TW200902694A - Polishing slurry - Google Patents

Polishing slurry Download PDF

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TW200902694A
TW200902694A TW097109775A TW97109775A TW200902694A TW 200902694 A TW200902694 A TW 200902694A TW 097109775 A TW097109775 A TW 097109775A TW 97109775 A TW97109775 A TW 97109775A TW 200902694 A TW200902694 A TW 200902694A
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honing
group
liquid
formula
mass
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TW097109775A
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Chinese (zh)
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TWI402336B (en
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Tetsuya Kamimura
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The object of this invention is related to provide a polishing agent for polishing solid grinding particles that are used for polishing the barrier layer consisting of barrier metal materials in the barrier CMP, which can maintain high polishing speed relative to the polished film during polishing the barrier layer, and can sufficiently inhibit the polishing speed relative to low dielectric constant Low-k film. The mean for solution is to use a polishing liquid for polishing the barrier layer of semiconductor, which is characterized by that the said polishing liquid contains antistatic agent.

Description

200902694 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種在半導體裝置製程所用之硏磨液， 詳言之，有關一種硏磨液，其係在半導體裝置配線步驟之 平坦化中，適用於主要由阻障金屬材料所構成的阻障層之 硏磨。 【先前技術】 於半導體積體電路（以下，稱爲「LSI」。）所代表之 半導體裝置之開發中，爲了小型化與高速化，近年來，正 尋求依照配線之微細化與積層化所導致的高密度化與高積 體化。爲了此技術係已逐漸採用化學機械硏磨（Chemical Mechanical Polishing’以下稱爲「CMP」。）等各種技術。 此C Μ P係於進行層間絕緣膜等被加工膜之表面平坦化、栓 塞形成、埋入金屬配線形成等情形下之必要技術，以進行 基板之平滑化、配線形成時之多餘金屬薄膜的去除、或是 絕緣膜上多餘阻障層的去除。 CMP之一般方法係將硏磨墊貼附於圓形之硏磨固定盤 (壓台（platen))上’利用硏磨液以浸漬硏磨墊表面，將基 板（晶圓）之表面按壓於墊上’從其背面施加既定之壓力 (硏磨壓力）的狀態下’使硏磨固定盤及基板二者予以旋 轉’藉由所產生的機械摩擦而將基板之表面予以平坦化。 於製造LSI等半導體裝置之際，進行多層微細配線， 於其各層中’於形成C u等金屬配線之際，以防止向層間絕 緣膜之配線材料的擴散’或使配線材料之緊貼性得以提高 200902694 爲目的，預先形成Ta或TaN、Ti、TiN等之阻障金屬所進 行的。 爲了形成各配線層，首先，利用電鍍法等，歷經一階 段或多階段以進行去除所碟裝之多餘配線材金屬膜之CMP (以下，稱爲「金屬膜CMP」。），接著，藉此以進行去 除露出於表面的阻障金屬材料（阻障金屬）之CMP (以下 ’稱爲「阻障金屬CMP」。）爲一般所實施的。然而，藉 由金屬膜CMP已造成配線部被過度硏磨之所謂薄碟化（ dishing ) ’或進一步引起過餘（erosion)的問題。 爲了減輕此薄碟化，正尋求於金屬膜C Μ P後所進行的 阻障金屬CMP中，調整金屬配線部之硏磨速度與阻障金屬 部之硏磨速度，最後形成薄碟化或過蝕等之高低差少的配 線層。亦即，於阻障金屬CMP中，相較於金屬配線材，阻 障金屬或層間絕緣膜之硏磨速度爲相對小的情形，由於配 線部被快速硏磨等之薄碟化，或其結果之過蝕將發生，期 望阻障金屬或絕緣膜層之硏磨速度爲適度大的。此係由於 具有提高阻障金屬CMP產量的優點以外，實際上，大多因 金屬膜CMP而發生淺薄化，基於上述之理由，因而期望尋 求相對提高阻障金屬或絕緣膜層的硏磨速度之觀點。 用於CMP之金屬用硏磨溶液，一般含有硏磨粒（例如 ，氧化鋁、二氧化矽）與氧化劑（例如，過氧化氫、過硫 酸）。認爲基本之機構係藉由氧化劑以氧化金屬表面，利 用硏磨粒以去除其氧化皮膜後而進行硏磨。 然而，一旦使用含有如此固體硏磨粒之硏磨液以進行 200902694 C Μ P時，將發生如下之情形：硏磨傷痕（刮傷）、整個硏 磨面被過度硏磨之現象（偏薄）、硏磨金屬面凹陷成碟狀 的現象（薄碟化）；除了金屬配線間之絕緣體被過度硏磨 的現象之外，複數個配線金屬面凹陷成碟狀的現象（過蝕 )等《 另外，藉由使用含有固體硏磨粒之硏磨液，於硏磨後 ，爲了去除殘留於半導體面之硏磨液，通常所進行的洗淨 步驟將變得複雜，再者，針對處理其洗淨後之液體（廢液 )，存在必須沈澱分離固體硏磨粒等之成本面上的問題點 〇 針對含有如此之固體硏磨粒，已進行如下之各種探討 0 例如，已分別有人提案：以幾乎不發生硏磨傷痕而進 行高速硏磨爲目的之CMP硏磨劑及硏磨方法（例如，參照 專利文獻1。）、使CMP中之洗淨性得以提高之硏磨組成 物及硏磨方法（例如，參照專利文獻2。）、及期望防止 硏磨粒凝聚的硏磨用組成物（例如，參照專利文獻3。） 〇 【專利文獻1】：專利特開2003 - 1 7446號公報 【專利文獻2】：專利特開2003-142435號公報 【專利文獻3】：專利特開2 0 0 0 - 8 4 8 3 2號公報 【發明内容】 曼JLBi欲解決之技術問頴 另外於最近，更低介電常數且強度小的絕緣膜（L〇w_k 200902694 膜）已被逐漸使用。此係由於最尖端裝置中之配線間距離 接近所致，歸因於使用介電常數高的絕緣膜之際，在配線 間之電性不良將發生。因爲如此Low-k膜的強度極小，有 於CMP時之加工中，被過度刮除的問題。 針對如此之課題，將相對於硏磨阻障層時之被硏磨膜的 硏磨速度維持於高硏磨速度，並且能夠充分抑制相對於低 介電常數Low-k膜之硏磨速度的技術，迄今仍未能夠得到 爲其現狀。 因而，本發明之目的係在於提供一種硏磨劑，其中硏磨 液係使用可用於硏磨由阻障金屬材料而成的阻障層之阻障 CMP的固體硏磨粒，能夠高硏磨速度地維持相對於硏磨阻 障層時之被硏磨膜的硏磨速度，並且能夠充分抑制相對於 低介電常數Low-k膜的硏磨速度。 解決問顆之技術手段 本發明人鑽硏探討之結果，藉由硏磨液含有抗靜電 劑’發現能夠解決上述問題而達成課題。 亦即，本發明係提供下列（1 )〜（1 〇 )之硏磨液及下 列（11 )之硏磨方法： (1 ) 一種硏磨液’其係爲了硏磨半導體積體電路阻障 層之硏磨液，其特徵在於含有抗靜電劑。 還有’以下將此稱爲「本發明之第1態樣硏磨液」。 (2) —種硏磨液，其係爲了硏磨半導體積體電路阻障 層之硏磨液’其特徵在於含有下列通式（丨）所示之化合物。 還有’以下將此稱爲「本發明之第2態樣硏磨液」。 200902694 另外，將本發明之第1及第2態樣之硏磨液合稱爲「本 發明之硏磨液」。 通式（1 ) ,(CH2CH20)a-H 、R2 (式中，R1、R2係表示各自獨立之由氫原子、碳數6〜30 之烷基、烯基、環烷基、芳基、芳烷基與聚環氧乙烷鏈（EO) 所構成族群中所選出之至少一種，R1、R2也可以相互鍵結’ a係1以上之整數）。 (3 )揭示於上述（2 )之硏磨液，其中相對於硏磨液 之所有質量，該通式（1)所示之化合物的濃度爲0.005〜 5 0 g/L。 (4)揭示於上述（1)〜（3)中任一項之硏磨液’其 中更含有腐蝕抑制劑與膠體二氧化矽，且PH爲2.5〜5.0 ° (5 )揭示於上述（4 )之硏磨液，其中相對於硏磨液 之所有質量，該膠體二氧化矽之濃度爲0.5〜15質量％ ° (6)揭示於上述（4)或（5)之硏磨液’其中該膠體 二氧化矽之—次平均粒徑爲20〜50nm之範圍。 (7 )揭示於上述（4 )〜（6 )項中任一項之硏磨液， 其中該腐蝕抑制劑爲由1，2,3-苯并***、5,6-二甲基-1，2,3-苯并***、卜（1，2 -二羧乙基）苯并***、1-〔N，N_雙（羥 乙基）胺甲基〕苯并***與1-(羥甲基）苯并***所構成 200902694 族群中所選出之至少一種的化合物。 (8 )揭示於上述（1 )〜（7 )中任一項之硏磨液，其 中更含有下列通式（2 )所示之二（四級銨）陽離子或下列 通式（3 )所示之一（四級銨）陽離子： 通式（2 ) 尽1 R4200902694 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a honing fluid used in a semiconductor device process, and more particularly to a honing fluid which is planarized in a wiring step of a semiconductor device. It is suitable for the honing of the barrier layer mainly composed of barrier metal materials. [Prior Art] In the development of a semiconductor device represented by a semiconductor integrated circuit (hereinafter referred to as "LSI"), in recent years, in order to reduce the size and speed of wiring, in recent years, it has been sought to reduce wiring and buildup. High density and high integration. Various techniques such as chemical mechanical polishing (hereinafter referred to as "CMP") have been gradually adopted in this technology. This C Μ P is a technique necessary for planarizing the surface of the film to be processed such as the interlayer insulating film, forming a plug, or embedding a metal wiring, etc., in order to smooth the substrate and remove the excess metal film during wiring formation. Or the removal of excess barrier layer on the insulating film. The general method of CMP is to attach a honing pad to a circular honing plate (platen) to immerse the surface of the lining pad with a honing liquid to press the surface of the substrate (wafer) onto the pad. 'Rotating both the honing fixed disk and the substrate from a state where a predetermined pressure (honing pressure) is applied from the back surface thereof] The surface of the substrate is flattened by the generated mechanical friction. When a semiconductor device such as an LSI is manufactured, a plurality of fine wirings are formed, and in each of the layers, when the metal wiring such as Cu is formed, the diffusion of the wiring material to the interlayer insulating film is prevented, or the adhesion of the wiring material is improved. For the purpose of raising 200,902,694, a barrier metal of Ta or TaN, Ti, TiN or the like is formed in advance. In order to form each of the wiring layers, first, CMP (hereinafter referred to as "metal film CMP") for removing the unnecessary wiring metal film of the disk is performed in one or more stages by a plating method or the like. CMP (hereinafter referred to as "barrier metal CMP") for removing a barrier metal material (barrier metal) exposed on the surface is generally performed. However, the metal film CMP has caused the so-called dishing of the wiring portion to be excessively honed or further caused a problem of erosion. In order to alleviate this thin disk formation, in the barrier metal CMP which is performed after the metal film C Μ P, the honing speed of the metal wiring portion and the honing speed of the barrier metal portion are adjusted, and finally a thin disk is formed or passed. A wiring layer with a low level of difference such as etch. That is, in the barrier metal CMP, the honing speed of the barrier metal or the interlayer insulating film is relatively small compared to the metal wiring material, and the wiring portion is quickly honed or the like, or the result thereof The overetch will occur, and the honing speed of the barrier metal or insulating film layer is expected to be moderately large. In addition to the advantage of improving the yield of the barrier metal CMP, in fact, most of the thinning occurs due to the metal film CMP. For the above reasons, it is desirable to seek a viewpoint of relatively improving the honing speed of the barrier metal or the insulating film layer. . The honing solution for metals used in CMP generally contains honing particles (e.g., alumina, ceria) and an oxidizing agent (e.g., hydrogen peroxide, persulfate). The basic mechanism is considered to be honing by oxidizing the metal surface with an oxidizing agent and using honing particles to remove the oxide film. However, once the honing liquid containing such solid honing particles is used to carry out 200902694 C Μ P, the following occurs: honing scars (scratches), excessive honing of the entire honing surface (thinning) a phenomenon in which the metal surface is recessed into a dish (small disc); in addition to the phenomenon that the insulator of the metal wiring compartment is excessively honed, a plurality of wiring metal faces are recessed into a dish shape (over-etching), etc. By using a honing liquid containing solid honing particles, after honing, in order to remove the honing liquid remaining on the semiconductor surface, the washing step usually performed is complicated, and further, the cleaning is performed for the treatment. After the liquid (waste liquid), there is a problem on the cost side where it is necessary to precipitate and separate the solid honing granules, etc. For the inclusion of such solid honing granules, various investigations have been made as follows. For example, it has been separately proposed: A CMP honing agent and a honing method (for example, refer to Patent Document 1) for high-speed honing without causing honing scars, and a honing composition and a honing method for improving the detergency in CMP ( For example, refer to Patent Document 2) and a composition for honing which is intended to prevent aggregation of honing particles (for example, refer to Patent Document 3). [Patent Document 1] Patent Publication No. 2003 - 1 7446 [Patent Literature] 2: Patent Publication No. 2003-142435 [Patent Document 3]: Patent Laid-Open No. 2 0 0 - 8 4 8 3 2 [Summary of the Invention] The technical problem that Man JLBi wants to solve is another recently, lower An insulating film (L〇w_k 200902694 film) having a low dielectric constant and low strength has been gradually used. This is due to the proximity of the wiring between the sharpest devices, and the electrical failure between the wirings occurs due to the use of an insulating film having a high dielectric constant. Because of this, the strength of the Low-k film is extremely small, which is a problem of excessive scraping during processing at the time of CMP. In order to solve such a problem, the honing speed of the honing film at the time of honing the barrier layer is maintained at a high honing speed, and the honing speed with respect to the low dielectric constant Low-k film can be sufficiently suppressed. So far, it has not been able to get its status quo. Accordingly, it is an object of the present invention to provide a honing agent wherein a honing liquid is a solid honing granule which can be used for damaging a barrier layer of a barrier layer made of a barrier metal material, and is capable of high honing speed. The honing speed of the honed film with respect to the honing of the barrier layer is maintained, and the honing speed with respect to the low dielectric constant Low-k film can be sufficiently suppressed. The technical means for solving the problem is that the inventors of the present invention have found that the above problem can be solved by the fact that the honing fluid contains an antistatic agent. That is, the present invention provides the following honing liquids of (1) to (1 〇) and the following honing method of (11): (1) A honing liquid 'for honing a semiconductor integrated circuit barrier layer The honing fluid is characterized by containing an antistatic agent. Further, the following is referred to as "the first aspect honing liquid of the present invention". (2) A honing liquid which is a honing liquid for honing a barrier layer of a semiconductor integrated circuit, and is characterized by containing a compound represented by the following formula (丨). Further, hereinafter, this is referred to as "the second aspect honing liquid of the present invention". 200902694 The honing liquids of the first and second aspects of the present invention are collectively referred to as "the honing liquid of the present invention". Formula (1), (CH2CH20)aH, R2 (wherein R1 and R2 represent independently a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; At least one selected from the group consisting of polyethylene oxide chains (EO), R1 and R2 may be bonded to each other 'a number of 1 or more integers'. (3) The honing liquid according to the above (2), wherein the concentration of the compound represented by the formula (1) is from 0.005 to 50 g/L with respect to all the masses of the honing liquid. (4) The honing liquid of any one of the above (1) to (3), further comprising a corrosion inhibitor and colloidal cerium oxide, and having a pH of 2.5 to 5.0 ° (5) is disclosed in the above (4) The honing liquid, wherein the concentration of the colloidal cerium oxide is 0.5 to 15% by mass relative to all the masses of the honing liquid. (6) The honing liquid of the above (4) or (5), wherein the colloid The cerium oxide has a sub-average particle diameter in the range of 20 to 50 nm. (7) The honing liquid according to any one of the above items (4) to (6), wherein the corrosion inhibitor is 1,2,3-benzotriazole, 5,6-dimethyl-1 , 2,3-benzotriazole, di(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole and 1- (Hydroxymethyl)benzotriazole constitutes a compound of at least one selected from the group of 200,902,694. (8) The honing liquid according to any one of the above (1) to (7), which further comprises a bis(quaternary ammonium) cation represented by the following formula (2) or represented by the following formula (3) One (quaternary ammonium) cation: general formula (2)

通式（3 )General formula (3)

