TWI252506B - CMP sizing material, polishing method and method for manufacturing semiconductor device - Google Patents

CMP sizing material, polishing method and method for manufacturing semiconductor device Download PDF

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Publication number
TWI252506B
TWI252506B TW093112543A TW93112543A TWI252506B TW I252506 B TWI252506 B TW I252506B TW 093112543 A TW093112543 A TW 093112543A TW 93112543 A TW93112543 A TW 93112543A TW I252506 B TWI252506 B TW I252506B
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Taiwan
Prior art keywords
particles
slurry
cmp
composite
resin
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TW093112543A
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Chinese (zh)
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TW200509184A (en
Inventor
Gaku Minamihaba
Yukiteru Matsui
Hiroyuki Yano
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Toshiba 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

There is disclosed a CMP slurry comprising composite type particles composed of a resin component and an inorganic component, which are complexed with each other, and resin particles, the CMP slurry having a viscosity of less than 10 mPas.

Description

1252506 九、發明說明： 相關申請案交叉參考 本申請案係以先前於2003年5月14日提出之日本特開 2003-136014號公報揭示之申請案為基礎，茲主張優先權， 並聲請其利益。該案之全部内容可經由參照方式引用於本 案。 【發明所屬之技術領域】 本發明係關於使用於CMP(Chemical Meehanieal Polishing;化學機械研磨法）之漿液、使用該漿液之研磨方 法及半導體裝置之製造方法。 【先前技#f】 對新一代之高性能LSI而言，元件之高積體化是必須條 件’利用CMP形成之金屬㈣配線之設計法則已逐漸採行 配線寬0.07〜3 0 μηι，膜厚1〇〇 nm之嚴格設計。 欲形成膜厚1〇〇 nm之金屬鑲嵌配線時，在以往之 中，研磨中⑯研磨布游離之研磨粒子會變成游離粒子而被 擠入被研磨面，結果會產生約8〇μιη之蓬部。此日寺，應該被 埋入溝内之配線材料（Cu、Α卜冒等）幾乎大部分會被除去。 產生過剩之窪部時，配線電阻會升高，故半導體裝置會降 低。又，在動作中也有斷線之虞，在可靠性方面也令人擔 憂。因此，窪部被要求需抑制在20 nm以下。 以往，認為減少研磨中之游離粒子可應付此種要求，檢 时採用使用游離粒子少之固定低粒型之墊（例如⑽公 司衣固疋砥粒型墊）之方法。使用此種墊時，雖可將窪部抑 92915.doc 1252506 制在20 nm以下，但卻留下加功能率、價格、加工面品質及 穩定性等問題。 另外，也有人提議採行提高研磨粒子與研磨墊之相互作 用之方法例如，採用使用作為研磨粒子之複合型粒子與 界面活性劑及有機酸等有機化合物之漿液，但因研磨力^ 足，故無實用性。 【發明内容】 本發明之一觀點之CMP用漿液係由包含複合化之樹脂成 分與無機成分之複合型粒子及樹脂粒子所紅成，且m攸之 黏度低於10 mPas者。 本發明之一觀點之研磨方法係包含使具有被研磨面之半 導體基板一面旋轉一面頂接於貼附在轉盤上之研磨布之工 序、及將CMP用漿液滴在前述研磨布上而研磨前述被研磨面 之工序；該CMP用漿液之黏度低於1〇 mPas，且由包含複合 化之樹脂成分與無機成分之複合型粒子及樹脂粒子所組成 者。 本發明之一觀點之半導體裝置之製造方法係包含在半導 體基板上形成絕緣膜之工序、在前述絕緣膜形成凹部之工 序、將導電性材料沉積於前述凹部之内部及前述絕緣膜上， 以形成具有導電性之層者、及使用CMP用漿液之CMP除去沉 積於前述絕緣膜上之前述導電性材料而露出前述絕緣膜之 表面，藉以將前述導電性材料留置於前述凹部之工序，·該 CMP用漿液之黏度低於丨〇 mPas，且由包含複合化之樹脂成 分與無機成分之複合型粒子及樹脂粒子所組成者。 929l5.doc 1252506 【實施方式】 以下，說明本發明之實施形態。 本發明人等為了將供應至研磨布上之漿液有效應用於被 研磨面，以便一面降低窪部及侵蝕，發現一面施行研磨， 使用複合型粒子與樹脂粒子之粒子混合物作為研磨粒子， 且將黏度規定於1 〇 mpas以下相當有效。 圖1係複合型粒子及樹脂粒子之模式圖。複合型粒子 係由作為树知成分11之聚合物粒子、與複合化於此聚合物 粒子之無機成分12所構成。所謂複合化，係指化學性的或 非化學性的鍵合之意。無機成分12例如可作為矽化合物部 或金屬化合物部。無機成分12如圖所示，不僅鍵合於樹脂 成^ 11之表面，也可被取入於内部。另一方面，樹脂粒子 b敢好表面具有例如C〇〇H等官能團。 作為複合型粒子10,例如可使用美國專利us 6,454,819 號公報所記載之粒子’一般可利用以下之方法合成。首先， 使石夕烧偶合料鍵合於作為樹脂成分u之二乙烯基苯聚合 物粒子等’於此使特定之钱醇鹽、膠f狀二氧化石夕起反 應。如此’即可在聚合物粒子之内部及表面形成作為無機 成分U之聚秒氧烧構造等構成之魏合物部等。碎化合物 部等也可不使用钱偶合劑等而形成。無機成分最好經由 石夕烧偶合劑等，或直接鍵合於聚合物粒子。另外，使用銘、 鈦或錯等化合物料無機成分12，也可獲得同樣構成之複 合型粒子10。 以下 詳細說明作為複合型粒 子1〇之樹脂成分11之聚合 92915.doc 1252506 物粒子。 聚合物粒子係由使各種單體聚合所得之聚合物組成之粒 子。作為單體’可使用苯乙烯、α·甲基苯乙烯、鹵化苯乙 烯及二乙烯基苯等不飽和芳香族化合物類、錯酸乙稀酯、 丙酸乙烯酯等不飽和酯、及丙烯腈等不飽和腈類等。另外， 也可使用丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲 基丙烯酸乙酯、丙稀酸2-乙基己酯、甲基丙稀酸2_乙基己 酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、乙二醇二丙烯酸 酯、.乙二醇二甲基丙烯酸酯、縮水甘油丙烯酸酯、縮水甘 油甲基丙烯酸酯、2-羥基丙烯酸乙酯、丙烯基丙烯酸酯及 丙烯基甲基丙烯酸酯等丙烯酸酯類或甲基丙烯酸酯類。 又，也可使用丁二烯、異戊二烯、丙烯酸、甲基丙烯酸、 丙烯醯胺、甲基丙烯醯胺、正羥甲基丙烯醯胺及正羥甲基 甲替丙烯醯胺等。此等單體可單獨使用或併用2種以上。 聚合物粒子可利用乳化聚合、懸濁聚合及分散聚合等各 種方法聚合而獲得如上述所示之單體。聚合物粒子之粒徑 可藉控制聚合條件任意加以調整。也可再將塊狀等之聚合 物粉碎成希望之粒徑之聚合物粒子。尤其，要求強度等較 大、耐熱性優異之聚合物粒子時，也可在製造聚合物粒子 之際，併用多官能之單體，將交聯構造導入分子内。交聯 構造也可在聚合物粒子之製造中或聚合物粒子之製造後， 利用化學交聯、電子線交聯等方法導入。 聚合物粒子之形狀雖無特別限定，但最好為較接近球 形。其平均粒徑以球相半徑〇〇3〜1〇〇 μχη較為理想，〇 〇5〜2〇 92915.doc 1252506 μπι更為理想，0.0 5〜1 · 0 μιη最為理想。平均粒徑0.03 μηι以 下時，粒徑太小，難以獲得充分之研磨性能。另一方面， 平均粒徑超過100 μπι時，聚合物粒子之分散性會惡化，保 存安定性有顯著降低之虞。 在所得之聚合物粒子最好導入羥基、環氧基、羧基等官 能團。此時，無需經由矽烷偶合劑等連結用化合物，可直 接使無機成分鍵合於聚合物粒子。併用具有可與導入聚合 物粒子之官能圑起反應之矽烷偶合劑等時，可進一步促進 無機成分與聚合物粒子之鍵合，獲得更優異之複合型粒子。 作為聚合物粒子，另外也可使用聚醯胺、聚酯、聚碳酸 酯及聚烴烯等各種聚合物組成之粒子。在此等聚合物粒子 中，也可與前述同樣地導入官能團，另外，也可將交聯構 造導入粒子内。 如上所述，雖可使用種種聚合物，但從工業上容易取得 之角度而言，尤以聚甲基丙烯酸甲酯（ΡΜΜΑ)及聚苯乙烯 (PST)較為理想。 其次，詳細說明作為無機成分12之矽化合物部及金屬化 合物部。無機成分雖其中至少一部分直接或間接鍵合於聚 合物粒子，但最好採用化學鍵合方式。如此，在研磨時， 較不會發生無機成分由聚合物粒子脫落而殘留於被研磨面 之問題。作為化學鍵合，有離子鍵合及配位鍵合，從更牢 固地鍵合之觀點而言，以共價鍵合較為理想。無機成分12 也可利用氫鍵合、表面電荷鍵合、互纏鍵合、錨定效應鍵 合等非化學鍵合而鍵合於聚合物粒子。 92915.doc -10- 1252506 如圖1所示，為了铋 必要小於作術於樹脂成分11之表面，無機成分有 、作為料粒子之聚合 無機成分之最長徑為 t由#异可求得：若 可均勻地鍵合。,4:子之粒徑之1/4以下程度，即 在H)nm以上。 保研磨力，無機成分之最長徑最好 氧切化合物部係由彻鍵合含有份及二 ^至少—方所構成。又，金屬化合物部可由 鍵合含有份、氧化銘”子部、二氧化鈦粒 D σ粒子部之群中之至少-種所構成。 此種無機成分既可形成於聚合物粒子之内部及其全表 面，也可形成於該等之一部分。石夕氧貌鍵合含有份及甲氧 院鍵合含有份可由單分子所構成，但最好為2分子以上之鍵 構造。鏈構造之情形雖也可為線狀之鏈構造，但3維構 為理想。 無機成分可直接或經由料偶合劑等連結用化合物鍵合 於聚合物粒子。作為連結用化合物，例如有矽烷偶合劑、 鋁系偶合劑、!太系偶合劑、及錘系偶合劑等，尤其以矽烷 偶合劑較為理想。作為矽烷偶合劑，有下列（a)、（…及卜）。 (a)乙烯基三氯矽烷、乙烯基三個[β_甲氧乙氧基]矽烷、 乙浠基二乙氧基矽烷、乙烯基三甲氧基矽烧、丫_曱基丙烯 醯氧丙基三甲氧基矽烷、γ-巯基丙基三甲氧基矽烷、及〜環 氧氯丙基甲氧基石夕烧等。 〇)γ-縮水甘油氧基丙基三曱氧基矽烧、及ρ縮水甘油氧 基丙基曱基乙氧基矽烷等。 92915.doc • 11 - !2525〇6 —(匀正β(氨乙基）_γ-氨丙基三甲氧基矽烷、正β(氨乙基）_ 丫一 虱丙基曱基二甲氧基矽烷、及γ_氨丙基三乙氧基矽烷等。 作為矽烷偶合劑，最好為具有容易與導入聚合物粒子之 官能團起反應之官能團之矽烷偶合劑。例如在表面導入羧 基之聚合物粒子之情形，最好為具有環氧基、氨基之及 (c)之矽烷偶合劑。其中尤其以縮水甘油氧基丙基三甲氧 基矽烷、及正β(氨乙基）-γ_氨丙基三甲氧基矽烷較為理想。 作為鋁系偶合劑，有乙醯環氧基異丙醇鋁等。作為鈦系 偶合劑’有異丙基三異硬脂鈦酸酯、異丙基十三烷苯琉醯 鈦酸酿等。此等各種偶合劑可單獨使用或併用2種以上。 又’也可併用不同種類之偶合劑。 偶合劑之使用量在導入聚合物粒子之官能團為1克分子 時，以0.1〜50克分子較為理想、，〇·5〜3〇克分子更為理想， 1 .〇 20克分子最為理想。偶合劑之使用量低於克分子 時，無機成分無法充分牢固地鍵合於聚合物粒子，在研磨 中’容易脫離聚合物粒子。另一方面，偶合劑之使用量超 過5〇克分子時，偶合劑分子會進行縮合反應而有產生預料 外之聚合物之虞。此時，有可能妨礙無機成分對聚合物粒 子之鍵合。 使偶合劑化學十生地鍵合於聚合物粒子之際，彳利用酸及 鹽等觸媒促進其反應。為促進其反應，也可將反應系統升 溫。 又’也可使用下列通式⑴所示之化合物作為無機成分之 原料： 92915.doc 1252506。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 . The entire contents of this case can be cited in the present document by reference. [Technical Field of the Invention] The present invention relates to a slurry used in CMP (Chemical Meehanieal Polishing), a polishing method using the slurry, and a method of producing a semiconductor device. [Previous technology #f] For a new generation of high-performance LSIs, the high integration of components is a must. 'The metal formed by CMP (four) wiring design method has gradually adopted a wiring width of 0.07~3 0 μηι, film thickness The strict design of 1〇〇nm. When a metal damascene wiring having a film thickness of 1 〇〇nm is to be formed, in the past, the polishing particles which are free from the polishing cloth in the polishing material are formed into free particles and are pushed into the surface to be polished, and as a result, a cloth portion of about 8 μm is produced. . On this day, most of the wiring materials (Cu, sputum, etc.) that should be buried in the trenches will be removed. When an excess of the crotch is generated, the wiring resistance is increased, so that the semiconductor device is lowered. In addition, there are also disconnections during the operation, which is also worrying about reliability. Therefore, the ankle is required to be suppressed below 20 nm. In the past, it has been considered that the reduction of free particles in the grinding can cope with such a requirement, and a method of using a fixed low-particle type pad having a small amount of free particles (for example, (10) a company-made granule type mat) is used. When using this type of pad, the 洼 抑 92915.doc 1252506 can be made below 20 nm, but the function rate, price, quality and stability of the machined surface are left. Further, there has been proposed a method of increasing the interaction between the abrasive particles and the polishing pad. For example, a slurry using a composite particle as an abrasive particle, an organic compound such as a surfactant and an organic acid is used, but the polishing force is sufficient. No practicality. SUMMARY OF THE INVENTION A slurry for CMP according to one aspect of the present invention is obtained by a composite particle containing a composite resin component and an inorganic component and resin particles, and having a viscosity of less than 10 mPas. A polishing method according to one aspect of the present invention includes a step of causing a semiconductor substrate having a surface to be polished to be rotatably attached to a polishing cloth attached to a turntable, and a CMP slurry to be dropped on the polishing cloth to polish the a step of polishing the surface; the CMP slurry has a viscosity of less than 1 μmPas, and is composed of composite particles and resin particles containing a composite resin component and an inorganic component. A method of manufacturing a semiconductor device according to one aspect of the present invention includes a step of forming an insulating film on a semiconductor substrate, a step of forming a recess in the insulating film, depositing a conductive material on the inside of the recess and the insulating film to form a layer having conductivity and a CMP using a slurry for CMP to remove the conductive material deposited on the insulating film to expose the surface of the insulating film, thereby leaving the conductive material in the concave portion. The viscosity of the slurry is less than 丨〇mPas, and is composed of composite particles and resin particles containing a composite resin component and an inorganic component. 