、100克/公升） 硝酸銨（0.01%) 2 15 比較例4 膠體二氧化矽（40奈米、100克/公升） - 9.5 8 比較例5 氣相法二氧化矽（40奈米、100克/公升） - 6 2 根據表1之結果，本發明之實施例1至1 8即達成非常 大的絶緣膜硏磨速度。與此相對，在脫離本發明方式之比 -28- 200826164 較例1至5，則無法達成足夠的硏磨速度。 【圖式簡單說明】 Μ 〇 【主要元件符號說明】 魅〇 -29-ί 1,2,3-benzotriazole (BTA: aromatic ring compound) Colloidal cerium oxide particles (PL-3) Total pH after addition of pure water (adjusted with ammonia and sulfuric acid) [Examples 2 to 18 And Comparative Examples 1 to 5] In addition to the preparation of the honing composition of Example 1, the honing particles (cerium oxide particles), the inorganic salts, and the pH were changed as shown in Table 1, and the others were The composition for honing was prepared in the same manner as in Example 1. (Horse test and evaluation) The honing device is a device (LGP-612) manufactured by Lapmaster SFT Co., Ltd., and the honing composition (slurry) prepared as described above is supplied under the following conditions. The honing film disposed on the wafer is honed and the honing speed at that time is measured. Specifically, the honing composition is supplied to the honing pad of the honing platform of the honing device, and the honing platform is opposed to the substrate while the substrate (the honed body) is pressed against the honing pad. Exercise to perform honing of the insulating film (BDI). -26- 200826164 A black diamond (blackdiam〇nd) (read, manufactured by Applied Materials, Inc.) was used as an insulating film material, and an insulating film was formed on a 8-inch wafer by CVD. One honing condition one • Turntable rotation number: 64 rpm • Honing head rotation number: 65 rpm (processing line speed = 丨.0 m / s) • Honing pressure: 6.89 kPa • Honing pad: Rohm and Haas Model IC-1400 (K-XY — grv) + (A21) manufactured by the company (Rohm and Haas Co.) • Slurry supply speed: 200 ml/min · One evaluation method one (1) Insulation film honing speed honing speed system The thickness difference of the insulating film (BDI) before and after the CMP is converted by the resistance 値 and is calculated by the following formula. The measurement of the film thickness difference was carried out using F20 manufactured by Matrix. BDI honing speed (nano / min) = (BDI thickness before honing - BDI thickness after honing) / honing time -27- 200826164 Table 1 honing grain (particle size (nano); g / liter i machine salt (% by mass) pH BDI honing rate (nano / min) Example 1 Colloidal cerium oxide (40 nm, 100 g / liter) Ammonium nitrate (1.0%) 9.5 72 Example 2 Gas phase method Ceria (20 nm, 100 g/L) Potassium Nitrate (1.0%) 9.5 35 Example 3 Colloidal cerium oxide (60 nm, 80 g/L) Ammonium sulphate (1.0%) 9.5 76 Example 4 Gas Phase method of cerium oxide (30 nm, 150 g / liter) Ammonium sulphate (3.0%) 9.5 95 Example 5 Colloidal cerium oxide (40 nm, 200 g / liter) Sodium chloride (1.0%) 9 68 Implementation Example 6 Gas phase ruthenium dioxide (15 nm, 150 g / liter) Potassium nitrate (1.0%) 9 20 Example 7 Colloidal cerium oxide (80 nm, 50 g / liter) Ammonium chloride (1.5%) 9.5 60 Example 8 Colloidal cerium oxide (20 nm, 200 g/L) Potassium nitrate (1.0%) 10.5 55 Example 9 Gas phase cerium oxide (20 nm, 100 g/L) Sodium nitrate (1.0 %) 10.5 65 Example 10 Colloidal cerium oxide (20 nm, 80 g/L) Ammonium sulphate (1.0%) 9.5 60 Example 11 Gas phase cerium oxide (60 nm, 100 g/L) Ammonium nitrate (4.0%) 10 90 Example 12 Colloidal silica sand (80 nm, 150 g/L) Ammonium chloride (1.0%) 9.5 70 Example 13 Vapor phase cerium oxide (40 nm, 100 g/L) Gas phase Method of cerium oxide (30 nm, 150 g / liter) Ammonium nitrate (1.0%) 8.5 51 Example 14 Gas phase cerium oxide (20 nm, 100 g / liter) Colloidal cerium oxide (40 nm, 100 g / liter) Ammonium nitrate (1.0%) 9.5 71 Example 15 Colloidal cerium oxide (10 nm, 10 g / liter) Colloidal cerium oxide (40 nm, 100 g / liter) Ammonium nitrate (1.0%) 9.5 68 Example 16 Colloidal cerium oxide (20 nm, 80 g/L) Colloidal cerium oxide (60 nm, 100 g/L) Ammonium nitrate (1.0%) 9.5 75 Example 17 Gas phase cerium oxide (10 nm, 40 g / liter) Gas phase sand dioxide (15 nm, 50 g / liter) Gas phase cerium oxide (30 nm, 100 g / liter) Ammonium nitrate (1.0% 10.5 105 Example 18 Gas phase ruthenium dioxide (10 nm, 40 g / liter) Gas phase sand dioxide (15 nm, 50 g / liter) Colloidal cerium oxide (80 nm, 150 g / Liters) Ammonium nitrate (3.0%) 9.5 110 Comparative Example 1 Colloidal cerium oxide (40 nm, 100 g/L) Ammonium nitrate (1.0%) 2 16 Comparative Example 2 Colloidal cerium oxide (40 nm, 100 g/ Liters) Ammonium nitrate (0.1%) 2 14 Comparative Example 3 Colloidal cerium oxide (40 nm, 100 g/L) Ammonium nitrate (0.01%) 2 15 Comparative Example 4 Colloidal cerium oxide (40 nm, 100 g/ Liters) - 9.5 8 Comparative Example 5 Gas phase ruthenium dioxide (40 nm, 100 g / liter) - 6 2 According to the results of Table 1, the inventive examples 1 to 18 achieved a very large insulating film. Grinding speed. On the other hand, in comparison with the examples 1 to 5 of the ratio -28-200826164 of the present invention, a sufficient honing speed cannot be achieved. [Simple description of the diagram] Μ 〇 [Description of main components] Charm -29-