〔通式（2)或通式（3)中，R1〜R7係表示各自獨立之由 碳數1〜20之烷基、烯基、環烷基、芳基與芳烷基所構成 族群中所選出之至少一種，R1〜R6中之二個也可以相互鍵 結，X係表示由碳數1〜1 0之伸烷基、伸烯基、伸環烷基、 伸芳基與組合此等基所構成族群中所選出之至少一種〕° (9)揭示於上述（1)〜（8)中任一項之硏磨液’其 中更含有具有羧基之化合物，該具有羧基之化合物爲下列 通式（4 )所示之化合物： 通式（4 )[In the general formula (2) or the general formula (3), R1 to R7 each represent a group consisting of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl group independently having a carbon number of 1 to 20; At least one selected, two of R1 to R6 may be bonded to each other, and X represents an alkyl group having an alkyl group of 1 to 10, an alkenyl group, a cycloalkyl group, an extended aryl group, and a combination thereof. (9) The honing liquid of any one of the above (1) to (8) which further contains a compound having a carboxyl group, and the compound having a carboxyl group is of the following formula (4) Compounds shown: General formula (4)

R7 - 0 - R8 - COOH -10- 200902694 〔通式（4)中’ R7與R8係表示各自獨立之烴基，尺7與r8 也可以相互鍵結而形成環狀構造〕。 (10) 揭示於上述（1)〜（9)中任一項之硏磨液， 其中更含有陰離子系界面活性劑或陽離子系界面活性劑。 (11) 一種硏磨方法，其係於半導體積體電路阻障層 之硏磨中，使用上述（1)〜（1〇)中任—項之硏磨液。 雖然本發明之作用並不明確，如下方式予以推測。 亦即’認爲因爲硏磨劑中之抗靜電劑係於硏磨中將附 著於Low-k膜之被硏磨面，控制被硏磨面之帶電狀態。更 具體而言’預料已附著抗靜電劑的被硏磨面之間與硏磨粒 之間的靜電親和力已降低。認爲依照靜電親和力之降低， 於墊硏磨粒-被硏磨面間之物理作用（物理性刮除作用）將 變弱’對於L 〇 w - k膜種之硏磨速度將受到抑制。 【發明之效果】 本發明之硏磨液能夠高硏磨速度地維持相對於硏磨阻 障層時之被硏磨膜的硏磨速度，並且能夠充分抑制相對於 低介電常數Low-k膜的硏磨速度。 【實施方式】 以下，針對本發明之具體態樣加以說明。 本發明之第1態樣硏磨液係爲了硏磨半導體積體電路 阻障層之硏磨液，其特徵在於含有抗靜電劑。 還有，於本發明中，所謂「硏磨液」意指不僅使用於 硏磨時的硏磨液（亦即，依需要所稀釋的硏磨液），也意 指包含硏磨液之濃縮液。所謂濃縮液或被濃縮之硏磨液， -11 - 200902694 也意指較硏磨時使用之際的硏磨液的溶質濃度爲高的、所 調製的硏磨液，於使用於硏磨之際’利用水或水溶液等加 以稀釋，而於硏磨所使用之物。一般而言’稀釋倍率係1 〜20體積倍。於本專利說明書中’所謂「濃縮」及「濃縮 液」係依循意指較使用狀態爲「濃稠」及「濃稠之液」的 慣用表現而加以使用，與隨蒸發等之物理性濃縮操作的〜 般用語之意義不同的用法而加以使用。 fs 以下，針對構成本發明之硏磨液的各成分加以詳細說 V .. 明。 〔抗靜電劑〕 本發明之第1態樣硏磨液係含有抗靜電劑。 於本發明之第1態樣硏磨液中所含之抗靜電劑只要爲 習知資料等（例如，「抗靜電材料之技術與應用」（CMC 出版）、「油化學辭典脂質·界面活性劑」（九善）、「界 面活性劑之機能與利用技術」（普及版）、「界面活性劑. ij 性能要覽」（技術情報協會））所習知之物的話，並未予 以特別限定。 其中，基於達成更充分抑制硏磨速度之觀點，較宜爲 下列通式（1 )所示之化合物： 通式（1 )R7 - 0 - R8 - COOH -10- 200902694 [In the formula (4), R7 and R8 represent each independently a hydrocarbon group, and the ruthenium 7 and r8 may be bonded to each other to form a cyclic structure]. (10) The honing liquid according to any one of the above (1) to (9), further comprising an anionic surfactant or a cationic surfactant. (11) A honing method for honing a barrier layer of a semiconductor integrated circuit using the honing liquid of any of the above (1) to (1). Although the effect of the present invention is not clear, it is presumed as follows. That is, it is considered that the antistatic agent in the honing agent is attached to the honed surface of the Low-k film in the honing to control the charged state of the honed surface. More specifically, it is expected that the electrostatic affinity between the honed surfaces of the adhered antistatic agent and the honing particles has been lowered. It is considered that according to the decrease in electrostatic affinity, the physical action (physical scraping action) between the mat granules and the honed surface will be weakened, and the honing speed for the L 〇 w - k film species will be suppressed. [Effects of the Invention] The honing liquid of the present invention can maintain the honing speed of the honed film with respect to the honing barrier layer at a high honing speed, and can sufficiently suppress the Low-k film with respect to the low dielectric constant The speed of honing. [Embodiment] Hereinafter, specific aspects of the invention will be described. The first aspect of the honing liquid of the present invention is characterized in that it contains an antistatic agent for honing the honing liquid of the semiconductor integrated circuit barrier layer. Further, in the present invention, the term "honing fluid" means not only the honing liquid used in honing (that is, the honing liquid diluted as needed), but also the concentrated liquid containing the honing liquid. . The so-called concentrate or concentrated honing liquid, -11 - 200902694 also means the honing liquid with a high solute concentration of the honing liquid used during honing, when used in honing 'Dilute with water or an aqueous solution, etc., and use it for honing. In general, the dilution ratio is 1 to 20 times the volume. In this patent specification, 'so-called "concentration" and "concentrate" are used in the context of the conventional performance of "thick" and "thick liquid", and physical concentration operations with evaporation, etc. The use of the meaning of the general term is used in different ways. Fs Hereinafter, each component constituting the honing liquid of the present invention will be described in detail. [Antistatic Agent] The first aspect of the present invention contains an antistatic agent. The antistatic agent contained in the honing liquid of the first aspect of the present invention is not limited to conventional materials (for example, "Technology and Application of Antistatic Materials" (published by CMC), "Oil Chemistry Dictionary Lipid / Surfactant" (Jiushan), "Functional Actuator Function and Utilization Technology" (Popular Edition), "Interacting Agents. ij Performance Overview" (Technical Information Association)) are not specifically limited. Among them, based on the viewpoint of achieving more sufficient suppression of the honing speed, it is preferred to be a compound represented by the following formula (1): Formula (1)

-12- 200902694 (式中’ R1、R2係表示各自獨立之由氫原子、碳數6〜3〇 之烷基、烯基、環烷基 '芳基、芳烷基與聚環氧乙烷鏈（E〇) 所構成族群中所選出之至少一種，、R2也可以相互鍵結， a係1以上之整數）。 針對通式（1 )所示之化合物’於本發明之第2態樣硏 磨液中詳加說明。 抗靜電劑能夠各自單獨使用或組合二種以上後而力口以 使用。 相對使用於硏磨之際的硏磨液（亦即，利用水或水溶 液加以稀釋之情形係稀釋後之硏磨液。以後之「使用於研; 磨之際的硏磨液」也爲同義的。），本發明中之抗靜電劑 的添加量較宜爲0.005g/L以上、50g/L以下，更佳爲〇.〇1 g/L 以上、30g/L以下。亦即，基於使硏磨速度得以充分抑制之 觀點，抗靜電劑之添加量較宜爲0.005 g/L以上，基於不妨 礙相對於其他膜種的硏磨速度之觀點，較宜爲5 Og/L以下。 本發明之第1態樣硏磨液，必要時也可以更含有例如 硏磨粒、腐蝕抑制劑、膠體二氧化矽、四級銨鹽、具有羧 基之化合物、陰離子系界面活性劑、陽離子系界面活性劑 等之任意成分。 針對任意成分，於本發明之第2態樣硏磨液中詳加說 明。 本發明之第1態樣硏磨液所含之各成分可以單獨使用 一種，也可以倂用二種以上。 接著，以下針對本發明之第2態樣硏磨液加以說明。 -13- 200902694 本發明之第2態樣硏磨液係一種爲了硏磨半導體積體 電路阻障層之硏磨液，其特徵在於含有下列通式（°所不 之化合物： 通式（1 )-12- 200902694 (wherein R1 and R2 represent independent alkyl, alkenyl, cycloalkyl 'aryl, aralkyl and polyethylene oxide chains from a hydrogen atom, a carbon number of 6 to 3 fluorene (E〇) At least one selected from the group consisting of, R2 may be bonded to each other, and a is an integer of 1 or more). The compound ' represented by the formula (1) is described in detail in the second aspect of the present invention. The antistatic agents can be used singly or in combination of two or more kinds. The honing fluid used for honing (that is, the dilution with water or an aqueous solution is the honing fluid after dilution. The later use of honing fluid for grinding; the honing fluid for grinding) is also synonymous. The amount of the antistatic agent to be added in the present invention is preferably 0.005 g/L or more and 50 g/L or less, more preferably 〇1 g/L or more and 30 g/L or less. That is, the amount of the antistatic agent added is preferably 0.005 g/L or more based on the viewpoint of sufficiently suppressing the honing speed, and is preferably 5 Og/based on the viewpoint of not impeding the honing speed with respect to other film types. L or less. The first aspect of the present invention may further contain, for example, honing particles, corrosion inhibitor, colloidal cerium oxide, quaternary ammonium salt, a compound having a carboxyl group, an anionic surfactant, and a cation interface. Any component such as an active agent. The optional component is described in detail in the second aspect of the honing fluid of the present invention. The components contained in the honing liquid of the first aspect of the present invention may be used singly or in combination of two or more. Next, the second aspect of the honing liquid of the present invention will be described below. -13- 200902694 The second aspect of the present invention is a honing fluid for honing a barrier layer of a semiconductor integrated circuit, which is characterized by containing a compound of the following formula: (1)

R1-NR1-N

(式中，R，、R2係表示各自獨立之由氫原子、碳數6〜30 之烷基、烯基、環烷基、芳基、芳烷基與聚環氧乙院鏈（E〇） 所構成族群中所選出之至少一種，R1、R2也可以相互鍵結’ a係1以上之整數）。 於上述通式（1)中，R1、R2係表示各自獨立之由氫原 子、碳數6〜30之烷基、烯基、環烷基、芳基、芳烷基與 聚環氧乙烷鏈（EO)所構成族群中所選出之至少一種’ Rl、 R2也可以相互鍵結，a係1以上之整數。 具體而言，該碳數6〜3 0之烷基，例如’可列舉：癸 基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷 基、三十烷基等，其中，較宜爲十二烷基、十四烷基、十 六烷基、十八烷基。 另外，具體而言，該烯基較宜爲碳數6〜30者，例如， 可列舉：癸烯基、十二烯基、十四烯基、十六烯基、十八 烯基、二十烯基、三十烯基等，其中，較宜爲十二稀基、 十四烯基、十六烯基、十八烯基。 具體而言，例如，該環烷基較宜爲環己基、院基取代 -14- 200902694 物環己基等。 具體而言，例如，該芳基可列舉：苯基、萘基等，其 中，較宜爲苯基。 該聚環氧乙院鏈（_ EO)較宜爲分子量100〜10000之範 圍，_更佳爲分子量200〜5000之範圍。 上述之各基也可以更具有取代基，作爲可導入之取代 基，例如，可列舉：羥基、胺基、羧基、磷酸基、亞胺基、 硫醇基、磺基、硝基等。 基於充分抑制相對於目的膜之硏磨速度的觀點，通式 (1 )中之a較宜爲1以上之整數；基於更充分抑制相對於 目的膜之硏磨速度的觀點，更佳爲1〜50之整數。 以下，顯示本發明中之通式（1 )所示之化合物的較佳 具體例（例示化合物D-1〜D-23 )，但是本發明並不受此 等化合物所限定。 D1(wherein R, R2 represent independently a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a polyepoxy chain (E〇) At least one selected from the group consisting of R1 and R2 may be bonded to each other 'a number of 1 or more integers'. In the above formula (1), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group and a polyethylene oxide chain. At least one selected from the group consisting of (EO) 'R1, R2' may be bonded to each other, and a is an integer of 1 or more. Specifically, the alkyl group having 6 to 30 carbon atoms, for example, may be exemplified by mercapto, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and thirties. The alkyl group or the like is preferably a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group. Further, specifically, the alkenyl group is preferably a carbon number of 6 to 30, and examples thereof include a nonenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecyl group, and 20 An alkenyl group, a triaconyl group or the like, among which, it is preferably a dozenyl group, a tetradecenyl group, a hexadecenyl group or an octadecyl group. Specifically, for example, the cycloalkyl group is preferably a cyclohexyl group, a hospital group-substituted -14-200902694 cyclohexyl group or the like. Specifically, examples of the aryl group include a phenyl group and a naphthyl group, and among them, a phenyl group is preferred. The polyepoxy chain (_EO) is preferably in the range of from 100 to 10,000 in molecular weight, more preferably in the range of from 200 to 5,000. Each of the above groups may have a more substituent. Examples of the substituent which can be introduced include a hydroxyl group, an amine group, a carboxyl group, a phosphoric acid group, an imido group, a thiol group, a sulfo group, a nitro group and the like. From the viewpoint of sufficiently suppressing the honing speed with respect to the target film, a in the general formula (1) is preferably an integer of 1 or more; more preferably 1 to 1 based on more sufficient suppression of the honing speed with respect to the intended film. An integer of 50. Hereinafter, preferred specific examples (exemplified compounds D-1 to D-23) of the compound represented by the formula (1) in the present invention are shown, but the present invention is not limited by these compounds. D1

Cl 2¾ >i—(CH2CH2〇)aH C12H25 D2 D3 D4Cl 23⁄4 >i—(CH2CH2〇)aH C12H25 D2 D3 D4

Cl6^33 C)jH37 C2〇H4ICl6^33 C)jH37 C2〇H4I

—(CH2CH20)aH 一(CH2CH2〇)aH 'N —(CH2CH20)aH C16H33 Cj8H37 C2〇H41 D5 D6 D7 D8—(CH2CH20)aH A(CH2CH2〇)aH 'N —(CH2CH20)aH C16H33 Cj8H37 C2〇H41 D5 D6 D7 D8

(CH2CH20)aH .(CH2CH2〇)aH ^,(CH2CH20)aH ^(CH2CH2〇)aH C10H2i-N C12H25—N C16H33—N C18H33 -(CH2CH20)aH .(CH2CH2〇)aH ^,(CH2CH20)aH ^(CH2CH2〇)aH C10H2i-N C12H25-N C16H33-N C18H33 -

\(CH2CH2〇)bH Nv(CH2CH20)bH (CH2CH20)bH (CH2CH20)1>H\(CH2CH2〇)bH Nv(CH2CH20)bH (CH2CH20)bH (CH2CH20)1>H

D9 DIO Dll D12 Ha(OH2CH2C)- C]2H25〇C c16H„oc、 C1UH37OC、 1—(CH2CH20)aH \- -(CH2CH20)aH 广 —(CH2CH2〇)aH i / / / I Hai〇H2CH2C) Cl2H25〇C c16h33oc CI8Hn〇C -15- 200902694 D13 D14 D15 D16D9 DIO Dll D12 Ha(OH2CH2C)- C]2H25〇C c16H„oc, C1UH37OC, 1—(CH2CH20)aH \- -(CH2CH20)aH Guang—(CH2CH2〇)aH i / / / I Hai〇H2CH2C) Cl2H25 〇C c16h33oc CI8Hn〇C -15- 200902694 D13 D14 D15 D16

-{CH2CH2〇)aH (CH2CH2〇)aH ACH2CH2〇)zH ^(CH2CH20)aH-{CH2CH2〇)aH (CH2CH2〇)aH ACH2CH2〇)zH ^(CH2CH20)aH

Cl0H21OC-N( c】2h25oc-n( c)6h33oc-n CibH33OC-NCl0H21OC-N(c)2h25oc-n(c)6h33oc-n CibH33OC-N

\(CH2CH20)bH \(CH2CH20)bH (CH2CH20)bH {CH2CH2〇)bH D17 D18 D19 D20\(CH2CH20)bH \(CH2CH20)bH (CH2CH20)bH {CH2CH2〇)bH D17 D18 D19 D20