929l5.doc 1252506 [Embodiment] Hereinafter, embodiments of the present invention will be described. In order to effectively apply the slurry supplied to the polishing cloth to the surface to be polished so as to reduce the flaw and the erosion, the present inventors have found that one side is subjected to grinding, and a mixture of particles of the composite particles and the resin particles is used as the abrasive particles, and the viscosity is increased. It is quite effective to be stipulated below 1 〇mpas. Fig. 1 is a schematic view showing a composite particle and a resin particle. The composite particles are composed of polymer particles as the component 11 and inorganic components 12 which are combined with the polymer particles. By compositing is meant chemical or non-chemical bonding. The inorganic component 12 can be, for example, a ruthenium compound portion or a metal compound portion. As shown in the figure, the inorganic component 12 is bonded not only to the surface of the resin, but also to the inside. On the other hand, the resin particles b have a surface having a functional group such as C〇〇H. As the composite type particle 10, for example, the particles described in U.S. Patent No. 6,454,819 can be generally synthesized by the following method. First, a sulphur coupling agent is bonded to a divinylbenzene polymer particle or the like as a resin component u. Here, a specific alkoxide or a gelatinous sulphur dioxide is reacted. Thus, a Wei compound portion or the like which is a polysecond oxygen-fired structure or the like which is an inorganic component U can be formed inside and on the surface of the polymer particles. The broken compound portion or the like may be formed without using a money coupling agent or the like. The inorganic component is preferably bonded to the polymer particles via a sulphur coupling agent or the like. Further, the composite particles 10 having the same constitution can be obtained by using the inorganic component 12 of a compound such as ingot, titanium or erroneous. The polymerization of the resin component 11 as a composite type particle is described in detail below. 92915.doc 1252506 Particles. The polymer particles are particles composed of a polymer obtained by polymerizing various monomers. As the monomer', unsaturated aromatic compounds such as styrene, α-methylstyrene, halogenated styrene, and divinylbenzene, unsaturated esters such as ethylene carbonate and vinyl propionate, and acrylonitrile can be used. Such as unsaturated nitriles and the like. In addition, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and lauryl acrylate can also be used. , lauryl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, acryl acrylate and propenyl Acrylates or methacrylates such as methacrylate. Further, butadiene, isoprene, acrylic acid, methacrylic acid, acrylamide, methacrylamide, n-hydroxymethyl acrylamide, or n-hydroxymethyl methacrylamide may also be used. These monomers may be used alone or in combination of two or more. The polymer particles can be polymerized by various methods such as emulsion polymerization, suspension polymerization, and dispersion polymerization to obtain a monomer as described above. The particle size of the polymer particles can be arbitrarily adjusted by controlling the polymerization conditions. Further, the polymer such as a block or the like may be pulverized into polymer particles having a desired particle diameter. In particular, when polymer particles having high strength and the like and excellent heat resistance are required, a crosslinked structure can be introduced into the molecule by using a polyfunctional monomer in the production of the polymer particles. The crosslinked structure may also be introduced by chemical crosslinking or electron beam crosslinking after the production of the polymer particles or after the production of the polymer particles. The shape of the polymer particles is not particularly limited, but is preferably closer to a spherical shape. The average particle diameter is preferably 球3~1〇〇 μχη with a spherical phase radius of 〇5~2〇 92915.doc 1252506 μπι is more ideal, and 0.0 5~1 · 0 μιη is most desirable. When the average particle diameter is 0.03 μηι or less, the particle diameter is too small, and it is difficult to obtain sufficient polishing performance. On the other hand, when the average particle diameter exceeds 100 μm, the dispersibility of the polymer particles is deteriorated, and the stability of the storage is remarkably lowered. It is preferable to introduce a functional group such as a hydroxyl group, an epoxy group or a carboxyl group into the obtained polymer particles. In this case, it is not necessary to directly bond the inorganic component to the polymer particles via a compound for coupling such as a decane coupling agent. When a decane coupling agent which can react with the function of introducing the polymer particles is used, the bonding of the inorganic component and the polymer particles can be further promoted, and a more excellent composite particle can be obtained. As the polymer particles, particles of various polymer compositions such as polyamine, polyester, polycarbonate, and polyalkylene can also be used. In these polymer particles, a functional group may be introduced in the same manner as described above, or a cross-linking structure may be introduced into the particles. As described above, although various polymers can be used, it is preferable to use polymethyl methacrylate (P) and polystyrene (PST) from the viewpoint of industrial availability. Next, the bismuth compound portion and the metal compound portion as the inorganic component 12 will be described in detail. Although at least a part of the inorganic component is directly or indirectly bonded to the polymer particles, it is preferred to employ a chemical bonding method. As described above, at the time of polishing, there is no problem that the inorganic component falls off from the polymer particles and remains on the surface to be polished. As the chemical bonding, there are ionic bonding and coordination bonding, and from the viewpoint of more firmly bonding, covalent bonding is preferred. The inorganic component 12 may be bonded to the polymer particles by non-chemical bonding such as hydrogen bonding, surface charge bonding, intertwining bonding, or anchoring effect bonding. 92915.doc -10- 1252506 As shown in Fig. 1, in order to be less than the surface of the resin component 11, the inorganic component has a longest diameter of the polymerized inorganic component as the material particle: It can be bonded evenly. 4: The particle size is less than 1/4 of the particle size, that is, above H) nm. The polishing strength is preferably the longest diameter of the inorganic component. The oxygen-cut compound portion is composed of a complete bonding component and at least two. Further, the metal compound portion may be composed of at least one of a group of a bonding component, an oxidized "sub-portion, and a titanium dioxide particle D σ particle portion. Such an inorganic component may be formed inside the polymer particle and its entire surface. It may be formed in one of these parts. The Shixia oxygen bonding content and the methoxy group bonding component may be composed of a single molecule, but it is preferably a bond structure of 2 or more molecules. It is a linear chain structure, but a three-dimensional structure is preferable. The inorganic component may be bonded to the polymer particles directly or via a linking compound such as a material coupling agent. Examples of the linking compound include a decane coupling agent and an aluminum coupling agent. It is preferred to use a coupling agent for a typhoon, a hammer coupling agent, etc., and a decane coupling agent is preferred. As a decane coupling agent, the following (a), (... and ib) are available. (a) Vinyl trichlorodecane, vinyl three [β_methoxyethoxy]decane, ethoxylated diethoxy decane, vinyl trimethoxy oxime, 丫_mercapto propylene oxypropyl trimethoxy decane, γ-mercaptopropyltrimethoxy Base decane, and ~epoxychloropropyl methoxy夕夕烧等. 〇) γ-glycidoxypropyl tridecyloxy oxime, and ρ glycidoxypropyl decyl ethoxy decane, etc. 92915.doc • 11 - !2525〇6 —( Neutralize β (aminoethyl) γ-aminopropyltrimethoxy decane, n-β (aminoethyl) 丫 虱 propyl propyl dimethoxy decane, and γ _ aminopropyl triethoxy decane The decane coupling agent is preferably a decane coupling agent having a functional group which is easily reacted with a functional group introduced into the polymer particles. For example, in the case of a polymer particle having a carboxyl group introduced on the surface, it is preferably an epoxy group or an amino group. And (c) a decane coupling agent, particularly preferably glycidoxypropyltrimethoxydecane and n-β(aminoethyl)-γ-aminopropyltrimethoxydecane. As an aluminum coupling agent, There are acetonitrile epoxy aluminum isopropoxide, etc. As a titanium coupling agent, there are isopropyl triisostearyl titanate, isopropyl tridecyl benzoquinone titanate, etc. These various coupling agents can be used. Two or more kinds may be used singly or in combination. Also, different types of coupling agents may be used in combination. The amount of the coupling agent used in the introduction of the polymer When the functional group of the particle is 1 gram, it is preferably 0.1 to 50 gram, and more preferably 〇 5 to 3 Å, and 〇 20 克 is most desirable. When the coupling agent is used in a lower amount than the ketone The inorganic component is not sufficiently firmly bonded to the polymer particles, and is easily detached from the polymer particles during polishing. On the other hand, when the coupling agent is used in an amount exceeding 5 Å, the coupling agent molecule undergoes a condensation reaction to produce At the same time, it is possible to prevent the bonding of the inorganic component to the polymer particles. When the coupling agent is chemically bonded to the polymer particles, the catalyst is promoted by a catalyst such as an acid or a salt. In order to promote the reaction, the reaction system can also be heated. Also, a compound represented by the following formula (1) can be used as a raw material for the inorganic component: 92915.doc 1252506

RnM(〇R，)z—n ⑴ 式中，R為碳數1〜82,有機基，具體上有甲基、乙基、 :丙基、異-丙基、正丁基、·丁基、第三丁基及正戊基 等院基苯基、乙烯基、及環氧丙基等。r，為碳數U之烧 基、碳數2〜6之醯基或碳數6〜9之芳基，具體上有甲基、乙 基、正丙基及異-丙基、乙醯基、丙醯基、丁醯基、戊醯基 :癸醯基、苯基及甲苯基等。RAR，有2個以上存在時，此 等化合物可以相同也可不同。RnM(〇R,)z—n (1) wherein R is a carbon number of 1 to 82, an organic group, specifically methyl, ethyl, propyl, iso-propyl, n-butyl, butyl, A phenyl group, a vinyl group, a glycidyl group or the like such as a third butyl group and a n-pentyl group. r, is a carbon number of the alkyl group, a carbon number of 2 to 6 fluorenyl group or a carbon number of 6 to 9 aryl group, specifically methyl, ethyl, n-propyl and iso-propyl, ethyl fluorenyl, Propyl fluorenyl, butyl fluorenyl, pentamidine: fluorenyl, phenyl and tolyl. When two or more RARs are present, these compounds may be the same or different.

Μ 為 A卜 Si、Ti、v、Cr、Mn、Fe、c〇 Ni、Cu Zn、Μ is A, Si, Ti, v, Cr, Mn, Fe, c〇 Ni, Cu Zn,

Ge、zr、Nb、Mo、Sn、Sb、Ta、w、p^Ce 尤其以ai、Ge, zr, Nb, Mo, Sn, Sb, Ta, w, p^Ce especially in ai,

Si、Ti及Zr較為理想。 又，z為M之原子價，11為〇〜之整數。 在此，京尤含有A卜Si、TiAZr作為歡化合物力口以說明。 作為Μ為Si之化合物，例如有四甲氧基㈣、四乙烯基錢 (TEOS)、四-異-丙氧基石夕烧、四.第三_ 丁氧基石夕烧、甲基三Si, Ti and Zr are preferred. Further, z is the atomic price of M, and 11 is an integer of 〇~. Here, Jingyou contains Abu Si and TiAZr as the Huan compound. As a compound of ruthenium Si, for example, there are tetramethoxy (tetra), tetravinyl (TEOS), tetra-iso-propoxy zephyr, tetra.

曱氧基㈣及甲基三乙氧基料等。利用此等化合物形成 作為無機成分之碎化合物。另外，有乙氧基叙等、 之乙氧基鈦等、之第三丁氧基錯等。利用此 專化5物可形成作為無機成分之甲氧基鍵合含有份、氧 化鋁粒子部、二氧化鈦粒子部或氧化锆粒子部。Alkoxy (tetra) and methyl triethoxy materials. These compounds are used to form a fragmented compound as an inorganic component. Further, there are ethoxylated or the like, ethoxytitanium or the like, a third butoxy group, and the like. By using this specialized material, a methoxy bond-containing fraction, an alumina particle portion, a titania particle portion, or a zirconia particle portion as an inorganic component can be formed.

、上述化合物可單獨使用或併用2種以上。又，也可使用MFurther, the above compounds may be used alone or in combination of two or more. Also, you can use M