C12H25 \—(CH2CH20)aHC12H25 \—(CH2CH20)aH

C16H33 C18H37 —(CH2CH20)aH Ή 一{CH2CH20)aHC16H33 C18H37 —(CH2CH20)aH Ή a {CH2CH20)aH

„(CH2CH20)aH„(CH2CH20)aH

s(CH2CH2〇)bH D2] c,2h25oc、 D22 D23s(CH2CH2〇)bH D2] c, 2h25oc, D22 D23

Ci6H33〇C c18h37oc、Ci6H33〇C c18h37oc,

N —(CH2CH20)aH 一(CH2CH20>H N —(CH2CH2〇)aH 基於充分發揮添加劑效果之觀點，上述D5〜D8、D 1 3 〜D16與D20中之b較宜爲各自獨立之1〜100之整數，更 佳爲1〜50之整數。 基於將相對於硏磨阻障層時之被硏磨膜的硏磨速度維 持於更高硏磨速度，並且更充分抑制相對於低介電常數 Low-k膜之硏磨速度的觀點，通式（1)所示之化合物，其 中較宜爲 Dl、D2、D3、D4、D5、D6、D7、D8、D9、D10、 Dll' D12、 D13、 D14、 D15、 D16。 通式（1 )所示之化合物能夠各自單獨使用或組合二種 以上後而加以使用。 相對使用於硏磨時之硏磨液（亦即，利用水或水溶液 加以稀釋之情形係稀釋後之硏磨液。以後之「使用於硏磨 時之硏磨液」也爲同義的。），本發明中之通式（1)所示 -16 - 200902694 之化合物的添加量較宜爲0,005 g/L以上、50g/L以下，更佳 爲0.01g/L以上、30g/L以下。亦即，基於使硏磨速度得以 充分抑制之觀點，通式（1 )所示之化合物的添加量較宜爲 0.005 g/L以上，基於不妨礙相對於其他膜種的硏磨速度之 觀點，較宜爲50g/L以下。 〔腐蝕抑制劑〕 本發明之硏磨液可列舉：吸附於被硏磨表面後而形成 皮膜，含有控制金屬表面腐蝕之腐蝕抑制劑爲較佳之一態 樣。 於本發明之硏磨液中所含之腐蝕抑制劑，較宜含有於 分子內具有三個以上氮原子，並且具有縮環構造之雜芳香 環化合物。於此，「三個以上氮原子」較宜爲構成縮環之 原子，如此雜芳香環化合物較宜爲苯并***、及該苯并三 唑中已導入各種取代基而成的衍生物。 可用於本發明之腐蝕抑制劑，例如，可列舉：苯并三 唑、1，2,3-苯并***、5,6-二甲基-1，2,3-苯并***、1-( 1,2-二羧乙基）苯并***、卜〔Ν,Ν-雙（羥乙基）胺甲基〕苯 并***、1-(羥甲基）苯并***等。 其中’基於充分抑制配線腐蝕之觀點，較宜爲由1，2,3-苯并***、5,6 -二甲基-1,2,3-苯并***、1-( 1,2 -二羧乙基） 苯并***、1-〔 Ν，Ν-雙（羥乙基）胺甲基〕苯并***及^ (羥甲基）苯并***所選出。 腐蝕抑制劑可以各自單獨使用或組合二種以上後而加 以使用。 -17- 200902694 相對使用於硏磨時之硏磨液的質量，腐蝕抑制劑的添 加量較宜爲0.01g/L以上、2g/L以下，更佳爲0.05g/L以上、 2g/L以下。亦即，基於使薄碟予以擴大之觀點，腐蝕抑制 劑的添加量較宜爲0.0 1 g/L以上，基於保存安定性之觀點， 較宜爲0.2g/L以下。 〔膠體二氧化砂〕 本發明之硏磨液可列舉：硏磨粒之至少一部分較宜爲 含有膠體二氧化矽之一態樣。 此膠體二氧化矽較宜於粒子內部不含有鹼金屬等之不 純物’藉由烷氧基矽烷之水解後而得到的膠體二氧化矽。 另一方面’雖然也能夠使用藉由從矽酸鹼金屬水溶液以去 除鹼金屬之方法製得的膠體二氧化砂，此情形下，擔憂殘 留於粒子內部之鹼金屬將慢慢溶出，對硏磨性能造成影 響。基於如此之觀點’更佳爲將藉由烷氧基矽烷的水解所 得之物作爲原料。 膠體二氧化矽可以各自單獨使用或組合二種以上後而 加以使用。 因應於硏磨粒之使用目的而加以適當選擇，一般而 膠體一氧化砍之粒徑約爲1 0〜2 0 0 n m，基於使硏磨刮 傷不予以發生之觀點，較宜爲20〜50nm之範圍。 相對使用於硏磨時之硏磨液質量，本發明硏磨液中之 膠體二氧化砍的含量（濃度）較宜爲〇.5質量％以上、15 質量％以下，更佳爲3質量％以上、12質量％以下，尤以 5質量％以上、1 2質量％以下特別理想。亦即，基於利用 -18- 200902694 充分之硏磨速度以硏磨阻障層之觀點，膠體二氧化矽的含 量較宜爲0.5質量％以上。基於保存安定性之觀點，較宜 爲1 5質量％以下。 於本發明之硏磨液中，只要不損害本發明效果，能夠 倂用膠體二氧化矽以外之硏磨粒，此情形下，所有硏磨粒 之中，膠體二氧化矽之含有比例較宜爲50質量％以上，尤 以8 0質量％以上特別理想。所含之全部硏磨粒也可以均爲 膠體二氧化矽。 相對於本發明之硏磨液，作爲可與膠體二氧化矽倂用 之硏磨粒，例如，可列舉：二氧化矽煙塵、二氧化鈽、氧 化銘、二氧化欽等。此等倂用硏磨粒之大小可與膠體粒子 相等，或是更大，另外，較宜爲2倍以下。 〔二（四級銨）陽離子、一（四級銨）陽離子〕 本發明之硏磨液也可以更含有由二（四級銨）陽離子及 一（四級銨）陽離子所構成族群中所選出之至少一種（以 下，也有將其簡稱爲「特定陽離子」之情形。）。 能夠含有本發明硏磨液之二（四級銨）陽離子，只要化 學構造中含有二個第四級氮之構造即可，並未予以特別限 定。 另外，只要一（四級銨）陽離子的化學構造中含有—個 第四級氮之構造即可，並未予以特別限定。 基於達成充分硏磨速度提高之觀點，特定陽離子較宜 爲二（四級銨）陽離子或一（四級銨）陽離子。 例如，二（四級錢）陽離子可列舉：下列通式（2 )所示 -19- 200902694 之陽離子。 例如，一（四級銨）陽離子可列舉：下列通式（3 )所示 之陽離子。 其中，基於達成充分硏磨速度之觀點，較宜爲下列通 式（2)所示之陽離子及下列通式（3)所示之陽離子中任 —種或二種。 通式（2 )N -(CH2CH20)aH - (CH2CH20>HN - (CH2CH2〇)aH From the viewpoint of giving full play to the effect of the additive, b in the above D5 to D8, D1 3 to D16 and D20 is preferably 1 to 100 each independently An integer, more preferably an integer from 1 to 50. Based on maintaining the honing speed of the honed film relative to the honing barrier layer at a higher honing speed, and more sufficiently suppressing the low dielectric constant Low- From the viewpoint of the honing speed of the k film, the compound represented by the formula (1) is preferably D1, D2, D3, D4, D5, D6, D7, D8, D9, D10, Dll' D12, D13, D14. D15, D16. The compounds represented by the formula (1) can be used singly or in combination of two or more. The honing liquid used in honing (that is, the case of dilution with water or an aqueous solution) The diluted honing liquid is also synonymous with "the honing liquid used in honing".) The compound of the formula (1) shown in the present invention is preferably added in the amount of -16 - 200902694 It is 0,005 g/L or more and 50 g/L or less, more preferably 0.01 g/L or more and 30 g/L or less. That is, based on the honing speed The amount of the compound represented by the formula (1) is preferably 0.005 g/L or more, and is preferably 50 g/L or less from the viewpoint of not inhibiting the honing speed with respect to other film types. [Corrosion Inhibitor] The honing liquid of the present invention may be exemplified by a film which is adsorbed on the surface to be honed to form a film, and a corrosion inhibitor which controls corrosion of the metal surface is preferred. In the honing liquid of the present invention The corrosion inhibitor contained therein preferably contains a heteroaromatic ring compound having three or more nitrogen atoms in the molecule and having a condensed ring structure. Here, "three or more nitrogen atoms" is preferably an atom constituting a condensed ring, The heteroaromatic ring compound is preferably a benzotriazole and a derivative in which various substituents have been introduced into the benzotriazole. The corrosion inhibitor of the present invention can be used, for example, benzotriazole, 1 , 2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1-( 1,2-dicarboxyethyl)benzotriazole, Bu [Ν, Ν-bis(hydroxyethyl)amine methyl]benzotriazole, 1-(hydroxymethyl)benzotriazole, etc. The viewpoint of suppressing wiring corrosion is preferably 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1-( 1,2-dicarboxyl Benzotriazole, 1-[anthracene, bis-(hydroxyethyl)amine methyl]benzotriazole and ^(hydroxymethyl)benzotriazole are selected. Corrosion inhibitors can be used alone or When two or more types are combined, they are used. -17- 200902694 Relatively used for the quality of the honing liquid used in honing, the addition amount of the corrosion inhibitor is preferably 0.01 g/L or more, 2 g/L or less, more preferably 0.05. g/L or more and 2 g/L or less. In other words, the amount of the corrosion inhibitor added is preferably 0.01 g/L or more based on the viewpoint of expanding the thickness of the thin disk, and is preferably 0.2 g/L or less from the viewpoint of storage stability. [Colloidal silica sand] The honing liquid of the present invention may be exemplified by the fact that at least a part of the honing particles is preferably one of colloidal cerium oxide. The colloidal cerium oxide is preferably a colloidal cerium which is obtained by hydrolysis of an alkoxy decane by an impurity which does not contain an alkali metal or the like inside the particles. On the other hand, although it is also possible to use colloidal silica produced by a method of removing an alkali metal from an aqueous alkali metal citrate solution, in this case, it is feared that the alkali metal remaining inside the particles will slowly elute. Performance has an impact. Based on such a viewpoint, it is more preferable to use a substance obtained by hydrolysis of an alkoxydecane as a raw material. The colloidal cerium oxide may be used singly or in combination of two or more. In view of the purpose of the use of the honing particles, the particle diameter of the colloidal oxidized cleavage is generally about 10 to 200 nm, which is preferably 20 to 50 nm based on the viewpoint that the honing and scratching does not occur. The scope. The content (concentration) of the colloidal oxidized chopping in the honing liquid of the present invention is preferably 5% by mass or more, 15% by mass or less, and more preferably 3% by mass or more, based on the mass of the honing liquid used in the honing. 12% by mass or less, particularly preferably 5% by mass or more and 12% by mass or less. That is, the content of the colloidal cerium oxide is preferably 0.5% by mass or more based on the use of the honing speed of -18-200902694 to honing the barrier layer. From the viewpoint of preservation stability, it is preferably 15% by mass or less. In the honing liquid of the present invention, the honing particles other than the colloidal cerium oxide can be used as long as the effect of the present invention is not impaired. In this case, among the honing grains, the content of the colloidal cerium oxide is preferably It is particularly preferable that it is 50% by mass or more, and particularly preferably 80% by mass or more. All of the honing particles contained may also be colloidal cerium oxide. With respect to the honing liquid of the present invention, examples of the honing particles which can be used for the colloidal cerium oxide include cerium oxide soot, cerium oxide, oxidized cerium, and dioxins. The size of the honing particles may be equal to or greater than that of the colloidal particles, and more preferably less than 2 times. [Bis(quaternary ammonium) cation, mono (quaternary ammonium) cation] The honing liquid of the present invention may further comprise a group selected from the group consisting of a bis(quaternary ammonium) cation and a (quaternary ammonium) cation. At least one (hereinafter, there is also a case where it is simply referred to as "specific cation"). The bis(quaternary ammonium) cation which can contain the honing liquid of the present invention is not particularly limited as long as it has a structure in which the chemical structure contains two fourth-order nitrogens. Further, the structure of the fourth-stage nitrogen is not particularly limited as long as it has a chemical structure of one (quaternary ammonium) cation. The specific cation is preferably a di(quaternary ammonium) cation or a (quaternary ammonium) cation based on the viewpoint of achieving a sufficient honing speed. For example, the cation of the divalent (quaternary money) can be exemplified by the cation of -19-200902694 represented by the following formula (2). For example, the one (quaternary ammonium) cation may be a cation represented by the following formula (3). In particular, it is preferably one or two of the cations represented by the following general formula (2) and the cations represented by the following general formula (3), from the viewpoint of achieving a sufficient honing speed. General formula (2)

通式（3 )General formula (3)

〔通式（2)或通式（3)中，R1〜R7係表示各自獨立之由 碳數1〜20之烷基、烯基、環烷基、芳基與芳烷基所構成 族群中所選出之至少一種，R1〜R6中之二個也可以相互鍵 結，X係表示由碳數1〜10之伸烷基、伸烯基、伸環烷基、 伸芳基與組合此等之基所構成族群中所選出之至少一種〕。 具體而言，上述碳數1〜20之烷基，例如，可列舉：甲 基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，其 中，較宜爲甲基、乙基、丙基、丁基、環己基。 -20- 200902694 另外，具體而Η’該烯基較宜爲碳數2〜l〇之基，例如， 可列舉：乙烯基、丙烯基等。 具體而言’例如’該環烷基可列舉：環己基、環戊基等， 其中，較宜爲環己基。 具體而言，例如，該芳基可列舉：丁炔基、戊炔基 '己 炔基、苯基、萘基等，其中，較宜爲苯基。 具體而言，例如，該芳烷基可列舉：苄基，其中，較宜 爲苄基。 上述之各基，也可以更具有取代基，可導入之取代基， 例如，可列舉：羥基、胺基 '羧基、磷酸基、亞胺基、硫 醇基、磺基、硝基等。 上述通式（2)中之X係表示由碳數1〜之伸烷基、 伸嫌基、伸環烷基、伸芳基及組合二種以上此等之基所組 成之群組中所選出之至少一種。 還有’除了含有上述之有機連結基之外，以X所示之連 結基也可以於其鏈中含有一 S—、一 s(=〇)2_、— 〇一、 —C ( — 0 )—。 具體而言’上述碳數1〜1 0之伸烷基，例如，可列舉： 亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸 庚基、伸辛基等，其中，較宜爲伸乙基、伸戊基。 具體而言，例如，該伸烯基可列舉：伸乙烯基、伸丙烯 基等’其中，較宜爲伸丙稀基。 具體而言，例如，該伸環烷基可列舉：伸環己基、伸環 戊基等’其中，較宜爲伸環己基。 -21 -[In the general formula (2) or the general formula (3), R1 to R7 each represent a group consisting of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl group independently having a carbon number of 1 to 20; At least one selected, two of R1 to R6 may be bonded to each other, and X represents an alkyl group having an alkyl group of 1 to 10, an alkenyl group, a cycloalkyl group, an extended aryl group, and a combination thereof. At least one selected from the group consisting of]. Specifically, the alkyl group having 1 to 20 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. Among them, a methyl group is preferred. , ethyl, propyl, butyl, cyclohexyl. -20- 200902694 Further, the alkenyl group is preferably a group having 2 to 10 carbon atoms, and examples thereof include a vinyl group and a propenyl group. Specifically, for example, the cycloalkyl group may, for example, be a cyclohexyl group or a cyclopentyl group, and among them, a cyclohexyl group is preferred. Specifically, examples of the aryl group include a butynyl group, a pentynyl 'hexynyl group, a phenyl group, a naphthyl group and the like. Among them, a phenyl group is preferred. Specifically, for example, the aralkyl group may, for example, be a benzyl group, and more preferably a benzyl group. Each of the above-mentioned groups may further have a substituent, and a substituent which may be introduced may, for example, be a hydroxyl group, an amino group 'carboxy group, a phosphoric acid group, an imido group, a thiol group, a sulfo group or a nitro group. X in the above formula (2) is selected from the group consisting of a C 1 -alkylene group, a stretched alkyl group, a stretched cycloalkyl group, an extended aryl group, and a combination of two or more of these groups. At least one of them. Further, in addition to the organic linking group described above, the linking group represented by X may also contain an S-, a s(=〇)2_, a 〇-, -C (- 0)- in its chain. . Specifically, the above-mentioned alkylene group having 1 to 10 carbon atoms may, for example, be a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an exo The base or the like, wherein it is preferably an ethyl group and a pentyl group. Specifically, for example, the alkenyl group may be, for example, a vinyl group, a propylene group or the like, and more preferably an exopropylene group. Specifically, for example, the cycloalkyl group may be exemplified by a cyclohexyl group, a cyclopentyl group or the like, and more preferably a cyclohexyl group. -twenty one -