為Si、Ah T^Zr之化合物。前述通式⑴中之(z_n#z以上 由於可形成更密緻之石夕氧烧鍵合含有份或甲氧基鍵合 含有份，故較為理想。 92915.doc -13· 1252506 不僅前述通式（1)所示之化合物，也可使用其加水分解物 及部分縮合物之至少-方。通式⑴所示之化合物即使未特 別紅作，也會加水分解或部分縮合，但可依需要預先施行 所需要之比率之加水分解或部分縮合。 此寺化合物以Si〇2、A12〇3、丁丨〇2或2^〇2換算，對聚合物 粒子，重量比以0.001〜100較為理想。此重量比以〇〇〇5〜5〇 更為里心以0.01〜10最為理想。此重量比低於〇·謝時，無 2成分不能充分形成於聚合物粒子之内部及表面，研磨Z 月b有IV低之虞。另一方面，重量比增大至超過時，也無 法期待顯著提高研磨性能。 又’也可使用選擇自膠質狀之二氧化石夕、膝質狀之氧化 銘、膠質狀之二氧化鈦及膠質狀之氧化錯組成之群中之至 少1種作為無機成分之原料。此種膠質狀之成分可利用使平 均粒徑5〜500 nm之微粒子狀之二氧切、氧化銘、二氧化 鈦或氧化錯分散於水等之分散媒體加以調製。微粒子可利 用使粒子在㈣水溶液巾生長之方法或氣相法等所獲得。 此等微粒子也可經由上述之矽氧烷鍵合含有份或甲氧基 鍵合含有份而鍵合於聚合物粒子。或，也可利用導入微： 子之經基等鍵合於聚合物粒子或梦氧㈣合含有份或甲氧 基鍵合含有份而構成各微粒子部。膠f之使用量以si〇” Al2〇3、彻2或Zr〇2換算，對聚合物粒子，重量比以請 較為理想。此重量比以0.01〜5〇更為理想，以〇ι〜ι〇最為理 想。此重量比低於0 · 〇 〇 i時，無機成分難以充分。另一方面， 超過100時，也無法期待顯著提高研磨性能。 92915.doc -14- 1252506 :吏上逑成分反應於聚合物粒子之際’可在以水或醇類 機溶劑為分散媒體之分散㈣中進行。分散媒體 可早獨使用或併用2種以上之混合物。含水之分散媒體之情 形’為了使聚合物粒子穩定而均勻地分散於分散系統，最 好預先將羥基、環氧基及羧基等親水性官能團導入聚人物 粒子。藉此等官能團之導入’可使上述無機成分更容易鍵 合於聚合物粒子。 可作為分散媒體使用之醇類，例如有甲醇、乙醇、1丙 醇、2-丙醇、丨·丁醇、2_ 丁醇、第三·丁醇等低級飽和脂肪 族醇類。醇類可單獨使用或併用2種以上。作為醇類以外之 有機溶劑，例如有甲基乙基甲酮及二甲替甲醯等。此種有 機溶劑也可以特定比率混合水及醇類使用。 在此際之反應中，分散媒體中之聚合物粒子含量以 0.001〜70重量％較為理想。此重量比以〇〇1〜5〇重量％更為理 想，以0.1〜25重量％最為理想。低於〇〇〇1重量％時，難以以 充刀之產1獲4于聚合物粒子。另一方面，超過7〇重量。、時， 聚合物粒子之分散穩定性會降低，可能發生在複合化階段 容易產生凝膠之不利現象。 使無機成分鍵合之反應可利用加熱或添加觸媒予以促 進。加熱時，最好將反應系統之溫度設定於40〜10(rc。作 為觸媒，例如可使用酸、鹽、鋁化合物及錫化合物，因酸 觸媒及鋁觸媒之反應促進效果較大，故特別理想。 又，也可使用利用機理熔化現象之熱接著之複合型粒子 (例如參照美國專利·· US 6,5 76,5 54號公報）。 92915.doc -15« 1252506 可使用上述各種複合型粒子。 另方面’作為樹脂粒子13，{列如可使用日本特開 测韻275號公報所載之樹脂粒子。具體上，樹脂粒子13 可利用兵上述複合型粒子之樹脂成分構成。其形狀最好為 球形。所謂球形，仙錢肖部分之略球形之意，未必需 要為正球形。 树脂粒子最好具有交聯構造，例如可利用交聯性單體與 其他單體共聚合方式加以合成。在共聚合之際，交聯性單 體之比率以5〜80重量％較為理想，以5〜60重量％更為理想， 以7〜60重量％最為理想。低於5重量％時，難以獲得具有充 分硬度之樹脂粒子。另一方面，超過8〇重量％時，硬度雖 較尚，但樹脂粒子有易碎之虞。因具有交聯構造，故可提 高樹脂粒子之硬度及強度。 樹脂粒子最好表面具有作為官能團之親水性基。可藉親 水性基控制樹脂粒子表面之ζ電位之極性，且除了硬度及強 度外，也可提咼帶電防止性、耐熱性及耐變色性等特性。 而且，表面具有親水性基之樹脂粒子與具有極性基團之化 合物之相溶性也優異。 具有親水性基之樹脂粒子可利用將經基、緩基及其鹽、 酸酐基、磺酸基及其鹽、氨基及其鹽等親水性基，以樹脂 粒子每100 g 0.1毫克分子以上，最好以1〜100毫克分子之比 率導入。 為了在漿液中，使親水性基鍵合於樹脂粒子表面，也可 另外摻合具有特定親水性基之界面活性劑。作為界面活性 92915.doc -16- 1252506 劑，可使用正離子系界面活性劑、負離子系界面活性劑、 及非離子系界面活性劑等之任何一種。作為正離子系界面 活性劑，例如有脂肪族氨鹽及脂肪族銨鹽等。作為負離子 系界面活性劑，例如有脂肪皂、烷基羧酸醚鹽等羧酸鹽、 烷基苯磧酸鹽、烷基萘磺酸鹽、心烯烴磺酸鹽等磺酸鹽、 高級醇硫酸酯鹽、烷基醚硫酸鹽、聚氧化乙烯烷基苯基醚 等硫酸酯鹽、及烷基磷酸酯等磷酸酯鹽等。作為非離子系 界面活性劑，例如有聚氧化乙烯烷基醚等醚型、甘油酯之It is a compound of Si, Ah T^Zr. In the above formula (1), it is preferable that z_n#z or more can form a denser component of the oxysulfide bond or a methoxy bond. 92915.doc -13· 1252506 The compound shown in (1) may be at least one of a hydrolyzed product and a partial condensate. The compound represented by the formula (1) may be hydrolyzed or partially condensed even if it is not particularly red, but may be added as needed Hydrolysis or partial condensation of the ratio required for the application. The compound of the temple is preferably converted from Si 〇 2, A12 〇 3, 丨〇 丨〇 2 or 2 〇 2 to the polymer particles, and the weight ratio is preferably 0.001 to 100. The weight ratio is preferably 〜5~5〇, and the center is preferably 0.01~10. When the weight ratio is lower than 〇·谢, no 2 components can not be formed sufficiently inside and on the surface of the polymer particles, grinding Z month b On the other hand, when the weight ratio is increased to exceed the above, it is not expected to significantly improve the polishing performance. Also, it is also possible to use a sulphur dioxide-like, sulphate-like, gelatinous shape selected from a colloidal shape. Of titanium dioxide and colloidal oxidized components At least one kind of raw material is used as an inorganic component. The gelatinous component can be prepared by dispersing a microparticle-shaped dioxo-cut, oxidized, titanium oxide or oxidative dispersion having an average particle diameter of 5 to 500 nm in water or the like. The fine particles can be obtained by a method of growing the particles in a (iv) aqueous solution, a gas phase method, etc. These fine particles can also be bonded to the polymer particles via the above-mentioned azepine-bonding component or a methoxy-bonding component. Alternatively, the microparticles may be formed by bonding the polymer particles or the dream oxygen (tetra) component or the methoxy bond component to the microparticles. In terms of Al2〇3, T2 or Zr〇2, the weight ratio of the polymer particles is preferably. The weight ratio is preferably 0.01 to 5 Torr, and most preferably 〇ι~ι〇. The weight ratio is lower than 0 · 〇〇i, the inorganic component is difficult to be sufficient. On the other hand, when it exceeds 100, it is not expected to significantly improve the polishing performance. 92915.doc -14- 1252506 : When the ruthenium component reacts with the polymer particle, Using water or alcohol solvent The dispersing medium is dispersed in (4). The dispersing medium may be used alone or in combination of two or more kinds. In the case of a water-dispersed medium, in order to stably disperse the polymer particles in the dispersion system, it is preferable to previously introduce a hydroxyl group and a ring. A hydrophilic functional group such as an oxy group or a carboxyl group is introduced into the poly-person particle, whereby the introduction of the functional group can make the inorganic component more easily bonded to the polymer particle. The alcohol which can be used as a dispersion medium, for example, methanol or ethanol, a lower saturated aliphatic alcohol such as a propanol, a 2-propanol, a hydrazine-butanol, a 2-butanol or a third butanol. The alcohols may be used singly or in combination of two or more. There are methyl ethyl ketone and dimethyl methacrylate. This organic solvent can also be used in a mixture of water and alcohol in a specific ratio. In this reaction, the content of the polymer particles in the dispersion medium is preferably 0.001 to 70% by weight. This weight ratio is more preferably 1 to 5 % by weight, more preferably 0.1 to 25% by weight. When it is less than 重量1% by weight, it is difficult to obtain 4 polymer particles by the production of a knife. On the other hand, it is more than 7 inches in weight. In this case, the dispersion stability of the polymer particles is lowered, and an unfavorable phenomenon that the gel is likely to be generated in the compounding stage may occur. The reaction of bonding the inorganic components can be promoted by heating or adding a catalyst. When heating, it is preferred to set the temperature of the reaction system to 40 to 10 (rc. As a catalyst, for example, an acid, a salt, an aluminum compound, and a tin compound can be used, and the reaction promoting effect by the acid catalyst and the aluminum catalyst is large. In particular, it is also possible to use a composite particle which utilizes the heat of the mechanism melting phenomenon (for example, see U.S. Patent No. 6,5,76,5,54). 92915.doc -15« 1252506 In the case of the resin particles 13, the resin particles contained in the Japanese Patent Publication No. 275 can be used. Specifically, the resin particles 13 can be composed of the resin component of the composite particles described above. The shape is preferably spherical. The so-called spherical shape, the spherical shape of the part of the celestial part, does not necessarily need to be a true spherical shape. The resin particles preferably have a crosslinked structure, for example, a crosslinkable monomer can be copolymerized with other monomers. In the case of copolymerization, the ratio of the crosslinkable monomer is preferably from 5 to 80% by weight, more preferably from 5 to 60% by weight, most preferably from 7 to 60% by weight, and most preferably less than 5% by weight. Hard to get On the other hand, when the amount is more than 8% by weight, the hardness is preferable, but the resin particles are brittle. Since the crosslinked structure is provided, the hardness and strength of the resin particles can be improved. It is preferable that the surface has a hydrophilic group as a functional group. The hydrophilicity group can control the polarity of the zeta potential of the surface of the resin particle, and in addition to hardness and strength, properties such as charge prevention, heat resistance, and discoloration resistance can be improved. Further, the resin particles having a hydrophilic group on the surface are also excellent in compatibility with a compound having a polar group. The resin particles having a hydrophilic group can utilize a base group, a slow base group and a salt thereof, an acid anhydride group, a sulfonic acid group and The hydrophilic group such as a salt, an amino group or a salt thereof is introduced in a ratio of 0.1 to 100 molecules per 100 g of the resin particles, preferably in a ratio of 1 to 100 mg. In order to bond the hydrophilic group to the surface of the resin particle in the slurry, It is also possible to additionally blend a surfactant having a specific hydrophilic group. As an interface activity of 92915.doc -16-1252506, a positive ion surfactant or an anion system can be used. Any one of a surfactant, a nonionic surfactant, etc. Examples of the positive ion surfactant include an aliphatic ammonium salt and an aliphatic ammonium salt. Examples of the negative ion surfactant include a fat soap and an alkane. a carboxylic acid salt such as a carboxylate ether salt, a sulfonate such as an alkyl benzoate, an alkylnaphthalene sulfonate or a heart olefin sulfonate, a higher alcohol sulfate salt, an alkyl ether sulfate, or a polyoxyethylene oxide. a sulfate salt such as a phenyl ether or a phosphate salt such as an alkyl phosphate. Examples of the nonionic surfactant include an ether type such as a polyoxyethylene alkyl ether or a glyceride.

聚氧化乙烯醚等醚酯型、聚乙二醇脂肪酸酯、甘油酯及山 梨糖酵野自旨等之醋型等。 本發明之貫施形態之漿液可利用組合上述之複合型粒子 與樹脂粒子使其呈現特定關係，並使其分散於水中之方式 加以調製。具體而言’係以表面呈現同極性方式組合複合 型粒子與樹脂粒子。 σ ζ電位例如可利用雷射多普勒法ζ電位測定:An ether ester type such as a polyoxyethylene ether, a polyethylene glycol fatty acid ester, a glycerin ester, and a vinegar type such as a sorbitan. The slurry of the present invention can be prepared by combining the above-mentioned composite particles with resin particles to have a specific relationship and dispersing them in water. Specifically, the composite particles and the resin particles are combined in such a manner that the surface exhibits the same polarity. The σ ζ potential can be measured, for example, by the laser Doppler method:

(BROOKHAVEN INSTRUMENTS 公司製、商品名「Zeta piut(BROOKHAVEN INSTRUMENTS company, product name "Zeta piut

^以測定。在ς電位測定之際，需事錢無機成分分散1^ 等之中’以調製特定ρΗ之分散體。利用前述ς電位测定哭〕 定分散體’可獲得任意ΡΗ之無機成分之ζ電位。為測定^ 團之ζ電位，只要使目的之官能團鍵合於樹脂粒子 I^ to determine. In the measurement of the zeta potential, it is necessary to disperse the inorganic component in a dispersion or the like to prepare a dispersion of a specific pH. The zeta potential of the inorganic component of any ruthenium can be obtained by measuring the above-mentioned zeta potential to determine the dispersion. In order to determine the zeta potential of the group, the functional group of the target is bonded to the resin particle I.

使其分散於水料，以料特定ΡΗ之溶液而同_定^可 设合型粒子之極性依存於無機成分H氧 電位在pH 1.4時，為零（等電點、，扣 平 石之 气μ )超過ΡΗ1.4時，成為負值， 乳化銘以電位在ΡΗ 7時，為零，ρΗ7以下時，成為⑻ 929i5.doc -17- 1252506 另-方面，樹脂粒子之⑻立由存在於表面<官能團加以決 定。例如缓基（C〇〇H)之情形，等電點不存在，在全PH區域 (〇·5〜14)中’ ζ電位均為負值。氨基（腿2)之㉘位在全师 域中，均為正值。 或者，複合型粒子及樹脂粒子中之一方為等電點也益 妨了謂料點，係指前述ζ電位測定器測定之ζ電位在〇±5mV 之乾圍而言。以ζ電位為。之阳為基準’即使在阳±1之範圍 ♦子表面之电位也會不穩定。因此，此種範圍也盥等 電位同樣地加以處理。例如，具有石黃酸基⑽H)之聚苯乙 = + %¾位在PH 2附近幾乎為〇。# ’複合型粒子與樹 曰粒子可、，且^成表面不構成反極性*加以使用。 在3有互相相反極性之複合型粒子與樹脂粒子之粒子混 合物作為研磨粒子之漿液中，粒子會強烈地電性相吸而發 生政聚’故漿液黏度會顯著提高至1〇mpas以上。如此高黏 度之聚液無法滴在研磨布上而施行被研磨®MMP。現在 使用之水液供應系統屬於依賴系之液體循環型，使用高黏 ，之漿液時’會發生衆液阻塞，且高黏度之聚液之保管安 定I·生也不良’容易沉澱而難以再分散。 人為將水液黏度限制於10mpas以下，需使用相同極性之複 :型=子及樹脂粒子。複合型粒子及樹脂粒子之一方為等 ^也將漿液黏度限制於10 mPas以下。 不管採用任人—絲Λ人 ^ 〇 種、、且5，樹脂粒子之粒徑也最好大於聚 ϋ + ^成分之最長徑。具體而言，樹脂粒子之粒 徑最好為無機成分之最長徑之2倍以上。如前所述，在複合 92915.doc -18 - 1252506 型粒子中，無機成分最好為樹脂粒子之ι/4以下靜，且複 合型粒子之粒徑最好為樹脂粒子之粒徑之2倍 樹脂粒子之粒徑最好至少大於盔 …、祙成分，以便在複合型粒 】 應力而變形、被破壞時，樹脂粒子可成為複合 支粒子之樹脂成分之替代粒子。考慮到此等因素時，樹脂 粒子之粒徑最好為複合型粒子之無機成分之2倍以上。但， 為確保研磨力，無機成分之最長徑最好為iGnm以上，考慮 到與研磨塾之相互作用時，樹脂粒子之粒徑以止於则㈣Disperse it in the water, and the polarity of the specific particles can be determined by the polarity of the specific particles. The oxygen content of the inorganic component H is zero at the pH 1.4 (the isoelectric point, the gas of the flat stone) When it exceeds ΡΗ1.4, it becomes a negative value, and the emulsification is based on the potential at ΡΗ7, which is zero, and when ρΗ7 or less, it becomes (8) 929i5.doc -17-1252506. Another aspect is that the resin particle (8) is present on the surface <; functional groups to decide. For example, in the case of a slow base (C〇〇H), the isoelectric point does not exist, and the ζ potential is negative in the full PH region (〇·5~14). The 28th position of the amino group (leg 2) is in the entire division and is positive. Alternatively, one of the composite particles and the resin particles may be an isoelectric point, and the zeta potential measured by the zeta potential measuring device is a dry circumference of 〇 ± 5 mV. Take the zeta potential as. The yang is the benchmark' even in the range of yang ±1 ♦ The potential of the subsurface is unstable. Therefore, this range is also treated in the same manner as the equal potential. For example, a polyphenylene group having a rhein acid group (10)H) = + %3⁄4 position is almost ruthenium near PH 2 . # ‘Complex particles and trees 曰 particles can be used, and the surface is not used to form a reverse polarity*. In the slurry in which the particles of the composite particles and the resin particles having opposite polarities are used as the abrasive particles, the particles are strongly electrically attracted to each other, and the viscosity of the slurry is remarkably increased to 1 mpas or more. Such a high-viscosity liquid cannot be dripped onto the abrasive cloth to perform the Grinding® MMP. The water supply system currently used belongs to the liquid circulation type of the dependent system. When the slurry is highly viscous, the liquid clogging will occur, and the storage of the high viscosity liquid will be stable and stable. It is easy to precipitate and difficult to redisperse. . Artificially limiting the viscosity of the water to below 10 mpas requires the use of the same polarity: type = sub- and resin particles. One of the composite particles and the resin particles is equal to ^ The slurry viscosity is also limited to 10 mPas or less. Regardless of the use of any one of the silkworms, and the particle size of the resin particles is preferably larger than the longest diameter of the poly(+) component. Specifically, the particle diameter of the resin particles is preferably twice or more the longest diameter of the inorganic component. As described above, in the composite 92915.doc -18 - 1252506 type particle, the inorganic component is preferably at least 1/8 of the resin particle, and the particle size of the composite particle is preferably twice the particle diameter of the resin particle. The particle diameter of the resin particles is preferably at least larger than that of the ruthenium and ruthenium components, so that the resin particles can be a substitute for the resin component of the composite support particles when the composite granules are deformed and destroyed by stress. In consideration of such factors, the particle diameter of the resin particles is preferably twice or more the inorganic component of the composite particles. However, in order to ensure the grinding force, the longest diameter of the inorganic component is preferably iGnm or more, and in consideration of the interaction with the polishing crucible, the particle diameter of the resin particle is stopped (4).