200902694 具體而言，例如，該伸芳基可列舉：伸苯基、伸萘基_ 其中，較宜爲伸苯基。 上述各連結基也可以更具有取代基，作爲可導入π 基，例如，可列舉：羥基、胺基、羧基、磷酸基、亞胺基、 硫醇基、磺基、硝基等。 以下，顯示能夠含有本發明硏磨液之二（四級銨）陽$ (例示化合物A-1〜A32 )、一（四級銨）陽離子（例示化合 物A- 3 3〜A44 )之具體例，但是本發明並不受此等例示彳七 合物所限定。 A1 A2ru A3 A4 ch3 ch3 CHj CH3 1 1 ch3 ch3 CHj CH3 H3C_N|f，(〇^)丨0，*+_〇^ H3C —N+ —N+—CH3 H3C-N 十，(CH2VN+-CH3 CHj ίπ3 1 ** 1 * H3C-N+*(CH2)8*N+-CH3 CH) CH3 CHj CHj CH, CH3 A5 A6 A7 A8 c2h5 c2h5 pHs C2H5 C3H7 C3H7 C4H9 C4H9 C2H5-N+ ·<ΟΗ2)2 · N+ -C2H5 C2H5—N+’(CH^. N+—C2H5 C2H5 CjH5 C3H7 — N+ '(CHjJj· N+ —C3H7 C4H§-N+ *tCH7)yn+~CAH9 1 1 C2Hj c2h5 C3H7 C3H7 C4H9 C4H9 A9 A10 All A12 CH3 ch3 ?h3 ch, ch3 ch3 ch3 ch3 C2H 广 N+ .(CH2>5.N+—C2H5 C4H9—N+ C6H,广 N+，iCH2VN+—C6H,3 C8Hj7-N+ '(CH3)5-N+-CbH)7 1 1 ch3 ch3 CH, CH, 1 1 CH3 CHj ch3 ch3 A13 A14 A15200902694 Specifically, for example, the aryl group may be exemplified by a phenyl group and a naphthyl group, and more preferably a phenyl group. Each of the above-mentioned linking groups may further have a substituent, and examples of the π group include a hydroxyl group, an amine group, a carboxyl group, a phosphoric acid group, an imido group, a thiol group, a sulfo group, a nitro group and the like. Hereinafter, specific examples of the bis(quaternary ammonium) cations (exemplified compounds A-1 to A32) and one (quaternary ammonium) cations (exemplary compounds A-3 3 to A44) which can contain the honing liquid of the present invention are shown. However, the invention is not limited by these exemplified ruthenium complexes. A1 A2ru A3 A4 ch3 ch3 CHj CH3 1 1 ch3 ch3 CHj CH3 H3C_N|f,(〇^)丨0,*+_〇^ H3C —N+ —N+—CH3 H3C-N X,(CH2VN+-CH3 CHj ίπ3 1 * * 1 * H3C-N+*(CH2)8*N+-CH3 CH) CH3 CHj CHj CH, CH3 A5 A6 A7 A8 c2h5 c2h5 pHs C2H5 C3H7 C3H7 C4H9 C4H9 C2H5-N+ ·<ΟΗ2)2 · N+ -C2H5 C2H5— N+'(CH^. N+-C2H5 C2H5 CjH5 C3H7 — N+ '(CHjJj· N+ —C3H7 C4H§-N+ *tCH7)yn+~CAH9 1 1 C2Hj c2h5 C3H7 C3H7 C4H9 C4H9 A9 A10 All A12 CH3 ch3 ?h3 ch, ch3 Ch3 ch3 ch3 C2H wide N+ .(CH2>5.N+-C2H5 C4H9-N+ C6H, wide N+, iCH2VN+-C6H,3 C8Hj7-N+ '(CH3)5-N+-CbH)7 1 1 ch3 ch3 CH, CH, 1 1 CH3 CHj ch3 ch3 A13 A14 A15

CH> CHjCH> CHj

H〇'C2H5-N+ '(CH2)2'N+-C2HjOH ch3 ch3 ch3 ch3 H0AH5-丫 .<CH2)5 ·Ν—C2H 广 oh ch3 ch3 -22 - 200902694 A16 A17H〇'C2H5-N+ '(CH2)2'N+-C2HjOH ch3 ch3 ch3 ch3 H0AH5-丫 .<CH2)5 ·Ν—C2H 广 oh ch3 ch3 -22 - 200902694 A16 A17

ch3 -N+-C I h2 ch3Ch3 -N+-C I h2 ch3

ch3 C—N+ —(CH2)2—S—(H2C>2 ·Ch3 C—N+ —(CH2)2—S—(H2C>2·

H2 I ch3 A20 H3c - 丁*CH3 C2H5 一 N+y/^+ -C2H5 〇-r0N+ H2H2 I ch3 A20 H3c - D *CH3 C2H5 A N+y/^+ -C2H5 〇-r0N+ H2

l A2]o~： A22 ch3 ch3 A23 CH H3C-N+ CHjl A2]o~: A22 ch3 ch3 A23 CH H3C-N+ CHj

N+ -CH3 I ch3N+ -CH3 I ch3

A26-JA26-J

CH3 y=\ CH C-N-+-(CH2>2-^ (CH2)2.M+-C ch3 A25 h3c- \v // ch3 h2CH3 y=\ CH C-N-+-(CH2>2-^ (CH2)2.M+-C ch3 A25 h3c- \v // ch3 h2

ch3 nL I CH, 0il CHi (CH2)2一S~(H2C)2 —N+-GH； CH, A26-2 A27 n3+hnSn N3+_sr^^2~NSN n3- •CH2OCO(CH2)4〇COCH2 -Ch3 nL I CH, 0il CHi (CH2)2-S~(H2C)2 -N+-GH; CH, A26-2 A27 n3+hnSn N3+_sr^^2~NSN n3- •CH2OCO(CH2)4〇COCH2 -

-N^N A28-N^N A28

CH, CH, A29 h3c、 c4h9〆 A30 /η3 ?h： 、C4Hy A31 ch5 CHn CHaCH, CH, A29 h3c, c4h9〆 A30 /η3 ?h: , C4Hy A31 ch5 CHn CHa

H3c - γ -(0^)2^+ -C2Hj〇HH3c - γ -(0^)2^+ -C2Hj〇H

A32 H3C-h A33 ch3 H3C—N*—CH3 ch3 Q-t：- A34 A35 A36 A37 ^ u C：Hs c2h5^-n 崎一c2h5 c3h7 C3H7—K*—C3H7 C4H9 c4h9—n+—c4h9 YaHi7 C8H17-^—c8h17 c2h5 c3H7 C4H9 c8h17 23 200902694A32 H3C-h A33 ch3 H3C—N*—CH3 ch3 Qt:- A34 A35 A36 A37 ^ u C:Hs c2h5^-n Saki-c2h5 c3h7 C3H7—K*—C3H7 C4H9 c4h9—n+—c4h9 YaHi7 C8H17-^— C8h17 c2h5 c3H7 C4H9 c8h17 23 200902694

CisHjl一C,〇H2i c10h21 C,H,lCisHjl-C, 〇H2i c10h21 C, H, l

C2H4OH HOCjl·^—N+— CaH4〇H C2H4〇H 還有，A43中之cycrohCftHi〗係表不環己基。 其中，基於硏磨劑中之分散安定性之觀點，較宜爲 Al、A2、A3、A4、A5、A6、A7、A8、A9、A10、All、A12、 A13 ' A14、A15、A18、A19 ' A23 ' A24、A29、A30、A31、 A32 、 A33 ' A34 、 A35 、 A36 、 A37 、 A41 、 A42 。 特定陽離子可以各自單獨使用或組合二種以上後而加 以使用。 本發明之硏磨液所能夠含有之特定陽離子，針對其製 造，並未予以特別限制，例如，能夠將氨或各種胺等發揮 作爲親核劑之功能，藉由置換反應而加以合成。 另外’也能夠爲以一般販售試藥之方式購入。 相對使用於硏磨時之硏磨液（亦即，利用水或水溶液 等加以稀釋之情形係稀釋後之硏磨液。以後之「使用於硏 磨時之硏磨液」也爲同義的。），本發明中之特定陽離子 的添加量較宜爲0.001g/L以上、i〇g/L以下，更佳爲〇.〇1 g/L 以上、3g/L以下。亦即，基於使硏磨速度得以充分提高之 觀點，如此特定陽離子之添加量較宜爲〇.〇〇lg/L以上，基 於充分硏磨劑安定性之觀點，更佳爲丨0g/L以下。 -24- 200902694 〔具有羧基之化合物〕 基於相對於低介電常數膜種以外之膜，達成充分硏磨 速度之觀點，本發明之硏磨液較宜爲含有一具有羧基之化 合物（以下，較宜稱爲「有機酸」）。具有羧基之化合物， 只要爲分子內具有至少一個羧基之化合物即可，並無特別 之限制，但是基於硏磨速度構造之觀點，較宜選擇下列通 式（4 )所示之化合物。 還有，存在於分子內之殘基較宜爲1〜4個，基於能夠 廉價使用之觀點，更佳爲1〜2個。 通式（4 )C2H4OH HOCjl·^—N+—CaH4〇H C2H4〇H Also, the cycrohCftHi in A43 is not cyclohexyl. Among them, based on the viewpoint of dispersion stability in the honing agent, it is preferable to be Al, A2, A3, A4, A5, A6, A7, A8, A9, A10, All, A12, A13 'A14, A15, A18, A19. ' A23 ' A24, A29, A30, A31, A32, A33 ' A34, A35, A36, A37, A41, A42. The specific cations may be used singly or in combination of two or more. The specific cation which can be contained in the honing liquid of the present invention is not particularly limited, and for example, ammonia or various amines can function as a nucleophilic agent, and can be synthesized by a substitution reaction. In addition, it can also be purchased as a general-purpose drug. The honing fluid used in the honing process (that is, the dilution with water or an aqueous solution is the honing fluid after dilution. The latter is also synonymous with the honing fluid used in honing.) The amount of the specific cation added in the present invention is preferably 0.001 g/L or more and i 〇 g/L or less, more preferably 〇1 /1 g/L or more and 3 g/L or less. That is, the addition amount of such a specific cation is preferably 〇.〇〇lg/L or more based on the viewpoint of sufficiently increasing the honing speed, and more preferably 丨0g/L or less based on the viewpoint of sufficient honing agent stability. . -24- 200902694 [Compound having a carboxyl group] The honing liquid of the present invention preferably contains a compound having a carboxyl group from the viewpoint of achieving a sufficient honing speed with respect to a film other than the low dielectric constant film type (hereinafter, It should be called "organic acid"). The compound having a carboxyl group is not particularly limited as long as it has at least one carboxyl group in the molecule, but the compound represented by the following formula (4) is preferably selected from the viewpoint of the honing speed structure. Further, the number of residues present in the molecule is preferably from 1 to 4, and more preferably from 1 to 2, based on the viewpoint of being inexpensive to use. General formula (4)

R7 - 0 — R8 - COOH 於上述通式（4)中，R7與R8係表示各自獨立之烴基， 較爲碳數1〜10之烴基。 R7係一價之烴基，例如，較宜爲碳數1〜i 〇之烷基（例 如’甲基、環烷基等）、芳基（例如，苯基等）、烷氧基、 芳氧基等。 R8係二價之烴基，例如，較宜爲碳數i〜1 0之伸烷基 (例如，亞甲基、伸環烷基等）、伸芳基（例如，伸苯基 等）、伸烷氧基等。 R7與R8所示之烴基也可以更具有取代基，作爲可進行 導入之取代基，例如，可列舉：碳數1〜3之烷基、芳基、 烷氧基、羧基等。還有’ R7與R8所示之烴基能夠更含有之 有取代基具有殘基的情形，此化合物成爲具有複數個竣基。 另外’ R7與R8也可以相互鍵結而形成環狀構造。例如， -25- 200902694 環狀構造可列舉：呋喃環' 四氫呋喃環。 該通式（4 )所示之化合物，例如，可列舉：2 -呋喃竣 酸、2,5-呋喃二羧酸、3-咲喃羧酸、2-四氫呋喃羧酸、二甘 醇酸、甲氧基醋酸、甲氧基苯基醋酸、苯氧基醋酸等，其 中，基於高速硏磨被硏磨面之觀點，較宜爲2,5 -呋喃二竣 酸、2-四氫呋喃羧酸、二甘醇酸、甲氧基醋酸、苯氧基醋 酸。 具有羧基之化合物可以各自單獨使用或組合二種以上 後而加以使用。 於本發明之硏磨液中，相對使用於硏磨時之硏磨液質 量，具有殘基之化合物（較宜爲通式（4)所示之化合物） 的添加量較宜爲0.01g/L以上、50g/L以下，更佳爲〇.〇5 g/；L 以上、20g/L以下。亦即，基於達成充分硏磨速度之觀點， 含有如此羧基之化合物（有機酸）的含量較宜爲〇.〇1 g/L 以上，基於不使過度之薄碟化發生之觀點，則其含量較宜 爲50g/L以下。 〔界面活性劑〕 本發明之硏磨液可列舉更含有界面活性劑之一較佳態 樣。 於本發明之硏磨液中’藉由調整界面活性劑之種類、 量，能夠使硏磨速度得以提高，或控制絕緣層之硏磨速度。 界面活性劑較宜使用陽離子系界面活性劑或陰離子系界面 活性劑。 陰離子系界面活性劑，例如，可列舉：下列通式（5 ) -26- 200902694 所示之化合物。 陽離子系界面活性劑，例如，可列舉：下列通式（6 ) 所示之化合物。 其中，基於使絕緣層之硏磨速度得以提高之觀點，較 宜爲下列通式（5)所示之化合物；基於使絕緣層之硏磨速 度得以抑制之觀點，較宜爲下列通式（6 )所示之化合物 通式（5 ) R- S〇3~ 於上述通式（5)中之R係表示羥基，較宜爲表示碳數 6〜20之羥基。 碳數6〜20之羥基，具體而言，例如，較宜爲碳數6 〜20之烷基、芳基（例如，苯基、萘基等）等，此烷基或 芳基也可以更含有烷基等之取代基。 通式（5 )所示之化合物的具體例，例如，可列舉：癸 基苯磺酸、十二烷基苯磺酸、十四烷基苯磺酸、十六烷基 苯磺酸、十二烷基萘磺酸、十四烷基萘磺酸等。 通式（6 )R7 - 0 - R8 - COOH In the above formula (4), R7 and R8 each represent a hydrocarbon group which is independent of each other and a hydrocarbon group having 1 to 10 carbon atoms. R7 is a monovalent hydrocarbon group, for example, preferably an alkyl group having a carbon number of 1 to i ( (e.g., 'methyl, cycloalkyl, etc.), an aryl group (e.g., phenyl group, etc.), an alkoxy group, an aryloxy group. Wait. R8 is a divalent hydrocarbon group, for example, preferably an alkylene group having a carbon number of i to 10 (for example, a methylene group, a cycloalkyl group, etc.), an extended aryl group (for example, a phenyl group, etc.), and an alkylene group. Oxyl and the like. The hydrocarbon group represented by R7 and R8 may have a more substituent. Examples of the substituent which can be introduced include, for example, an alkyl group having 1 to 3 carbon atoms, an aryl group, an alkoxy group, and a carboxyl group. Further, in the case where the hydrocarbon group represented by R7 and R8 can further contain a substituent having a residue, the compound has a plurality of fluorenyl groups. Further, 'R7 and R8' may be bonded to each other to form a ring structure. For example, the -25-200902694 ring structure may be exemplified by a furan ring 'tetrahydrofuran ring. Examples of the compound represented by the formula (4) include 2-furanic acid, 2,5-furandicarboxylic acid, 3-decanecarboxylic acid, 2-tetrahydrofurancarboxylic acid, diglycolic acid, and A. Oxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid, etc., among which, based on the viewpoint of high-speed honing of the honed surface, it is preferably 2,5-furandyric acid, 2-tetrahydrofurancarboxylic acid, and digan Alkyd, methoxyacetic acid, phenoxyacetic acid. The compound having a carboxyl group may be used singly or in combination of two or more. In the honing liquid of the present invention, the compound having a residue (preferably a compound represented by the formula (4)) is preferably added in an amount of 0.01 g/L, relative to the mass of the honing liquid used in honing. Above 50 g/L, more preferably 〇.〇5 g/; L or more, 20 g/L or less. That is, the content of the compound (organic acid) having such a carboxyl group is preferably 〇.〇1 g/L or more based on the viewpoint of achieving a sufficient honing speed, and the content thereof is based on the viewpoint of not causing excessive thinning. It is preferably 50 g/L or less. [Interfacial Agent] The honing liquid of the present invention may be exemplified by a preferred one of the surfactants. In the honing liquid of the present invention, the honing speed can be improved or the honing speed of the insulating layer can be controlled by adjusting the kind and amount of the surfactant. As the surfactant, a cationic surfactant or an anionic surfactant is preferably used. The anionic surfactant may, for example, be a compound represented by the following formula (5) -26-200902694. The cationic surfactant may, for example, be a compound represented by the following formula (6). Among them, from the viewpoint of improving the honing speed of the insulating layer, it is preferably a compound represented by the following formula (5); and based on the viewpoint of suppressing the honing speed of the insulating layer, it is preferably the following formula (6) The compound represented by the formula (5) R-S〇3~ in the above formula (5) represents a hydroxyl group, and preferably represents a hydroxyl group having 6 to 20 carbon atoms. The hydroxyl group having 6 to 20 carbon atoms is specifically, for example, an alkyl group having 6 to 20 carbon atoms, an aryl group (for example, a phenyl group, a naphthyl group, etc.), and the like, and the alkyl group or the aryl group may be further contained. a substituent such as an alkyl group. Specific examples of the compound represented by the formula (5) include, for example, mercaptobenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, cetylbenzenesulfonic acid, and twelve. Alkyl naphthalenesulfonic acid, tetradecyl naphthalenesulfonic acid, and the like General formula (6)

於上述通式（6)中’ Ra〜Rd係表示各自獨立之碳數1 〜1 8之烴基。但是，Ra〜Rd並非全部爲相同的烴基。In the above formula (6), 'Ra to Rd' means a hydrocarbon group having independently carbon numbers of 1 to 18. However, not all of Ra to Rd are the same hydrocarbon group.

Ra〜Rd所示之烴基，例如，可列舉：烷基、芳基、苯 基等’其中，較宜可列舉：碳數1〜20之直鏈及分枝鏈烷 -27- 200902694 基。 還有，Ra〜Rd中之二者相互鍵結，例如，吡啶構造、 吡略烷構造、哌啶構造、吡咯構造等之環狀構造。 通式（6 )所示之化合物的具體例’例如’可列舉：月 桂基三甲基銨、月桂基三乙基銨、十八烷基三甲基銨、十 六烷基三甲基銨、辛基三甲基銨、十二烷基吡啶鎗、癸基 吡啶鎗、辛基吡啶鑷等之化合物。 本發明之界面活性劑也可以使用該通式（5)、或通式 (6 )所示之化合物以外，該通式（5 )所示之化合物以外 之陰離子性界面活性劑，例如，可列舉：羧酸鹽、硫酸酯 鹽、磷酸酯鹽。 更具體而言，例如，羧酸鹽能夠較宜使用肥皂、N-醯 胺基酸鹽、聚環氧乙烷或聚環氧丙烷烷基醚羧酸鹽、醯化 肽； 例如，硫酸酯鹽能夠較宜使用硫酸化油、烷基硫酸鹽、 烷基醚硫酸鹽、聚環氧乙烷或聚環氧丙烷烷基芳基醚硫酸 鹽、烷基醯胺硫酸鹽； 例如，磷酸酯鹽能夠較宜使用烷基磷酸鹽、聚環氧乙 烷或聚環氧丙烷烷基醚磷酸鹽。 界面活性劑可以各自單獨使用或組合二種以上後而加 以使用。 使用於硏磨時之硏磨液1 L中，界面活性劑之添加量， 其總量較宜設爲0.001〜10g，更佳設爲〇.〇1〜5g，尤以設 爲0·01〜1 g特別理想。亦即，得到充分之效果上，界面活 -28- 200902694 性劑之添加量較宜爲ο. 0 lg以上’基於防止c Μ P速度降低 之觀點，較宜爲1 g以下。 〔其它之成分〕 本發明之硏磨液係於不損害本發明之效果、目的之範 圍內，能夠更含有添加劑。例如，添加劑可列舉：氧化劑、 pH調整劑、螯合劑等。 (氧化劑） 本發明之硏磨液’可列舉：更含有能夠氧化硏磨對象 金屬之化合物（氧化劑）之一較佳態樣。 例如，氧化劑可列舉：過氧化氫、過氧化物、硝酸鹽、 碘酸鹽、過碘酸鹽、次氯酸鹽、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（II) 鹽、鐵（III)鹽，其中，較宜使用過氧化氫。 例如，鐵（III )鹽較宜使用硝酸鐵（III )、氯化鐵（III )、 硫酸鐵（III)、溴化鐵（III)等無機鐵（III)鹽之外，較 宜使用鐵（III )之有機錯鹽。 氧化劑之添加量能夠根據阻障CMP初期之薄碟化量而 加以調整。於阻障CMP初期之薄碟化量爲大的情形下，亦 即，於阻障C Μ P中，欲不過度硏磨配線材之情形下，期望 使氧化劑成爲少的添加量；薄碟化量爲充分的小’以高速 欲硏磨配線材之情形，期望增多氧化劑的添加量。如此方 式，由於期望根據阻障CMP初期之薄碟化狀況以使氧化劑 之添加量予以改變，於使用於硏磨時之硏磨液1 L中’較宜 設爲O.Olmol〜lmol，尤以設爲O.〇5mol〜0_6mol特別理想。 -29- 200902694 (pH調整劑） 基於達成高硏磨速度之觀點，本發明之硏磨液較宜爲 PH2.5〜5.0，更佳爲pH3.0〜4.5之範圍。將硏磨液之pH控 制於此範圍之情形，更顯著進行層間絕緣膜之硏磨速度調 整將成爲可能，發揮特別優異的效果。 爲了使pH調整至上述較佳的範圍內，能夠使用鹼/酸 或緩衝劑。 例如，鹼/酸或緩衝劑較宜可列舉：氨、氫氧化銨及四 甲基銨氫氧化物等之有機氫氧化銨；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；磷酸三鈉等之磷酸 鹽；硼酸鹽、四硼酸鹽、羥基安息香酸鹽等。特別理想之 鹼劑爲氫氧化銨、氫氧化鉀、氫氧化鋰及四甲基銨氫氧化 物。 鹼/酸或緩衝劑之添加量最好爲使P H得以維持於較佳 之範圍的量，於使用於硏磨時之硏磨液1 L中’較宜設爲 O.OOOlmol 〜l.Omol，更佳設爲 〇.003mo1 〜〇.5mo1。 (螯合劑） 本發明之硏磨液係爲了使所混入之多價金屬離子等之 不良影響得以減低，再者，必要時較宜含有螯合劑（亦即’ 硬水軟化劑）。 例如，螯合劑可列舉：釣或鎂之沈殿防止劑的泛用硬 水軟化劑或其類似化合物，具體而言’例如’可列舉：氮 -30- 200902694 基三醋酸、二伸乙基三胺五醋酸、伸乙基二胺四 N，N，N_三亞甲基膦酸、伸乙基二胺-Ν,Ν,Ν’，Ν’-四亞 酸、反式環己院二胺四醋酸、丨，2_二胺基丙院四醋酸 醇醚二胺四醋酸、伸乙基二胺鄰羥苯基醋酸、伸乙 二琥拍酸（SS體）、N-(2 -竣化乙基）-L -天冬胺@ 丙胺酸二酿酸、2-膦基丁院-1，2,4-三竣酸、1-經亞乙 二膦酸、N，N’ -雙（2 -徑节基）伸乙基二胺- N，N’ -二 1,2-二羥基苯_4,6 —二磺酸等。 必要時，螯合劑也可以倂用二種以上。 針對封鎖所混入之多價金屬離子等之金屬離子 劑之添加量最好爲充分量’例如’使用於硏磨時之 1L中，使其能夠成爲0_0003mo丨〜〇.〇7mol之方式來 加。 本發明之硏磨液’針對其製造，並未予以特別 例如，必要時能夠使用抗靜電劑或通式（1 )所示之仰 並能夠藉由混合腐蝕抑制劑、膠體二氧化矽、雙四 離子或單四級銨陽離子、有機酸、界面活性劑、添 水後而得到。 另外，本發明之硏磨液係作成使用此硏磨液之 例如’可列舉：1 _爲一種濃縮液，於使用時，添加 溶液予以稀釋後而作成使用液之情形；2.各成分係 之水溶液態樣予以準備，再加以混合，必要時加水 而作成使用液之情形：3.作成使用液後而予以調 形。 醋酸、 甲基膦 、乙二 基二胺 I ' /S -基-1，1 -醋酸、 ，螯合 硏磨液 加以添 限制。 1合物， 級銨陽 加劑與 態樣， 水或水 以後述 稀釋後 製之情 -31 - 200902694 一般而言，本發明之硏磨液係存在於由銅金屬及/或銅 合金而成的配線與層間絕緣膜之間，適合於爲了防止銅擴 散之由阻障金屬材料而成的阻障層之硏磨。 接著’以下針對本發明之硏磨方法加以說明。 本發明之硏磨方法’其特徵係於半導體積體電路阻障 層之硏磨中，使用本發明之硏磨液。 本發明之硏磨方法所使用之硏磨液，只要爲本發明之 硏磨液的話’並未予以特別限制。 另外’本發明之硏磨方法所使用之半導體積體電路， 只要爲具有阻障層之物的話，並未予以特別限制。 於本發明之硏磨方法中’半導體積體電路阻障層之硏 磨’可列舉：CMP爲較佳之一態樣。 〔阻障金屬材料〕 一般而言’構成本發明硏磨液的硏磨對象之阻障層的 材料可以爲低電阻之金屬材料，較宜爲Ru、Ru〇4、TlN、 Tiw、Ta ' TaN、w、WN，其中，尤以 Ta、TaN ' Ru、Ru〇4 特別理想。 〔層間絕緣膜〕 作爲本發明硏磨液的硏磨對象之層間絕緣膜，除了 T E〇s等通常所用之層間絕緣膜以外，例如，可列舉：含有 比介電常數約爲3.5〜2.0之低介電常數材料（例如，可列 舉：有機聚合物系之Sl0C系、Sl〇F系等，通常簡稱爲L〇w_k 膜。）之層間絕緣膜。 具體而W ’使用於低介電常數之層間絕緣膜形成材 -32- 200902694 料’ S i 0 C系之情形’可列舉：H S G - R 7 (日立化成工業）、 BLACKDIAMOND ( Applied Materials, Inc)等。 〔配線金屬原材料〕 於本發明中’例如，硏磨對象之被硏磨物較宜爲如L SI 等之半導體裝置所適用之具有由.銅金屬及/或銅合金而成 的配線。尤其，此配線原材料較宜爲銅合金。於銅合金中， 更佳爲含有銀之銅合金。 還有，銅合金中所含之銀含量較宜爲40質量％以下， 尤以10質量％以下，更佳爲1質量％以下，於0.0000 1〜 0.1質量％之範圍的銅合金中，發揮最爲優越之效果。 〔配線之寬度〕 於本發明中，例如，硏磨對象之被硏磨物適用於DRAM 裝置系之情形，較宜爲具有半間距〇. 1 5 /z m以下之配線， 更佳爲0.10/zm以下，最好爲0.08//m以下。 另—方面，例如，被硏磨物適用於MPU裝置系之情形， 較宜爲具有以下之配線，更佳爲〇.〇9/zm以下’ 最好爲0.07/zm以下。 對於具有如此配線之被硏磨物’上述本發明中之硏磨 液發揮特別優越之效果。 〔硏磨方法〕 於本發明之硏磨方法中，硏磨液係作成其使用之態 樣’例如，可列舉：1 .爲一種濃縮液’於使用時，添加水 或水溶液予以稀釋後而作成使用液之情形；2 ·各成分係以 下項所述之水溶液態樣予以準備，再加以混合，必要時加 -33- 200902694 水稀釋後而作成使用液之情形；3.作成使用液後而予以調 製之情形。 於本發明之硏磨方法中，任一種情形之硏磨液皆可適 用。 本發明之硏磨方法可列舉：將硏磨液供應至硏磨固定 盤上之硏磨墊，與被硏磨物之被硏磨面相接觸，使被硏磨 面與硏磨墊予以相對運動之方法爲較佳之一態樣。 用於硏磨之裝置能夠使用如下之一般硏磨裝置·保持 具有被硏磨面之被硏磨物（例如，導電性材料膜所形成的 晶圓等）之支撐架，與貼附硏磨墊（裝設可變更旋轉數之 馬達等）之硏磨固定盤。硏磨墊能夠使用一般之不織布、 發泡聚胺甲酸酯樹脂、多孔質氟樹脂等，並無特別之限制。 另外，針對硏磨條件並無特別之限制，硏磨固定盤之旋轉 速度較宜使被硏磨物不被飛出之方式來進行200rpm以下 之低旋轉。具有被硏磨面（被硏磨膜）之被硏磨物硏磨墊 的按壓較宜爲0.68〜34.5KPa，爲了符合硏磨速度之被硏磨 物的面內均勻性及圖案平坦性，更佳爲3.4 0〜2 0.7 K P a。 進行硏磨期間，能夠利用泵等以將硏磨液連續供應至 硏磨墊。 於本發明中，如該1.之方法，於稀釋濃縮液之際，能 夠使用顯示於下列之水溶液。水溶液係預先含有氧化劑、 有機酸、添加劑、界面活性劑中之至少一種的水，使合計 此水溶液中所含之成分與予以稀釋的濃縮液中所含之成 分’成爲於硏磨時之所使用的硏磨液（使用液）之成分的 -34- 200902694 方式來加以進行。 如此方式，利用水溶液以稀釋濃縮液後而使用之情形 下’由於能夠以水溶液形式，隨後摻合難溶解之成分，故 能夠調製更濃縮之濃縮液。 另外，將水或水溶液添加於濃縮液中進行稀釋的方 法，例如，可列舉：使供應所濃縮的硏磨液之配管 '與供 應水或水溶液之配管’於途中予以合流後而混合，將所混 合、稀釋後之硏磨液的使用液供應至硏磨墊的方法。濃縮 液與水或水溶液之混合能夠採用通常所進行的方法：於施 加壓力之狀態下，通過狹窄的通路而衝撞混合彼此溶液的 方法；於配管中，重複進行裝入玻璃管等之塡充物，使液 體之流動予以分流分離、合流的方法；於配管中，設置利 用動力加以旋轉的槳葉的方法等。 硏磨液之供應速度較宜爲10〜lOOOml/min，爲了符合 硏磨速度之被硏磨面內均勻性及圖案的平坦性，更佳爲1 7 0 〜800ml/min 〇 進一步一面藉由水或水溶液等以稀釋濃縮液，並一面 進行硏磨的方法，例如，可列舉：獨立設置供應硏磨液之 配管、與供應水或水溶液之配管，分別從各自配管而將既 定量之溶液供應至硏磨墊，一面利用硏磨墊與被硏磨面之 相對運動予以混合，並一面進行硏磨的方法。另外’也能 夠利用將既定量之濃縮液與水或水溶液加入一容器中，混 合後而將此混合後的硏磨液供應至硏磨墊，進行硏磨的方 法。 -35- 200902694 另外，別的硏磨方法可列舉：將硏磨液所應含有之成 分分成至少二個構造成分，使用此等構造成分之際，添加 水或水溶液加以稀釋後而供應至硏磨固定盤上之硏磨墊’ 與被硏磨面相接觸，使被硏磨面與硏磨墊予以相對運動後 而加以硏磨的方法。 例如，能夠將氧化劑作爲構造成分（A )，將抗靜電劑 或以通式（1 )所示之化合物、有機酸、添加劑、界面活性 劑與水作爲構造成分（B )，於使用此等構造成分之際，能 夠添加水或水溶液以稀釋構造成分（A )與構造成分（B ) 後而加以使用。 另外，將溶解度低的添加劑分成二個構造成分（A )與 (B )，例如’將氧化劑、添加劑、界面活性劑作爲構造成 分（A )，將抗靜電劑或以通式（1 )所示之化合物、有機 酸、添加劑、界面活性劑與水作爲構造成分（B )，於使用 此等之際，能夠利用水或水溶液以稀釋構造成分（A )與構 造成分（B )後而加以使用。 如上述例子的情形，必須要有分別供應構造成分（A )、 構造成分（B )與水或水溶液之三條配管，稀釋混合的方法 爲將三條配管接合於供應至硏磨墊的一條配管，於此配管 內加以混合的方法，此情形下，接合二條配管後而接合另 一條配管也爲可能的。具體而言，混合難以溶解之添加劑 的構造成分與其他的構造成分，增長混合路徑以確保溶解 時間後而進一步接合水或水溶液之配管。 其他之混合方法可列舉：如上所述，直接將三條配管 -36- Φ 200902694 分別引導至硏磨墊，藉由硏磨墊與被硏磨面 加以混合的方法；於一容器內，混合三個構 將經稀釋後之硏磨液供應至硏磨墊的方法。 於上述之硏磨方法中，使含有氧化劑之 爲4 0 °C以下，將其他之構造成分從室溫加熱 圍，於混合一構造成分與其他構造成分之際 水或水溶液加以稀釋之際，能夠使液溫成爲 式來加以進行。此方法係一種利用高溫與溶 象，用以提高硏磨液溶解度低的原料之較佳 藉由從室溫起，將上述之其他構造成分 之範圍後而予以溶解之原料’由於一旦温度 溶液中加以析出，使用低溫狀態之其他構造 必須使預先加熱後而析出的原料予以溶解。 夠採用：經加熱並輸送原料溶解後之其他: 置；及預先攪拌含有析出物之溶液、溶液輸 後而予以溶解之裝置。經加熱後之其他構造 含有氧化劑之一構造成分的溫度提高至4 〇 °c 擔憂氧化劑將分解，混合此加熱之其他構造 化劑之一構造成分之情形，較宜成爲4(TC以 以進行。 如此方式，於本發明中，也可以將硏磨 成二分割以上後而供應至被硏磨面。此情形 成含有氧化物之成分與含有有機酸之成分後 另外，也可以將硏磨液作成濃縮液，再將稀 之相對運動而 造成分，其後 一構造成分成 至100°C之範 ，或是於添加 40°C以下之方 解度變高之現 方法。 加熱至100°C 降低時，將於 成分的情形， 針對於此，能 構造成分的裝 送、加熱配管 成分，一旦使 以上時，因爲 成分與含有氧 下之方式來加 液之成分分割 下，較宜分割 而加以供應。 釋水另外供應 -37- 200902694 至被硏磨面。 於本發明中，採用將硏磨液之成分分割成二分割以上 後而供應至被硏磨面的方法之情形，其供應量係表示來自 各配管之供應量的合計。 〔墊〕 可適用於本發明硏磨方法之硏磨用的硏磨墊，無論是 無發泡構造墊或是發泡構造墊中任一種均可。前者係如塑 膠板，將硬質之合成樹脂整塊材用於硏磨墊。另外，後者 更具有獨立發泡物（乾式發泡系）、連續發泡物（濕式發 泡系）、二層複合物（積層系）之三種，尤其較宜爲二層 複合物（積層系）。發泡可以均勻也可以不均勻。 一般也可以爲更含有用於硏磨之硏磨粒（例如，二氧 化鈽、二氧化矽、氧化鋁、樹脂等）之物。另外，硬度分 別有軟質者與硬質者’任一種均可，於積層系中，較宜將 不同硬度之物用於各自之層中。材質較宜爲不織布、人工 皮革、聚醯胺、聚胺甲酸酯、聚酯、聚碳酸酯等。另外， 與被硏磨面接觸之面上，也可以實施格子溝/洞/同心溝/螺 旋狀溝等之加工。 〔晶圓〕 作爲利用本發明硏磨方法中之硏磨液而進行CMP之被 硏磨物對象的晶圓，其直徑較宜爲2〇〇mm以上，尤以300mm 以上特別理想。當300mm以上時，顯著發揮本發明之效果。 〔硏磨裝置〕 使用本發明之硏磨液而能夠實施硏磨之裝置並未予以 -38- 200902694 特別限定，例如，可列舉：Mirra Mesa CMP、Reflexion CMP (Applied Materials)、FREX200、FREX300(荏原製作所）、 NPS3301、NPS 23 0 1 ( Nikon ) 、A-FP-310A ' A-FP-210A (東 足精密）、2300 TERES( Lam Research)、Momentum( Speedfam IPEC )等。 於本發明之硏磨方法中，予以硏磨的被硏磨物（例如， 晶圓）係於硏磨結束後，於水流中予以充分洗淨，使用旋 、 轉乾燥機等以拭去附著於被硏磨物上之水滴，使其乾燥， 乾燥後利用例如習知方法予以切斷，能夠作成半導體積體 電路。 利用本發明之硏磨液予以硏磨之半導體積體電路，其 硏磨面爲平坦的，幾乎無阻障層。 【實施例】 以下，根據實施例，更詳細說明本發明，但是本發明 並不受此等實施例所限定。 〔實施例1〕 調製顯示於下列組成的硏磨液，進行硏磨實驗。 <組成（1 ) >Examples of the hydrocarbon group represented by Ra to Rd include an alkyl group, an aryl group, a phenyl group and the like. Among them, a linear or branched alkane having a carbon number of 1 to 20 is preferably exemplified by a straight chain or a branched alkane -27-200902694. Further, two of Ra to Rd are bonded to each other, for example, a cyclic structure such as a pyridine structure, a pyridylene structure, a piperidine structure, or a pyrrole structure. Specific examples of the compound represented by the formula (6) include, for example, lauryl trimethylammonium, lauryl triethylammonium, octadecyltrimethylammonium, and cetyltrimethylammonium. A compound such as octyltrimethylammonium, dodecylpyridyl gun, mercaptopyridine gun, octylpyridinium or the like. The surfactant of the present invention may be an anionic surfactant other than the compound represented by the formula (5), in addition to the compound represented by the formula (5) or the formula (6), for example, : Carboxylates, sulfates, phosphates. More specifically, for example, a carboxylate can be preferably used with soap, N-decylamine, polyethylene oxide or polypropylene oxide alkyl ether carboxylate, deuterated peptide; for example, sulfate salt It is preferred to use a sulfated oil, an alkyl sulfate, an alkyl ether sulfate, a polyethylene oxide or a polypropylene oxide alkyl aryl ether sulfate, an alkyl decylamine sulfate; for example, a phosphate salt can It is preferred to use an alkyl phosphate, polyethylene oxide or polypropylene oxide alkyl ether phosphate. The surfactants may be used singly or in combination of two or more. When used in honing liquid 1 L, the amount of surfactant added is preferably 0.001 to 10 g, more preferably 〇.〇1 to 5 g, especially 0. 01~ 1 g is especially ideal. That is, in order to obtain a sufficient effect, the amount of the surfactant -28-200902694 agent is preferably ο. 0 lg or more ‘based on the viewpoint of preventing the decrease in the c Μ P speed, it is preferably 1 g or less. [Other components] The honing liquid of the present invention can further contain an additive within a range not impairing the effects and objects of the present invention. For example, the additive may, for example, be an oxidizing agent, a pH adjuster, a chelating agent or the like. (Oxidant) The honing liquid of the present invention is a preferred embodiment of a compound (oxidizing agent) which further contains a metal capable of oxidizing the object to be honed. For example, examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, and heavy Chromate, permanganate, ozone water, and silver (II) salt, iron (III) salt, of which hydrogen peroxide is preferably used. For example, iron (III) salt is preferably iron (III) nitrate, iron (III) chloride, iron (III) sulfate, iron (III) iron or the like, and iron ( III) organic wrong salt. The amount of the oxidizing agent to be added can be adjusted in accordance with the amount of the thin disk in the initial stage of the barrier CMP. In the case where the amount of the thin disk in the initial stage of the barrier CMP is large, that is, in the case of the barrier C Μ P, in the case where the wiring member is not excessively honed, it is desirable to reduce the amount of the oxidizing agent; The amount is sufficiently small. In the case where the wiring material is honed at a high speed, it is desirable to increase the amount of the oxidizing agent added. In this way, it is desirable to change the amount of the oxidizing agent according to the condition of the thin disk in the initial stage of the barrier CMP, and it is preferably set to O.Olmol~lmol in the pulverizing solution 1 L used for honing, especially It is particularly preferable to set it as O.〇5mol~0_6mol. -29- 200902694 (pH adjuster) The honing liquid of the present invention is preferably in the range of pH 2.5 to 5.0, more preferably pH 3.0 to 4.5, from the viewpoint of achieving high honing speed. When the pH of the honing liquid is controlled to this range, it is possible to significantly adjust the honing speed of the interlayer insulating film, and to exhibit particularly excellent effects. In order to adjust the pH to the above preferred range, a base/acid or a buffer can be used. For example, an alkali/acid or a buffering agent is preferably an organic ammonium hydroxide such as ammonia, ammonium hydroxide or tetramethylammonium hydroxide; an alkanolamine such as diethanolamine, triethanolamine or triisopropanolamine. Non-metal alkaline agents such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; inorganic acids such as nitric acid, sulfuric acid and phosphoric acid; carbonates such as sodium carbonate; phosphates such as trisodium phosphate Borate, tetraborate, hydroxybenzoate, and the like. Particularly preferred alkali chemicals are ammonium hydroxide, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide. The amount of the alkali/acid or the buffer is preferably such that the pH is maintained in a preferred range, and is preferably set to 0.001 ml to 1.0 mol of the honing liquid used in the honing. Good set to 003.003mo1 ~ 〇.5mo1. (chelating agent) The honing liquid of the present invention is preferably a chelating agent (i.e., a 'hard water softener), in order to reduce the adverse effects of the polyvalent metal ions or the like mixed therein. For example, the chelating agent may be exemplified by a general hard water softening agent for fishing or magnesium inhibitors, or the like, and specifically, for example, nitrogen-30-200902694-based triacetic acid, di-extended ethyltriamine-five Acetic acid, ethyl diamine tetra N, N, N_trimethylene phosphonic acid, ethyl diamine-oxime, hydrazine, hydrazine, Ν'-tetramethylene, trans-cycloheximide diamine tetraacetic acid,丨, 2_Diaminopropyl propylene terephthalate ether diamine tetraacetic acid, ethylidene diamine o-hydroxyphenylacetic acid, ethylene succinate (SS body), N-(2 - hydrazine ethyl) -L - aspartame @ alanine di-branched acid, 2-phosphinodin-1,2,4-tridecanoic acid, 1-diethylenediphosphonic acid, N,N'-double (2-veans) Ethyl diamine - N, N' - di 1,2-dihydroxybenzene - 4,6 - disulfonic acid and the like. If necessary, the chelating agent may be used in combination of two or more kinds. The amount of the metal ionic agent to be added to the polyvalent metal ion or the like to be blocked is preferably a sufficient amount, for example, to be used in 1 L of honing, so that it can be added in an amount of 0 to 0003 mol 丨 〇 〇 7 mol. The honing fluid of the present invention is produced for the purpose of, for example, an antistatic agent or a compound represented by the formula (1) and can be mixed by a corrosion inhibitor, a colloidal cerium oxide, a double It is obtained by ion or a single quaternary ammonium cation, an organic acid, a surfactant, and water. In addition, the honing liquid of the present invention is used as the honing liquid, for example, 1 _ is a concentrated liquid, and when used, a solution is added and diluted to prepare a use liquid; 2. Each component is The aqueous solution is prepared, mixed, and if necessary, water is added to form a use liquid: 3. After the use liquid is used, the shape is adjusted. Acetic acid, methylphosphine, ethylenediamine, I' /S-yl-1,1-acetic acid, chelated honing fluid are added to limit. 