程度特別理想。 為確保更高之研磨速度，複合型粒子之平均粒子徑山與 樹脂粒子之平均粒子徑d2之粒徑比（di/d2)最好在2以上。# 制粒徑比，可獲得希望之研磨速度H確保混合粒子 之效果，將粒徑比之上限限制於10程度。對複合型粒子， 樹脂粒子太小之情形，係因為接近於添加體積小的界面活 性劑之狀態之故。 樹脂粒子之平均粒子徑以0 05〜i μη1較為理想。低於0 05 pm 時，難以獲得球體。另一方面，超過丨μη1時，如上所述， 粒徑比（di/d2)設定在2以上之際之複合型粒子之平均粒子 徑會超過2 μιη。此時，因粒子表面面積之降低，而有研磨 力不足之虞。樹脂粒子之平均粒子徑以〇1〜〇·5 pm最為理 想，以0·1〜0.3 |1111最為理想。複合型粒子、樹脂粒子之平均 粒子徑可由ΤΕΜ(透光型電子顯微鏡）觀察獲得。 又’複合型粒子與樹脂粒子之粒子混合物中之比率最好 在10重量％以上9〇重量％以下之範圍内。使用以此種比率含 92915.doc -19- I252506 有樹脂粒子之粒子混合物時，可獲得特別高之研磨速度。 例如若為w膜，則可獲得100nm/min以上之高研磨速度。 複D型粒子與樹脂粒子之粒子混合物總粒子濃度在漿液 :以0_1重量。/。以上40重量％以下較為理想。不足〇1重量% =，難以獲得充分之研磨效果。另一方面，超過4〇重量％ 時，有粒子凝聚之虞。總粒子濃度在漿液中以0·5重量％以 上30重量％以下更為理想。 如必要時，可添加氧化劑、ΡΗ調整劑等各種添加劑，以調 製本發明之實施形態之漿液。 在本發明之實施形態之漿液中，因含有複合型粒子與樹 脂粒子之粒子混合物作為研磨粒子，故此等粒子在研磨中 έ在研磨布上形成最密填充構造。因此，可產生適切之堵 ^，將粒子固定於研磨布表面，以降低游離粒子。其結果， 可一面抑制窪部，一面以充分高之研磨速度施行研磨。且 口 ？夂合型粒子及樹脂粒子之表面為同極性或—方處於等電 點’故可充分降低漿液之黏度。 複合型粒子之無機成分即使受到研磨應力，也可牢固地 鍵合而不會脫離作為樹脂成分之聚合物粒子，—方之樹脂 成分可能受到研磨應力而變形或被破壞。因此，在研磨中， 有研磨力之無機成分會鍵合於被破壞之樹脂成分之表面而 成為小徑化之複合型粒子。此種小徑化之複合型粒子可均 勻地與樹脂粒子混合。 又，樹脂粒子為疏水性，研磨布表面也為疏水性。因此， 可一面捲入小徑化之複合型粒子，一面被吸著於研磨布表 92915.doc 1252506 面。其結果，可降低游離粒子而施行研磨。 本發明之實施形態之複合型粒子之樹脂成分與無機成分 均破使用於樹脂粒子以作為個別之成分時，無法獲得上述 ^效果。在此情形，樹脂粒子與無機成分會被埋入樹脂成 之間隙而使粒子被固定化。由於有研磨力之無機成分存 在於表面不充分，故不能進行研磨。 又，將複合型粒子置換成同等粒徑之無機粒子時，有研 磨力之热機成分對樹脂粒子而言，會顯得過大。施 緻之研磨無機成分之粒徑被要求需在1〇〇 nm以下 <，為充分 抑制，最好在50 nm以下。含有與複合型粒子同尊之無機粒 子日守，難以抑制窪部之形成，無法達成目的。 使用本發明之實施形態之漿液時，可全部解決加工能 率、價格、加工面品質、及穩定性等以往之固定砥粒型^ 之課題。 又，適切地選擇保持半導體基板之頂環時，可將研磨粒 子更有效固定於研磨布，進一步提高本發明之實施形態之 漿液之效果。 " 圖2A及2B係表示可使用之頂環之一例之概略構造之剖 面圖。 圖2A所示之頂環67係由設於空氣供應管64之框體〇、保 持環61、夾定板65及氣囊66所構成。保持於此種構造之頂 裱67之半導體基板60之被研磨面實質上係與保持環“成同 一面。也可以使被研磨面位於保持環61之端面上方〇·2卬瓜 程度方式保持著半導體基板60。 92915.doc -21 · 1252506 因此’保持環61會以與半導體基板60相同之壓力被推向 研磨布62。有時，保持環6丨會以超過半導體基板6〇以上之 壓力被推向研磨布62。被供應至研磨布62之漿液（未圖示） 首先’被保持環61壓入研磨布62，而將研磨粒子固定，然 後’漿液被供應至半導體基板6〇之被研磨面，在降低游離 粒子之狀態下施行研磨。 對此’使用如圖2B所示之頂環68時，則在被研磨面之研 磨别不此將研磨粒子固定於研磨布6 2。即，由於經由襯 墊膜69而被保持於頂環68之半導體基板6〇之被研磨面會突 出於保持環61之端面，故被供應至研磨布62上之漿液（未圖 示）會直接被供應至半導體基板6〇之被研磨面。因此，研磨 粒子會被半導體基板6〇固定於研磨布62,而可同時施行研 磨粒子之固定與研磨。 本發明之實施形態之漿液因含有複合型粒子與樹脂粒 子，故在同時施行研磨粒子之固定與研磨之情形，也可降 低游離粒子。但，為更進一步提高粒子之固定固定效果， 與圖2A所示之頂環67組合使用尤其理想。 (實施形態1) 首先，將甲基丙烯酸甲酯94份（以下，「份」指的是「重 量份」）、甲基丙烯酸1份、羥甲基丙烯酸甲酯5份、月桂基 &酸知:0.03份、過硫酸銨〇·6份及離子交換水4〇〇份收容於容 量2公升之燒瓶中。將此混合物在含氮氣之環境氣體下，一 面攪拌，一面升溫至70。〇使其聚合6小時。藉此獲得含有表 面具有羧基之平均粒子徑200 nmipMMA粒子2〇重量％之 929l5.doc -22- 1252506 樹脂粒子之原液。 另一方面，複合型粒子係利用使作為無機成分之二氧化 矽鍵合於作為樹脂成分之PMMA粒子中所調製。作為PMMA 粒子，係使用前述方法所合成之粒子。二氧化叾夕粒子之粒 子徑為1 5 nm，藉改變PMMA粒子之平均粒子徑，而使複合 型粒子之平均粒子徑（d〇發生變化。具體上，準備100 nm、 200 nm、300 nm、400 nm及1 000 nm五種平均粒子徑之複合 型粒子。 在複合化之際，首先，將含PMMA粒子10重量％之水分散 體100份收容於容量2公升之燒瓶中，並添加甲基三甲氧基 矽烷1份。將此混合物以40°C攪拌2小時，然後，添加硝酸 以便將pH調整至2，而獲得樹脂成分之水分散體。又，使膠 態二氧化石夕（曰產化學株式會社製、商品名「snowtexO」） 以10重量％之濃度分散於水中，利用氫氧化鈣將pH調整至 8，而獲得無機成分之水分散體。其後，將無機成分之水分 散體50份在2小時中徐徐地添加於樹脂成分之水分散體100 份中加以混合，再攪拌2小時，而獲得含有作為樹脂成分之 PMMA粒子中附著二氧化矽粒子之預備粒子之水分散體。 接著，在此水分散體中添加乙烯基三乙氧基矽烷2份，攪拌 1小時後，添加TEOS 1份而升溫至60°C，然後，繼續攪拌3 小時，經冷卻而獲得以10重量％濃度含有複合型粒子之複 合型粒子之原液。 將如此所得之複合型粒子之原液與前述樹脂粒子之原液 組合而獲得5種（0.5、1、1.5、2及5)之粒徑比（複合型粒子dj 92915.doc -23- 1252506 樹脂粒子d〗）之粒子混合物 使用複合型粒子與樹脂粒子之粒子混合物作為研磨粒 子’以以下之處方調製本發明之實施形態之漿液。 首先’混合前述樹脂粒子之原液與複合型粒子之原液， 以水稀釋後，再混合作為氧化劑之硝酸鐵5重量％及作為、容 劑之純水90重量％而加以調製，俾以5重量％之濃度含有: 磨粒子。由於含有硝酸鐵，故所得之漿液之仲為2.5程度， 處於酸性區域。另外，藉改變2種原液之配合比率而改^樹 脂粒子與複合型粒子之比率，以調製多數漿液。 使用如此所準備之錢漿液，利用以下之方法施行 W-CMP，調查W研磨速度。 圖3A及3B係表示W-CMP之製程剖面圖。 首先，如圖3A所示，在半導體基板2〇上以3〇〇nm膜厚沉 積絕緣膜21，形成孔2取1μπ4Β外，在其全面“ 之TiN膜23沉積200 nm之w膜24。 利用CMP除去蘭膜23及_24之不要部分，而如圖邛 所示露出絕緣膜21之表面。 _ 24之研磨係使用iC1嶋(羅德尼塔公司幻作為研磨 布’利用上述漿液以下列方式研磨。即，如圖4所示，一面 以100 rPm使貼附研磨布31之轉盤3〇旋轉，一面以3⑻gf/cm2 之研磨負载頂接保持半導體基板32之頂環％。頂環^之轉 數為102 rpm，由聚液供應噴嘴35以2⑼ee/min之流量將聚 液37供應至研磨布3卜又，在圖4中_併顯示水供應喷嘴Μ 及打磨機3 6。 92915.doc -24- !2525〇6 圖5之曲線係表示|膜24之研磨速度與漿液中之粒子混 合物之樹脂粒子之比率之關係。在圖5之曲線中，—:: c、d及⑽分別表示粒子混合物之粒徑比（心）為υ、1、 15、2及5之漿液之結果。 士如圖5之曲線所示’分別單獨使用複合型粒子或樹脂粒子 扦’ w研磨速度在10nm/min以下。對此，在混合使用複合 型粒子與樹脂粒子之漿液之情形，不管任何—種粒徑比， W研磨速度均呈現上升之傾向。此係由於複合型粒子與樹The degree is particularly good. In order to secure a higher polishing rate, the particle diameter ratio (di/d2) of the average particle diameter of the composite particles to the average particle diameter d2 of the resin particles is preferably 2 or more. # The particle size ratio is obtained, and the desired polishing rate H can be obtained to ensure the effect of the mixed particles, and the upper limit of the particle diameter ratio is limited to 10 degrees. In the case of the composite particles, the resin particles are too small because they are close to the state in which the interface active agent is added in a small volume. The average particle diameter of the resin particles is preferably 0 05 to i μη1. Below 0 05 pm, it is difficult to obtain a sphere. On the other hand, when 丨μη1 is exceeded, as described above, when the particle diameter ratio (di/d2) is set to 2 or more, the average particle diameter of the composite particles exceeds 2 μm. At this time, there is a shortage of the polishing force due to a decrease in the surface area of the particles. The average particle diameter of the resin particles is most desirable from 〇1 to 〇5 pm, and is most preferably from 0·1 to 0.3 |1111. The average particle diameter of the composite particles and the resin particles can be observed by ΤΕΜ (light transmission electron microscope). Further, the ratio of the particle mixture of the composite particles and the resin particles is preferably in the range of 10% by weight or more and 9% by weight or less. When a mixture of particles containing 92915.doc -19- I252506 resin particles is used in such a ratio, a particularly high polishing speed can be obtained. For example, if it is a w film, a high polishing rate of 100 nm/min or more can be obtained. The total particle concentration of the particle mixture of the complex D-type particles and the resin particles is in the slurry: 0_1 by weight. /. The above 40% by weight or less is preferable. Less than 1% by weight =, it is difficult to obtain a sufficient grinding effect. On the other hand, when it exceeds 4% by weight, there is a tendency for particles to aggregate. The total particle concentration is more preferably 0.5% by weight or more and 30% by weight or less in the slurry. If necessary, various additives such as an oxidizing agent and a cerium adjusting agent may be added to adjust the slurry of the embodiment of the present invention. In the slurry according to the embodiment of the present invention, since the particle mixture containing the composite particles and the resin particles is used as the polishing particles, the particles are formed on the polishing cloth to form the closest packing structure during polishing. Therefore, an appropriate blockage can be generated to fix the particles to the surface of the polishing cloth to reduce free particles. As a result, it is possible to perform polishing at a sufficiently high polishing rate while suppressing the crotch portion. And mouth ? The surface of the chelating particles and the resin particles are of the same polarity or the square is at the isoelectric point, so that the viscosity of the slurry can be sufficiently reduced. Even if the inorganic component of the composite particles is subjected to polishing stress, it can be firmly bonded without desorbing from the polymer particles as the resin component, and the resin component may be deformed or destroyed by the polishing stress. Therefore, in the polishing, the inorganic component having the polishing force is bonded to the surface of the resin component to be broken, and the composite particles having a small diameter are formed. Such a reduced-diameter composite particle can be uniformly mixed with the resin particles. Further, the resin particles are hydrophobic, and the surface of the polishing cloth is also hydrophobic. Therefore, the composite particles having a small diameter can be immersed in the surface of the polishing cloth table 92915.doc 1252506. As a result, the free particles can be reduced and the polishing can be performed. When both the resin component and the inorganic component of the composite particles of the embodiment of the present invention are used as the individual components in the resin particles, the above effects cannot be obtained. In this case, the resin particles and the inorganic component are buried in the gap between the resins to immobilize the particles. Since the inorganic component having the abrasive force is insufficient in the surface, the polishing cannot be performed. Further, when the composite particles are replaced by inorganic particles having the same particle diameter, the heat generating component having a grinding force is excessively large for the resin