1 compound, ammonium cation additive and state, water or water, which will be described later. -31 - 200902694 Generally, the honing fluid of the present invention is formed from copper metal and/or copper alloy. Between the wiring and the interlayer insulating film, it is suitable for honing the barrier layer made of a barrier metal material in order to prevent copper from diffusing. Next, the honing method of the present invention will be described below. The honing method of the present invention is characterized in that the honing liquid of the present invention is used in the honing of the semiconductor integrated circuit barrier layer. The honing liquid used in the honing method of the present invention is not particularly limited as long as it is the honing liquid of the present invention. Further, the semiconductor integrated circuit used in the honing method of the present invention is not particularly limited as long as it has a barrier layer. In the honing method of the present invention, the honing of the semiconductor integrated circuit barrier layer can be exemplified as the preferred aspect of CMP. [Barrier Metal Material] Generally, the material of the barrier layer constituting the honing agent of the present invention may be a low-resistance metal material, and is preferably Ru, Ru〇4, TlN, Tiw, Ta ' TaN. , w, WN, among them, especially Ta, TaN 'Ru, Ru〇4 is particularly desirable. [Interlayer insulating film] The interlayer insulating film to be honed by the honing liquid of the present invention may be, for example, a dielectric constant having a specific dielectric constant of about 3.5 to 2.0, in addition to an interlayer insulating film which is generally used for TE〇s or the like. The dielectric constant material (for example, an organic polymer-based S10C system, an S1FF system or the like, and is usually simply referred to as an L〇w_k film) is an interlayer insulating film. Specifically, W 'interlayer insulating film forming material for low dielectric constant-32-200902694 'S i 0 C system' can be cited as: HSG - R 7 (Hitachi Chemical Industry), BLACKDIAMOND ( Applied Materials, Inc) Wait. [Wiring metal material] In the present invention, for example, the honed object to be honed is preferably a wiring made of a copper metal and/or a copper alloy, which is suitable for a semiconductor device such as L SI. In particular, the wiring material is preferably a copper alloy. Among the copper alloys, copper alloys containing silver are more preferred. In addition, the content of silver contained in the copper alloy is preferably 40% by mass or less, particularly preferably 10% by mass or less, more preferably 1% by mass or less, and most of the copper alloys in the range of 0.0000 1 to 0.1% by mass. For superior results. [Width of Wiring] In the present invention, for example, the honed object to be honed is suitable for use in a DRAM device system, and is preferably a wiring having a half pitch of 11 5 /zm or less, more preferably 0.10/zm. Hereinafter, it is preferably 0.08//m or less. On the other hand, for example, when the honed object is applied to the MPU apparatus, it is preferable to have the following wiring, and more preferably 〇. 9/zm or less, preferably 0.07/zm or less. The honing liquid of the present invention described above has a particularly superior effect on the honed material having such wiring. [Horse method] In the honing method of the present invention, the honing liquid is used in the form of its use. For example, a concentrated liquid is prepared by adding water or an aqueous solution to be diluted. In the case of using the liquid; 2) Each component is prepared by the aqueous solution described in the following items, and then mixed, if necessary, by adding -33-200902694 water to prepare the use liquid; 3. after using the liquid The situation of modulation. In the honing method of the present invention, the honing liquid in any of the cases can be applied. The honing method of the present invention may be characterized in that the honing liquid is supplied to the honing pad on the honing fixed plate, and is in contact with the honed surface of the honed object, so that the honed surface and the honing pad are relatively moved. The method is one of the preferred aspects. The apparatus for honing can use the following general honing apparatus, a support frame for holding a honed object (for example, a wafer formed of a film of a conductive material, etc.) having a honed surface, and a honing pad attached thereto A honing fixed disk (with a motor that can change the number of revolutions, etc.). The honing pad can be a general non-woven fabric, a foamed polyurethane resin, a porous fluororesin or the like, and is not particularly limited. Further, there is no particular limitation on the honing condition, and the rotation speed of the honing fixed disk is preferably such that the honed object does not fly out to perform a low rotation of 200 rpm or less. The pressing of the honed object honing pad having the honed surface (the honed film) is preferably 0.68 to 34.5 KPa, and the in-plane uniformity and pattern flatness of the honed object in order to meet the honing speed are further Good for 3.4 0~2 0.7 KP a. During the honing, a pump or the like can be used to continuously supply the honing liquid to the honing pad. In the present invention, as in the method of 1., when the concentrate is diluted, an aqueous solution shown below can be used. The aqueous solution contains water containing at least one of an oxidizing agent, an organic acid, an additive, and a surfactant, and the total amount of the component contained in the aqueous solution and the diluted concentrated liquid is used in the honing. The composition of the honing fluid (using liquid) is carried out in the manner of -34-200902694. In this manner, in the case where an aqueous solution is used to dilute the concentrate, it is possible to prepare a more concentrated concentrate because it can be blended with an insoluble component in the form of an aqueous solution. In addition, a method of adding water or an aqueous solution to the concentrated liquid for dilution, for example, mixing and mixing the piping for supplying the concentrated honing liquid with the piping for supplying water or an aqueous solution, and mixing them The method of supplying the mixed and diluted honing liquid to the honing pad. The mixing of the concentrate with water or an aqueous solution can be carried out by a method generally employed in which a solution is mixed by a narrow passage in a state where pressure is applied, and in the piping, the filling of the glass tube or the like is repeated. A method of splitting and merging the flow of the liquid, and a method of providing a blade that is rotated by the power in the pipe. The supply speed of the honing liquid is preferably 10 to 1000 ml/min, and the flatness of the surface to be honed and the flatness of the pattern are more suitable for the honing speed, more preferably 170 to 800 ml/min, further by water In the method of diluting the concentrate with an aqueous solution or the like, and honing the surface, for example, a pipe for supplying the honing liquid and a pipe for supplying water or an aqueous solution are separately provided, and a predetermined amount of the solution is supplied from each pipe to the respective pipes. The honing pad is a method in which the honing pad is mixed with the relative movement of the honed surface and honed on one side. Further, it is also possible to use a method in which a predetermined amount of the concentrated liquid and water or an aqueous solution are added to a container, and the mixed honing liquid is supplied to the honing pad to perform honing. -35- 200902694 In addition, for other honing methods, the components to be contained in the honing liquid are divided into at least two structural components. When these structural components are used, water or an aqueous solution is added and diluted to supply to the honing. The honing pad on the fixed plate is in contact with the honed surface to honing the honed surface and the honing pad. For example, an oxidizing agent can be used as the structural component (A), and an antistatic agent or a compound represented by the formula (1), an organic acid, an additive, a surfactant, and water can be used as the structural component (B). In the case of the component, water or an aqueous solution can be added to dilute the structural component (A) and the structural component (B) and then used. In addition, the additive having low solubility is divided into two structural components (A) and (B), for example, 'the oxidizing agent, the additive, and the surfactant are used as the structural component (A), and the antistatic agent is represented by the general formula (1). The compound, the organic acid, the additive, the surfactant, and water are used as the structural component (B), and when used, the structural component (A) and the structural component (B) can be diluted with water or an aqueous solution. In the case of the above example, it is necessary to supply three pipes of the structural component (A), the structural component (B), and the water or the aqueous solution separately, and the method of diluting and mixing is to join the three pipes to one pipe supplied to the honing pad. A method in which the piping is mixed, and in this case, it is also possible to join the other piping after joining the two pipings. Specifically, the structural components of the insoluble additive and the other structural components are mixed, and the mixing path is increased to ensure the connection of the water or the aqueous solution after the dissolution time. Other mixing methods include: as described above, directly guiding the three pipes -36-Φ 200902694 to the honing pad, respectively, by mixing the honing pad with the honed surface; mixing three in one container A method of supplying a diluted honing fluid to a honing pad. In the honing method described above, when the oxidizing agent is contained at 40 ° C or lower, the other structural components are heated from room temperature, and when water or an aqueous solution is mixed while the structural component and the other structural components are mixed, The liquid temperature is made into a formula. The method is a raw material which utilizes high temperature and dissolved image to improve the solubility of the honing liquid, preferably by dissolving the above-mentioned other structural components from room temperature, since the temperature is in the solution. To precipitate, it is necessary to dissolve the raw material which has been precipitated before heating, using another structure in a low temperature state. It is sufficient to: heat and transport the raw materials after dissolving: and; and pre-stirring the solution containing the precipitates, and the solution is dissolved and dissolved. The temperature of the other constituents containing the oxidizing agent after heating is increased to 4 〇 ° c. It is feared that the oxidizing agent will decompose, and it is preferable to use 4 (TC) to mix the constituent components of the other structuring agent heated. In this manner, in the present invention, the honing may be supplied to the surface to be honed after being halved or more. In this case, the component containing the oxide and the component containing the organic acid may be formed, and the honing liquid may be formed. Concentrate, and then the relative movement of the dilute, resulting in a composition of the composition to 100 ° C, or the addition of 40 ° C below the degree of solution becomes higher. Heating to 100 ° C lower In the case of the component, the component of the chargeable component and the heating pipe component of the structure can be divided and supplied as a component and a component which is added by means of oxygen. The water supply is additionally supplied -37-200902694 to the surface to be honed. In the present invention, a method of dividing the component of the honing liquid into two or more divisions and supplying it to the surface to be honed is used. The amount of the supply is the total amount of supply from each pipe. [Mat] The honing pad which can be applied to the honing method of the present invention, whether it is a non-foamed structural pad or a foamed structural pad The former is a plastic plate, and a hard synthetic resin block is used for the honing pad. In addition, the latter has a separate foam (dry foaming system), a continuous foaming (wet foaming system), Three kinds of two-layer composites (layered systems), especially two-layer composites (layered systems). The foaming may be uniform or non-uniform. Generally, it may also be more abrasive grains for honing (for example, Separate cerium oxide, cerium oxide, aluminum oxide, resin, etc. In addition, the hardness may be either soft or hard, and in the laminated layer, it is preferable to use different hardness materials for the respective layers. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate, etc. In addition, lattice groove/hole/concentricity can also be implemented on the surface in contact with the honed surface. Processing of grooves/spiral grooves, etc. The wafer to be honed by the CMP in the honing method of the present invention has a diameter of preferably 2 mm or more, particularly preferably 300 mm or more. When 300 mm or more, it is remarkable. [Effects of the present invention] [Mulching device] The device capable of performing honing using the honing liquid of the present invention is not particularly limited to -38 to 200902694, and examples thereof include Mirra Mesa CMP and Reflexion CMP (Applied Materials). FREX200, FREX300 (荏原株式会社), NPS3301, NPS 23 0 1 (Nikon), A-FP-310A 'A-FP-210A (Toho Precision), 2300 TERES ( Lam Research), Momentum (Speedfam IPEC), etc. In the honing method of the present invention, the honed material (for example, a wafer) to be honed is sufficiently washed in a water stream after honing, and is wiped and attached by using a spin dryer, a rotary dryer, or the like. The water droplets on the object are dried, dried, and cut by a conventional method, for example, to form a semiconductor integrated circuit. The semiconductor integrated circuit which is honed by the honing liquid of the present invention has a honing surface which is flat and has almost no barrier layer. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples. [Example 1] A honing liquid shown in the following composition was prepared and subjected to a honing test. <Composition (1) >

• 抗靜電劑：D-ι所示之化合物、0_8g/L• Antistatic agent: compound represented by D-ι, 0_8g/L

• 雙四級銨陽離子：氯化六羥季銨、〇.2g/L• Double quaternary ammonium cation: hexahydroxy quaternary ammonium chloride, 〇.2g/L

• 腐蝕抑制劑：苯并***（BTA ) 、0.5g/L• Corrosion inhibitor: benzotriazole (BTA), 0.5g/L

*膠體二氧化矽：二次粒徑：65nm、PL3硏磨劑、日本扶 桑化學工業公司製、200g/L •具有羧基的化合物：二甘醇酸（和光純藥工業（股）製）、 -39- 200902694* Colloidal cerium oxide: secondary particle size: 65 nm, PL3 honing agent, manufactured by Japan Fuso Chemical Industry Co., Ltd., 200 g/L • Compound with carboxyl group: diglycolic acid (manufactured by Wako Pure Chemical Industries, Ltd.), - 39- 200902694

lg/L •添加純水後之總量··丨〇 〇 〇 m L、p Η 3 _ 5 (以氨水與硝酸加 以調整） •氧化劑：3 0 %過氧化氫水、1 〇 m 1 (評估方法） 硏磨裝置係使用Lapmaster公司製之裝置「LGP-612」， 利用下列之條件，一面供應硏磨劑，並一面硏磨下列所示 之各晶圓膜： • 平台旋轉數：90rpm • 噴頭旋轉數：85rpm • 硏磨壓力·· 13.79kPa •硏磨墊：RodelNitta股份有限公司製之p〇l〇texpad • 硏磨液供應速度：200ml/min (硏磨速度評估：硏磨對象物） 硏磨對象物係於Si基板上，使用已長成Ta膜、TE0S 膜、S i 0 C膜的8吋晶圓。 <硏磨速度> 硏磨速度係藉由分別測定CMP前後之Ta膜（阻障層 )、TE0S膜（絕緣膜）、SiOC ( BD-II )之膜厚，再由下 列式子進行換算後而求出。 硏磨速度（A/分鐘）=(硏磨前之膜厚-硏磨後之膜厚 )/硏磨時間 將所得的結果顯示於表1。 〔實施例2〜3 5、及比較例1〜2〕 -40- 200902694 使用將實 示之組成後而 條件，進行硏 施例1中之組成 調製的硏磨液， 磨實驗。將結果 (1 )變更爲下表 利用與實施例1 顯示於表1至表 1至表3揭 胃樣之硏磨 3 〇Lg/L • Total amount after adding pure water··丨〇〇〇m L, p Η 3 _ 5 (adjusted with ammonia and nitric acid) • Oxidizer: 30% hydrogen peroxide water, 1 〇m 1 (evaluation Method) The honing device uses a device "LGP-612" manufactured by Lapmaster Co., Ltd., and supplies the honing agent on one side under the following conditions, and honing the wafer films shown below: • Platform rotation number: 90 rpm • Nozzle Number of rotations: 85 rpm • Honing pressure · · 13.79 kPa • Honing pad: p〇l〇texpad made by RodelNitta Co., Ltd. • Supply rate of honing liquid: 200 ml/min (honing speed evaluation: honing object) 硏The object to be polished was placed on a Si substrate, and an 8-inch wafer which had grown into a Ta film, a TEOS film, or a S i 0 C film was used. <honing speed> The honing speed is measured by the following formula by measuring the film thicknesses of the Ta film (barrier layer), the TEOS film (insulating film), and the SiOC (BD-II) before and after the CMP, respectively. Then find it. Honing speed (A/min) = (film thickness before honing - film thickness after honing) / honing time The results obtained are shown in Table 1. [Examples 2 to 3 5 and Comparative Examples 1 to 2] -40 - 200902694 The honing liquid prepared by the composition of Example 1 was subjected to the conditions of the composition and the grinding test was carried out. Change the result (1) to the following table. Use the example 1 shown in Table 1 to Table 1 to Table 3 to slap the stomach sample 3 〇