particles. The particle size of the abrasive inorganic component is required to be below 1 〇〇 nm <, for adequate suppression, preferably below 50 nm. It is difficult to suppress the formation of the crotch and it is impossible to achieve the purpose by containing the inorganic particles of the same type as the composite particles. When the slurry of the embodiment of the present invention is used, the problems of the conventional fixed particle type such as processing energy, price, surface quality, and stability can be solved. Further, when the top ring of the semiconductor substrate is appropriately selected, the abrasive particles can be more effectively fixed to the polishing cloth, and the effect of the slurry of the embodiment of the present invention can be further enhanced. " Figs. 2A and 2B are cross-sectional views showing a schematic configuration of an example of a top ring which can be used. The top ring 67 shown in Fig. 2A is composed of a frame body provided on the air supply pipe 64, a retaining ring 61, a clamping plate 65, and an air bag 66. The surface to be polished of the semiconductor substrate 60 held by the top electrode 67 of such a structure is substantially flush with the retaining ring. The surface to be polished may be held above the end surface of the retaining ring 61. The semiconductor substrate 60. 92915.doc -21 · 1252506 Therefore, the holding ring 61 is pushed toward the polishing cloth 62 at the same pressure as the semiconductor substrate 60. Sometimes, the holding ring 6丨 is pressed at a pressure exceeding 6 〇 of the semiconductor substrate. Pushing on the polishing cloth 62. The slurry (not shown) supplied to the polishing cloth 62 is first pressed into the polishing cloth 62 by the holding ring 61, and the abrasive particles are fixed, and then the slurry is supplied to the semiconductor substrate 6 to be ground. In the case where the free particles are lowered, the polishing is carried out. When the top ring 68 shown in Fig. 2B is used, the polishing particles are fixed to the polishing cloth 62 by grinding on the surface to be polished. The surface to be polished of the semiconductor substrate 6 held by the top ring 68 via the liner film 69 protrudes from the end surface of the holding ring 61, so that the slurry (not shown) supplied to the polishing cloth 62 is directly supplied to Semiconductor substrate 6〇 Therefore, the polishing particles are fixed to the polishing cloth 62 by the semiconductor substrate 6 and the polishing particles can be fixed and polished at the same time. Since the slurry of the embodiment of the present invention contains the composite particles and the resin particles, In the case where the polishing particles are fixed and polished, the free particles can be reduced. However, in order to further improve the fixing and fixing effect of the particles, it is particularly preferable to use them in combination with the top ring 67 shown in Fig. 2A. (Embodiment 1) First, 94 parts of methyl methacrylate (hereinafter, "parts" means "parts by weight"), 1 part of methacrylic acid, 5 parts of methyl methacrylate, lauryl & acid: 0.03 parts, ammonium persulfate 6 parts of 〇 and 4 parts of ion-exchanged water were contained in a 2 liter flask. The mixture was heated to 70 while stirring under a nitrogen-containing ambient gas. Let it be polymerized for 6 hours. Thus, a stock solution of 929l5.doc -22-1252506 resin particles having an average particle diameter of 200 nmipMMA particles having a carboxyl group on the surface was obtained. On the other hand, the composite particles are prepared by bonding ruthenium dioxide as an inorganic component to PMMA particles as a resin component. As the PMMA particles, the particles synthesized by the above methods are used. The particle diameter of the cerium dioxide particles is 15 nm. By changing the average particle diameter of the PMMA particles, the average particle diameter (d〇 of the composite particles changes. Specifically, 100 nm, 200 nm, 300 nm, Composite particles of five average particle diameters at 400 nm and 1 000 nm. At the time of compounding, first, 100 parts of an aqueous dispersion containing 10% by weight of PMMA particles was placed in a 2 liter flask and methyl group was added. 1 part of trimethoxydecane. The mixture was stirred at 40 ° C for 2 hours, and then nitric acid was added to adjust the pH to 2 to obtain an aqueous dispersion of the resin component. Further, the colloidal silica stone was produced. The product name "snowtexO" manufactured by Chemical Co., Ltd. was dispersed in water at a concentration of 10% by weight, and the pH was adjusted to 8 with calcium hydroxide to obtain an aqueous dispersion of an inorganic component. Thereafter, an aqueous dispersion of an inorganic component was obtained. 50 parts were gradually added to 100 parts of the aqueous dispersion of the resin component in 2 hours, and the mixture was further stirred for 2 hours to obtain an aqueous dispersion containing the preliminary particles of the cerium oxide particles attached to the PMMA particles as a resin component.2 parts of vinyltriethoxy decane was added to the aqueous dispersion, and after stirring for 1 hour, 1 part of TEOS was added and the temperature was raised to 60 ° C, and then stirring was continued for 3 hours, and 10% by weight was obtained by cooling. A stock solution of the composite particles containing the composite particles at a concentration. The raw material of the composite particles thus obtained is combined with the raw material of the resin particles to obtain a particle size ratio of five kinds (0.5, 1, 1.5, 2, and 5) (composite type) Particle dj 92915.doc -23- 1252506 Particle mixture of the resin particles d)) A slurry mixture of the composite particles and the resin particles is used as the polishing particles. The slurry of the embodiment of the present invention is prepared in the following manner. First, the resin particles are mixed. The stock solution of the raw liquid and the composite particles is diluted with water, and then mixed with 5% by weight of iron nitrate as an oxidizing agent and 90% by weight of pure water as a solvent, and the cerium is contained at a concentration of 5% by weight: Since the iron nitrate is contained, the obtained slurry is in the acid region at a level of 2.5, and the resin particles and the composite particles are modified by changing the mixing ratio of the two kinds of stock solutions. The ratio is used to prepare a majority of the slurry. Using the thus prepared money slurry, W-CMP was performed by the following method to investigate the W polishing speed. Figs. 3A and 3B are cross-sectional views showing the process of W-CMP. First, as shown in Fig. 3A It is shown that the insulating film 21 is deposited on the semiconductor substrate 2 with a film thickness of 3 Å, and the hole 2 is formed to be 1 μπ 4 ,, and the film 24 of 200 nm is deposited on the entire TiN film 23. The blue film 23 is removed by CMP. The portion of the _24 is not shown, and the surface of the insulating film 21 is exposed as shown in Fig. . The grinding of _ 24 is performed by using the above-mentioned slurry in the following manner using iC1 嶋 (Rodney Tower Corporation as a polishing cloth). That is, as shown in Fig. 4, the turntable 3 贴 to which the polishing cloth 31 is attached is rotated at 100 rPm, and the top ring % of the semiconductor substrate 32 is held by the polishing load of 3 (8) gf/cm 2 . The number of revolutions of the top ring is 102 rpm, and the liquid supply 37 is supplied to the polishing cloth 3 by the liquid supply nozzle 35 at a flow rate of 2 (9) ee/min. In FIG. 4, the water supply nozzle Μ and the sander 3 6 are displayed. . 92915.doc -24- !2525〇6 The graph of Fig. 5 shows the relationship between the polishing rate of the film 24 and the ratio of the resin particles of the particle mixture in the slurry. In the graph of Fig. 5, -:: c, d, and (10) respectively indicate the results of the particle size ratio (heart) of the particle mixture being 浆, 1, 15, 2, and 5. As shown in the graph of Fig. 5, 'the composite particle or the resin particle 扦' is used alone, and the polishing rate is 10 nm/min or less. On the other hand, in the case where a slurry of the composite particles and the resin particles is used in combination, the W polishing rate tends to increase regardless of the particle size ratio. This is due to composite particles and trees