抗靜電劑 (含量） 特定陽離子 (含量） 有機酸 (含量） 膠體二 氧化矽 (含量） 其它之成分 (含量） pH Ta 硏磨速度 (nm/min) TEOS 硏磨 (nm/min) SiOC mmmm (nm/min ) 實施例1 D-1 (〇.8g/L) A-l (〇.2g/L) B-l (lg/L) C-l (5質量％) BTA (lg/L) 3.5 55 85 15 實施例2 D-1 (〇-8g/L) A-33 (〇.4g/L) B-l (lg/L) C-2 (5質量％) BTA (lg/L) DNS(0.5g/L) 3.2 59 90 10 實施例3 D-2 (〇-8g/L) A-8 (〇-2g/L) B-2 Og/t) C-2 (5質量％) DBTA(lg/L) 3.5 60 105 1$ 實施例4 D-3 (〇.8g/L) A-5 (〇.2g/L) B-l (lg/L) C-4 (5質童％) DCEBTA (lg/L) DP (0.5g/L) 3.5 65 85 13 實施例5 D-3 C〇.8g/L) A-10 (〇.2g/L) B-3 (lg/L) C-l (2.5質量％ ) C-3 (：2.5 質量％) BTA (lg/L) DBS(0.5g/L) 3.5 66 90 16 實施例6 D-4 C〇.8g/L) A-32 (〇.2g/L) B-5 (lg/L) C-2 (5質量％) HMBTA (lg/L) 3.5 70 100 17 實施例7 D-4 (〇.8g/L) A-33 (〇.4g/L) B-l (lg/L) C-4 (5質量％) BTA (lg/L) LTM(0.5g/L) 3.0 70 90 18 寅施例8 D-5 (O.Sg/L) A-5 (〇.2g/L) B-I (lg/L) C-2 (5質量％) BTA (lg/L) 3.5 68 85 15 實施例9 D-6 (〇.8g/L) A-16 (〇.2g/L) B-3 (lg/L) C-l (2.5質量％) C-3 (2,5質量％) HEABTA Og/L) DP (0.5g/L) 3.5 59 115 16 寅施例10 D-6 (〇-8g/L) A-20 (〇.2g/L) B-3 (lg/L) C-2 (2.5質量％) C-3 (2.5質量％) BTA (lg/L) DBS(0.5g/L) 3.8 50 105 17 實施例11 D-6 (〇.8g/L) A-41 (〇.4g/L) B-4 (lg/L) C-2 (5質量％) BTA (lg/L) DP (0.5g/L) 3.5 46 90 15 實施例12 D-6 (〇.8g/L) A-12 (〇.2g/L) B-l (lg/L) C-l (5質置％) BTA (lg/L) 3.0 48 85 12 -41 - 200902694 【表2】 抗靜電劑 (含量） 特定陽離子 (含量） 有機酸 (含量） 膠體二 氧化砂 (含量） 其它之成分 (含量） pH Ta 硏磨速度 (nm/min) TEOS 硏磨速度 (nm/min) SiOC 硏磨速度 (nm/min) 實施例13 D-7 (〇-8g/L) A-13 (〇.2g/L) B-l (lg/L) C-2 (5質量％) HMBTA (lg/L) 3.5 68 80 10 實施例14 D-7 (〇.8g/L) A-2 (〇.2g/L) B-5 (lg/L) C-l (5質量％) DBTA(lg/L) ' DNS(0.5g/L) 2.5 65 90 12 實施例15 D-8 (〇.8g/L) A-15 (〇.2g/L) B-l (lg/L) C-4 (5質量％) DCEBTA (lg/L) 3.5 63 80 15 實施例16 D-8 (〇.8g/L) A-5 (〇.2g/L) B-l (lg/L) C-4 (2.5質量％) C-5 (2.5質量％) BTA (lg/L) 3.5 58 80 18 實施例17 D-9 (〇.8g/L) A-10 (〇.2g/L) B-2 (lg/L) C-3 (5質量％) BTA (lg/L) 3.5 55 95 13 實施例18 D-10 (〇.8g/L) A-32 (〇-2g/L) B-l (lg/L) C-l (5質量％) DBTA(lg/L) 3.5 70 90 15 實施例19 D-ll (〇-8g/L) A-8 (〇.2g/L) B-3 (lg/L) C-2 (5質量％) DCEBTA (lg/L)、 DBS(0.5g/L) 3.5 75 80 12 實施例20 D-12 (〇-8g/L) A-13 (〇.2g/L) B-l (lg/L) C-4 (5質量％) BTA (lg/L) 3.2 65 85 15 實施例21 D-12 (〇.8g/L) A-21 (〇.2g/L) B-2 (lg/L) C-2 (5質量％) BTA( lg/L) ' DP (0.5g/L) 3.5 66 95 20 實施例22 D-13 (〇.8g/L) A-36 (〇.4g/L) B-2 (lg/L) C-l (2.5質量％) C-3 (2.5質量％) BTA(lg/L)、 LTM(0.5g/L) 3.5 68 95 13 實施例23 D-13 (〇.8g/L) A-23 (〇-2g/L) B-l (lg/L) C-2 (2.5質量％) C-3 (2.5質量％) BTA(lg/L)、 DP (0.5g/L) 3.8 70 105 14 實施例24 D-14 (〇.8g/L) A-2 (〇.2g/L) B-2 (lg/L) C-2 (5質量％) BTA (lg/L) 3.5 68 115 12 -42- 200902694 【表3】 抗靜電劑 (含量） 特定陽離子 (含量） 有機酸 (含量） 膠體二 氧化矽 (含量） 其它之成分 (含量） pH Ta 硏磨速度 (nm/min) TEOS 硏磨速度 (nm/min ) SiOC 硏磨速度 (nm/min) 實施例25 D-15 (〇.8g/L) A-25 (〇.2g/L) B-l (lg/L) C-3 (5質量％) DCEBTA (lg/L) 3.5 60 105 11 實施例26 D-16 (〇.8g/L) A-10 (〇.2g/L) B-l Og/L) C-2 (5質量％) BTA (lg/L) DP (0.5g/L) 3.8 75 100 10 實施例27 D-17 (〇.8g/L) A-8 (〇.2g/L) B-l (lg/L) C-4 (5質量％) HEABTA (lg/L) DP (0.5g/L) 3.5 70 95 15 實施例28 D-18 (〇.8g/L) A-5 (〇.2g/L) B-4 (lg/L) C-l (5質量％) BTA (lg/L) 3.5 68 85 20 實施例29 D-19 (〇.8g/L) A-2I (〇-2g/L) B-l (lg/L) C-l (5質量％) BTA (lg/L) DNS(0.5g/L) 3.5 59 80 18 實施例30 D-19 (〇.8g/L) A-20 (〇.2g/L) B-2 (lg/L) C-2 (5質量％) BTA (lg/L) 3.5 60 85 17 實施例31 D-20 (〇.Sg/L) A-31 (〇.2g/L) B-l (lg/L) C-4 (5質量％) BTA (lg/L) 3.8 58 75 16 實施例32 D-21 (〇.8g/L) A-36 (〇.4g/L) B-5 Og/L) C-l (2.5質量％) C-3 (2.5質量％) BTA (lg/L) DP (0.5g/L) 3.5 59 90 15 實施例33 D-22 (〇.8g/L) A-16 (〇.2g/L) B-2 Og/L) C-2 (5質量％) BTA (lg/L) 3.5 70 80 14 實施例34 D-23 (〇.8g/L) A-41 (〇.4g/L) B-l (lg/L) C-4 (5質量％) BTA (lg/L) 3.5 65 85 13 實施例35 D-23 (〇-8g/L) A-33 (〇-4g/L) B-5 (lg/L) C-l (2.5質量％) C-3 (2.5 mm%) BTA (lg/L) DP (0.5g/L) 3.5 60 90 19 比較例1 c-l (5質量 %) 乳酸a〇g/u BTA (l.〇lg/L) 3.5 60 85 45 比較例2 C-2 (2.5 mm.%) C-3 (2.5質量％) 乳酸a〇g/L) BTA (l.〇lg/L) 9.5 40 30 75 -43- 200902694 於上述表1至表3所揭示之D-1〜D-23、A-1〜A-45係 指上述之說例化合物。 另外，於上述表1至表3中所簡稱之化合物的詳細內 容顯示如下： 腐蝕抑制劑 BTA : 1 ,2,3-苯并*** DBTA ·· 5,6-二甲基-1，2,3-苯并*** DCEBTA ：卜（1,2 -二羧乙基）苯并*** HEABTA ： 1-〔N,N-雙（羥乙基）胺甲基〕苯并*** 溶膠 HMBTA ： 1-(羥甲基）苯并*** 界面活性劑 DBS:十二烷基苯磺酸 D N S :十二烷基萘苯磺酸 LTM :硝酸月桂基三甲基銨 D P :硝酸十二烷基吡啶鏺 再者，針對表1至表3所揭示之膠體二氧化矽C-1〜 C-5之形狀、一次粒徑，顯示於下表4。還有，下表4揭示 之膠體二氧化矽全部爲扶桑化學工業公司製。 【表4】 硏磨粒名〔一次粒徑/nm.，形狀〕 C - 1 P L 3 [ 3 5 n m > 繭形〕 C-2 PL3L〔 35nm，球形〕 C-3 PL3H〔 35nm，聚集體〕 C -4 PL2〔 25nm，繭形〕 C-5 PL2L〔 20nm，球形〕 -44- 200902694 另外’將具有表1至表3所揭示之羧基的化合物（有 機酸）B-1〜B-5之化合物名顯示於下表5。 【表5】 化合物名 B-1 二甘醇酸 B-2 2，5 -呋喃二羧酸 B-3 2 -四氫呋喃羧酸 B-4 甲氧基乙酸 B-5 無有機酸 若根據表1至表3得知：使用實施例1〜3 5之硏磨液 的情形’相較於比較例丨〜2，Ta及TE0S之硏磨速度爲高 的’另外’相對於Low-k膜之硏磨速度將被充分抑制。Antistatic agent (content) Specific cation (content) Organic acid (content) Colloidal cerium oxide (content) Other components (content) pH Ta honing speed (nm/min) TEOS honing (nm/min) SiOC mmmm ( Nm/min ) Example 1 D-1 (〇.8g/L) Al (〇.2g/L) Bl (lg/L) Cl (5 mass%) BTA (lg/L) 3.5 55 85 15 Example 2 D-1 (〇-8g/L) A-33 (〇.4g/L) Bl (lg/L) C-2 (5 mass%) BTA (lg/L) DNS(0.5g/L) 3.2 59 90 10 Example 3 D-2 (〇-8g/L) A-8 (〇-2g/L) B-2 Og/t) C-2 (5 mass%) DBTA(lg/L) 3.5 60 105 1$ Example 4 D-3 (〇.8g/L) A-5 (〇.2g/L) Bl (lg/L) C-4 (5% child%) DCEBTA (lg/L) DP (0.5g/L 3.5 65 85 13 Example 5 D-3 C〇.8g/L) A-10 (〇.2g/L) B-3 (lg/L) Cl (2.5% by mass) C-3 (:2.5% by mass BTA (lg/L) DBS (0.5g/L) 3.5 66 90 16 Example 6 D-4 C〇.8g/L) A-32 (〇.2g/L) B-5 (lg/L) C -2 (5 mass%) HMBTA (lg/L) 3.5 70 100 17 Example 7 D-4 (〇.8g/L) A-33 (〇.4g/L) Bl (lg/L) C-4 ( 5 mass%) BTA (lg/L) LTM (0.5 g/L) 3.0 70 90 18 Example 8 D-5 (O.Sg/L) A-5 (〇.2g/L) BI (lg/L ) C-2 (5 %) BTA (lg/L) 3.5 68 85 15 Example 9 D-6 (〇.8g/L) A-16 (〇.2g/L) B-3 (lg/L) Cl (2.5% by mass) C-3 (2,5 mass%) HEABTA Og/L) DP (0.5g/L) 3.5 59 115 16 Example 10 D-6 (〇-8g/L) A-20 (〇.2g/L) B-3 (lg/L) C-2 (2.5 mass%) C-3 (2.5 mass%) BTA (lg/L) DBS (0.5 g/L) 3.8 50 105 17 Example 11 D-6 (〇. 8g/L) A-41 (〇.4g/L) B-4 (lg/L) C-2 (5 mass%) BTA (lg/L) DP (0.5g/L) 3.5 46 90 15 Example 12 D-6 (〇.8g/L) A-12 (〇.2g/L) Bl (lg/L) Cl (5 mass%) BTA (lg/L) 3.0 48 85 12 -41 - 200902694 [Table 2 】 Antistatic agent (content) Specific cation (content) Organic acid (content) Colloidal silica sand (content) Other components (content) pH Ta honing speed (nm / min) TEOS honing speed (nm / min) SiOC Honing speed (nm/min) Example 13 D-7 (〇-8g/L) A-13 (〇.2g/L) Bl (lg/L) C-2 (5 mass%) HMBTA (lg/L) 3.5 68 80 10 Example 14 D-7 (〇.8g/L) A-2 (〇.2g/L) B-5 (lg/L) Cl (5 mass%) DBTA(lg/L) ' DNS (0.5g/L) 2.5 65 90 12 Example 15 D-8 (〇.8g/L) A-15 (〇.2g/L) Bl (lg/L) C -4 (5 mass%) DCEBTA (lg/L) 3.5 63 80 15 Example 16 D-8 (〇.8g/L) A-5 (〇.2g/L) Bl (lg/L) C-4 ( 2.5 mass%) C-5 (2.5 mass%) BTA (lg/L) 3.5 58 80 18 Example 17 D-9 (〇.8g/L) A-10 (〇.2g/L) B-2 (lg /L) C-3 (5 mass%) BTA (lg/L) 3.5 55 95 13 Example 18 D-10 (〇.8g/L) A-32 (〇-2g/L) Bl (lg/L) Cl (5 mass%) DBTA (lg/L) 3.5 70 90 15 Example 19 D-ll (〇-8g/L) A-8 (〇.2g/L) B-3 (lg/L) C-2 (5 mass%) DCEBTA (lg/L), DBS (0.5 g/L) 3.5 75 80 12 Example 20 D-12 (〇-8g/L) A-13 (〇.2g/L) Bl (lg/ L) C-4 (5 mass%) BTA (lg/L) 3.2 65 85 15 Example 21 D-12 (〇.8g/L) A-21 (〇.2g/L) B-2 (lg/L C-2 (5 mass%) BTA (lg/L) 'DP (0.5 g/L) 3.5 66 95 20 Example 22 D-13 (〇.8g/L) A-36 (〇.4g/L) B-2 (lg/L) Cl (2.5% by mass) C-3 (2.5% by mass) BTA (lg/L), LTM (0.5 g/L) 3.5 68 95 13 Example 23 D-13 (〇.8g /L) A-23 (〇-2g/L) Bl (lg/L) C-2 (2.5% by mass) C-3 (2.5% by mass) BTA (lg/L), DP (0.5g/L) 3.8 70 105 14 Example 24 D-14 (〇.8g/L) A-2 (〇.2g/L) B-2 (lg/L) C-2 (5 Mass%) BTA (lg/L) 3.5 68 115 12 -42- 200902694 [Table 3] Antistatic agent (content) Specific cation (content) Organic acid (content) Colloidal cerium oxide (content) Other components (content) pH Ta honing speed (nm/min) TEOS honing speed (nm/min) SiOC honing speed (nm/min) Example 25 D-15 (〇.8g/L) A-25 (〇.2g/L) ) Bl (lg/L) C-3 (5 mass%) DCEBTA (lg/L) 3.5 60 105 11 Example 26 D-16 (〇.8g/L) A-10 (〇.2g/L) Bl Og /L) C-2 (5 mass%) BTA (lg/L) DP (0.5 g/L) 3.8 75 100 10 Example 27 D-17 (〇.8g/L) A-8 (〇.2g/L ) Bl (lg/L) C-4 (5 mass%) HEABTA (lg/L) DP (0.5 g/L) 3.5 70 95 15 Example 28 D-18 (〇.8g/L) A-5 (〇 .2g/L) B-4 (lg/L) Cl (5 mass%) BTA (lg/L) 3.5 68 85 20 Example 29 D-19 (〇.8g/L) A-2I (〇-2g/ L) Bl (lg/L) Cl (5 mass%) BTA (lg/L) DNS (0.5 g/L) 3.5 59 80 18 Example 30 D-19 (〇.8g/L) A-20 (〇. 2g/L) B-2 (lg/L) C-2 (5 mass%) BTA (lg/L) 3.5 60 85 17 Example 31 D-20 (〇.Sg/L) A-31 (〇.2g /L) Bl (lg/L) C-4 (5 mass%) BTA (lg/L) 3.8 58 75 16 Example 32 D-21 (〇.8g/L) A-36 (〇.4g/L) B-5 Og/L) Cl (2.5% by mass) C-3 (2.5% by mass) BTA (lg/L) DP (0.5 g/L) 3.5 59 90 15 Example 33 D-22 (〇.8g/L) A-16 (〇.2g/L) B-2 Og/L) C-2 (5 mass%) BTA ( Lg/L) 3.5 70 80 14 Example 34 D-23 (〇.8g/L) A-41 (〇.4g/L) Bl (lg/L) C-4 (5 mass%) BTA (lg/L 3.5 65 85 13 Example 35 D-23 (〇-8g/L) A-33 (〇-4g/L) B-5 (lg/L) Cl (2.5% by mass) C-3 (2.5 mm%) BTA (lg/L) DP (0.5 g/L) 3.5 60 90 19 Comparative Example 1 cl (5 mass%) Lactic acid a〇g/u BTA (l.〇lg/L) 3.5 60 85 45 Comparative Example 2 C- 2 (2.5 mm.%) C-3 (2.5 mass%) lactic acid a〇g/L) BTA (l.〇lg/L) 9.5 40 30 75 -43- 200902694 D as disclosed in Tables 1 to 3 above -1 to D-23 and A-1 to A-45 refer to the above-mentioned compounds. Further, the details of the compounds referred to in the above Tables 1 to 3 are as follows: Corrosion inhibitor BTA: 1, 2,3-benzotriazole DBTA ··5,6-dimethyl-1,2, 3-benzotriazole DCEBTA: Bu (1,2-dicarboxyethyl)benzotriazole HEABTA : 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole sol HMBTA : 1 -(Hydroxymethyl)benzotriazole surfactant DBS: Dodecylbenzenesulfonic acid DNS: Dodecylnaphthalenesulfonic acid LTM: Lauryl trimethylammonium nitrate DP: Dodecylpyridinium nitrate Further, the shapes and primary particle diameters of the colloidal ceria C-1 to C-5 disclosed in Tables 1 to 3 are shown in Table 4 below. Further, the colloidal cerium oxides disclosed in Table 4 below were all made by Fuso Chemical Industry Co., Ltd. [Table 4] honing grain name [primary particle diameter / nm., shape] C - 1 PL 3 [ 3 5 nm > 茧 shape] C-2 PL3L [35 nm, spherical] C-3 PL3H [35 nm, aggregate C -4 PL2 [25 nm, 茧] C-5 PL2L [20 nm, spherical] -44- 200902694 In addition, the compound (organic acid) B-1 to B-5 having the carboxyl group disclosed in Tables 1 to 3 The compound names are shown in Table 5 below. [Table 5] Compound name B-1 diglycolic acid B-2 2,5-furandicarboxylic acid B-3 2 -tetrahydrofurancarboxylic acid B-4 methoxyacetic acid B-5 No organic acid according to Table 1 Table 3 shows that the case of using the honing liquids of Examples 1 to 35 is compared with the comparative example 丨~2, and the honing speed of Ta and TEOS is high, and the 'other' is honed with respect to the Low-k film. The speed will be fully suppressed.

另一方面，得知：雖然比較例1之硏磨液，Ta及TEOS 2研1磨速度上並無問題，相對於L〇w-k膜之硏磨速度並未 被抑制。另外，得知：比較例2之硏磨液，其Ta及TEOS I 之研"磨速度爲低的，並且相對於Low-k膜之硏磨速度變成 非常得快。 *以上之事實，得知：本發明之硏磨液具優越之Ta、 TE〇S W磨速度，相對於Low-k膜之硏磨速度並未被充分抑 制。 【圖式簡單說明】 無。 【主要元件符號說明】 細。 -45-On the other hand, it was found that although the honing liquid of Comparative Example 1 had no problem in the polishing speed of Ta and TEOS 2, the honing speed with respect to the L〇w-k film was not suppressed. Further, it was found that the honing liquid of Comparative Example 2 had a low grinding speed of Ta and TEOS I, and the honing speed with respect to the Low-k film became very fast. * The above facts show that the honing liquid of the present invention has a superior Ta, TE 〇 S W grinding speed, and the honing speed with respect to the Low-k film is not sufficiently suppressed. [Simple description of the diagram] None. [Main component symbol description] Fine. -45-

Claims (1)

200902694 十、申請專利範圍： 1. 一種硏磨液，其係爲了硏磨半導體積體電路阻障層之硏 磨液，其特徵在於含有抗靜電劑。 2. —種硏磨液，其係爲了硏磨半導體積體電路阻障層之硏 磨液，其特徵在於含有下列通式（1 )所示之化合物： 通式（1 ) R1——N200902694 X. Patent application scope: 1. A honing liquid, which is used for honing the ramming fluid of the semiconductor integrated circuit barrier layer, and is characterized by containing an antistatic agent. 2. A honing fluid for honing a turmeric fluid of a semiconductor integrated circuit barrier layer, characterized by containing a compound represented by the following formula (1): Formula (1) R1 - N (式中，R1、R2係表示各自獨立之由氫原子、碳數6〜 30之烷基、烯基、環烷基、芳基、芳烷基與聚環氧乙烷 鏈（EO )所構成族群中所選出之至少一種，V、R2也可 以相互鍵結，a係1以上之整數）。 3 .如申請專利範圍第2項之硏磨液，其中相對於硏磨液之 所有質量，該通式（1 )所示之化合物的濃度爲〇·〇〇5〜 5 0 g/L。 4.如申請專利範圍第1至3項中任一項之硏磨液’其中更 含有腐蝕抑制劑與膠體二氧化矽，且pH爲2.5〜5.0 ° 5 .如申請專利範圍第4項之硏磨液，其中相對於硏磨液之 所有質量，該膠體二氧化矽之濃度爲0.5〜15質量％。 6.如申請專利範圍第4或5項之硏磨液，其中該膠體二氧 化砍之一次平均粒徑爲20〜50nm之範圍。 7 .如申請專利範圍第4至6項中任一項之硏磨液，其中該 腐蝕抑制劑爲由1，2,3-苯并***、5,6-二甲基-1，2,3-苯并 -46 - 200902694 ***、卜（1,2-二羧乙基）苯并***、1-〔N，N-雙（羥乙 基）胺甲基〕苯并***與1 -(羥甲基）苯并三11坐所構成 族群中所選出之至少一種的化合物。 8 .如申請專利範圍第1至7項中任一項之硏磨液’其中更 含有下列通式（2 )所示之二（四級錢）陽離子或下列通 式（3)所示之一（四級銨）陽離子： 通式（2 ) 卒1 R4(wherein R1 and R2 represent each independently consisting of a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a polyethylene oxide chain (EO). At least one selected from the group, V and R2 may be bonded to each other, and a is an integer of 1 or more. 3. The honing liquid according to item 2 of the patent application, wherein the concentration of the compound represented by the formula (1) is 〇·〇〇5 to 50 g/L with respect to all the masses of the honing liquid. 4. The honing fluid of any one of claims 1 to 3, which further comprises a corrosion inhibitor and colloidal cerium oxide, and has a pH of 2.5 to 5.0 ° 5 as claimed in claim 4 The grinding liquid, wherein the concentration of the colloidal ceria is from 0.5 to 15% by mass based on the total mass of the honing liquid. 6. The honing fluid according to claim 4, wherein the primary chlorination of the colloidal oxidized cut is in the range of 20 to 50 nm. The honing liquid according to any one of claims 4 to 6, wherein the corrosion inhibitor is 1,2,3-benzotriazole, 5,6-dimethyl-1,2, 3-Benzo-46 - 200902694 Triazole, Bu (1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole and 1 -(Hydroxymethyl)benzotriene 11 is a compound of at least one selected from the group consisting of. 8. The honing fluid of any one of claims 1 to 7 which further comprises a bis (four-grade) cation represented by the following formula (2) or one of the following formula (3) (Quaternary Ammonium) Cation: General Formula (2) Stroke 1 R4 通式（3 )General formula (3) 〔通式（2)或通式（3)中，R1〜R7係表示各自獨立之 由碳數1〜20之烷基、烯基、環烷基、芳基與芳烷基所 構成族群中所選出之至少一種，R1〜R0中之二個也可以 相互鍵結，X係表示由碳數1〜1 〇之伸烷基、伸烯基、 伸環烷基、伸芳基與組合此等基所構成族群中所選出之 至少一種〕。 9 ·如申請專利範圍第1至8項中任一項之硏磨液，其中更 含有羧基之化合物，具有該羧基之化合物爲下列通式（4) 所示之化合物： -47- 200902694 通式（4 ) R7- 0 - r8_ c〇〇H 〔通式（4)中’ R7與R8係表示各自獨立之烴基，…與 R8也可以相互鍵結而形成環狀構造〕。 10. 如申請專利範圍第1至9項中任一項之硏磨液，其中更 含有陰離子系界面活性劑或陽離子系界面活性劑。 11. 一種硏磨方法，其係於半導體積體電路阻障層之硏磨中 ，使用如申請專利範圍第1至丨0項中任一項之硏磨液。 -48- 200902694 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: ίΕ 〇 J » \Ν 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 通式（1) (CH2CH20)a-H[In the general formula (2) or the general formula (3), R1 to R7 each represent a group consisting of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl group independently having a carbon number of 1 to 20; At least one selected, two of R1 to R0 may be bonded to each other, and X represents an alkyl group, an alkenyl group, a cycloalkyl group, an extended aryl group, and a combination thereof having a carbon number of 1 to 1 fluorene. At least one selected from the group consisting of]. The honing liquid according to any one of claims 1 to 8, wherein the compound further contains a carboxyl group, and the compound having the carboxyl group is a compound represented by the following formula (4): -47- 200902694 (4) R7- 0 - r8_ c〇〇H [In the formula (4), 'R7 and R8 each represent a hydrocarbon group which is independent, and R8 may be bonded to each other to form a cyclic structure. 10. The honing fluid of any one of claims 1 to 9 which further comprises an anionic surfactant or a cationic surfactant. A honing method for honing a barrier layer of a semiconductor integrated circuit using the honing liquid according to any one of claims 1 to 10. -48- 200902694 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Ε 〇 J » \Ν VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: General formula (1) (CH2CH20)a-H
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