，粒子會在研磨布上形成最密填充構造而產生適切之堵 塞，將粒子固定之故。 在粒徑比2以上，且樹脂粒子之 區域中’可以1〇〇 nm/min以上 尤其’如曲線d、e所示， 比率在10重量％〜9〇重量。/〇之 之高研磨速度研磨w膜。 =次，將粒徑比設定為2，將樹脂粒子之比率固定在ι〇 :里°/〇而艾更樹脂粒子之材料，其他以相同於前述處方調The particles form a densely packed structure on the polishing cloth to create a suitable plug to fix the particles. In the particle diameter ratio of 2 or more, and in the region of the resin particles, 'may be 1 〇〇 nm/min or more, especially as shown by the curves d and e, and the ratio is 10% by weight to 9 〇. /〇The high grinding speed grinds the w film. = times, the particle size ratio is set to 2, and the ratio of the resin particles is fixed to ι〇: °°/〇 and the material of the resin particles is the same as the above prescription

衣°種n利用所得之漿液，以前述相同條件研磨w膜， 乂。周查w膜之研磨速度。將其結果與各襞液之黏度、粒子 此口物之組成及各粒子之ς電位之極性共同地匯總於下列 表1。由於漿液之ΡΗ為2·5，故各粒子之ζ電位之極性係在 PH 2.5之環境下之測定結果。 92915.doc -25- 1252506 * #命im诙&舛淼繆渰·· 0b5t t% 1—^ 00 •<1 σ\ U\ U) K) h—a 二氧化矽 二氧化矽 二氧化矽 乳化在呂 氧化鋁 二氧化矽 二氧化矽 二氧化矽 二氧化矽i 二氧化矽i 無機成分 複合型粒子 1 1 1 + + 1 I 1 1 1 ζ電位 PMMA PMMA PST PST PST PST (交聯） PST $ S 习外η PST PST 樹脂成分i MA PMMA PST PST PST PST PST PST PST PMMA 樹脂材料 樹脂粒子 COOH * 00 〇 U) nh2 COOH COOH COOH COOH COOH COOH 官能團 1 物 物 + 1 1 1 1 1 1 ζ電位 170 1—^ 〇 140 120 不能CMP H-* Lh 170 175 180 150 W研磨速度 (nm/min) H—^ h—^ 1—^ Η—^ 1—^ 1—λ h—^ 1—^ 黏度 92915.doc -26- 1252506 如表1所不’複合型粒子與樹脂粒子之ζ電位均為負值時 (Ν〇1 5 1〇)及均為正值時（Ν〇·7)，漿液之黏度為impas。 同樣情形，樹脂粒子之ζ電位為零時（Ν〇·8、9)之聚液也為 1 mPas之低黏度。使用此等漿液時，110 nm/min以上之高 研磨速度研磨W膜。任何一種情形，其研磨後之窪部均被 液至於10 nm以下。 又更树知粒子表面之官能團時，以及再添加界面活性劑 日守也同樣可獲得高研磨速度。複合型粒子之樹脂成分之 樹脂粒子之材料未必需要相同，不同時也可獲得同樣之結 果又’複合型粒子及樹脂粒子分別組合使用2種以上時， 也可期待馬研磨速度。The resulting slurry was used to grind the w film and the crucible under the same conditions as described above. Weekly check the grinding speed of the w film. The results are collectively summarized in Table 1 below, together with the viscosity of each mash, the composition of the particles, and the polarity of the zeta potential of each particle. Since the enthalpy of the slurry was 2·5, the polarity of the zeta potential of each particle was measured in the environment of pH 2.5. 92915.doc -25- 1252506 * #命im诙&舛淼缪渰·· 0b5t t% 1—^ 00 •<1 σ\ U\ U) K) h—a cerium oxide cerium dioxide dioxide矽Emulsified in Lu-alumina, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, inorganic component, composite particle 1 1 1 + + 1 I 1 1 1 zeta potential PMMA PMMA PST PST PST PST (crosslinking) PST $ S η PST PST Resin Composition i MA PMMA PST PST PST PST PST PST PST PMMA Resin Material Resin Particle COOH * 00 〇U) nh2 COOH COOH COOH COOH COOH COOH Functional Group 1 Matter + 1 1 1 1 1 1 ζ Potential 170 1—^ 〇140 120 Cannot CMP H-* Lh 170 175 180 150 W Grinding speed (nm/min) H—^ h—^ 1—^ Η—^ 1—^ 1—λ h—^ 1—^ Viscosity 92915.doc -26- 1252506 As shown in Table 1, when both the composite particles and the resin particles have negative zeta potentials (Ν〇1 5 1〇) and both are positive values (Ν〇·7), the slurry The viscosity is impas. In the same case, when the zeta potential of the resin particles is zero (Ν〇·8, 9), the poly-liquid is also a low viscosity of 1 mPas. When such a slurry is used, the W film is polished at a high polishing rate of 110 nm/min or more. In either case, the ground crotch is ground to below 10 nm. When the functional group on the surface of the particle is further known, and the surfactant is added, the high polishing rate can also be obtained. The material of the resin particles of the resin component of the composite particles is not necessarily the same, and the same result can be obtained at the same time. When the composite particles and the resin particles are used in combination of two or more kinds, the horse polishing rate can also be expected.

No.l〜1〇之漿液ipH為2·5程度，如此即使在pH較低之情 形，本發明之實施形態之漿液也可充分確保高研磨速度。 反之，在10以上之高？11中，本發明之實施形態之漿液也可 期待發揮同樣之效果。 作為研磨粒子’卓獨含有樹脂粒子或複合型粒子之以往 之漿液只能使用於3〜7程度之窄的pH範圍。此係由於為提高 研磨粒子與研磨墊之相互作用，而添加界面活性劑極有機 化5物所致。在強酸及強驗之區域，此種添加劑會失去活 性而無法獲得效果。 在本發明之實施形態中，由於混合複合型粒子與樹脂粒 子而使用作為研磨粒子，故在研磨粒子與研磨墊之間可獲 得充分之相互作用，因此，在以往不可能之pH廣範圍中也 可使用。 92915.doc -27- 1252506 如表1所示，含有ζ電位為正值之複合型粒子與ζ電位為負 值之樹脂粒子之粒子混合物時（1^〇 6)，漿液之黏度非常高， 為12 mPas。如此高黏度之漿液難以由漿液供應喷嘴37滴在 研磨布31上，無法施行cmp。 (實施形態2) 在Cu之金屬鑲嵌配線形成處理中，施行Cu2nd研磨之 際，除Cu膜以外，也需要將例如TaN膜及Si〇2膜等不同種材 料平坦地研磨。以往，在此種情形下，通常將研磨速度比 約設定為1而施行非選擇性之研磨。但，在有機系絕緣膜之 ί*月幵y，受到硬度及表面疏水性等物性之影響，以前述條件 研磨時，會發生大的侵蝕。 使用本發明之實施形態之漿液，即使將研磨速度比設定 為1以上而施行非選擇性之研磨時，也可低侵蝕地形成以 金屬鑲肷配線，且在研磨後之有機絕緣膜及膜之表面， 幾乎不會發生擦傷。 圖6A〜6C係表示Cu-CMP之工序剖面圖。 首先，如圖6A所示，預先將絕緣膜41沉積於形成有元件 (未圖示）之半導體基板4〇上，以形成接觸部42。在絕緣膜Ο 上沉積作為低介電常數膜43之LKD51〇9(JSR製）2〇〇 nm，並 利用CVD法沉積作為蓋膜44之黑金剛石（AMAT製，以下稱 BD)l〇〇 nm。利用RIE(反應性離子蝕刻法）在低介電常數絕 緣膜43及蓋膜44形成溝45後，在全面上，利用濺射法及電 鍍法沉積TaN 膜 46(20 nm)及Cu 膜 47(500 nm)。 其次，以下列條件利用CMP除去Cu膜47之不要部分，而 92915.doc • 28 - 1252506 如圖6B所示，露出TaN膜46。 漿液·· CMS7303/7304(JSR公司） 流量：250 cc/min 研磨布：IC1000(羅德尼塔公司製） 負載：300 gf/cm2 游星承載齒輪及轉盤之旋轉數均為100 rpm，施行1分鐘 之研磨。在此工序中，因在TaN膜46停止研磨，故不露出疏 水性之蓋膜44。因此，可使用市售品之漿液加以研磨。 其後，利用修整工序，如圖6C所示，除去TaN膜46之不 要部分。此時之CMP使用本發明之實施形態之漿液。 在漿液之調製之際，準備平均粒子徑（1)200 nm之複合型 粒子與平均粒子徑（d2) 100 nm之樹脂粒子之粒子混合物作 為研磨粒子。複合型粒子與樹脂粒子之粒徑比（1/(12)為2。 複合型粒子係包含作為樹脂成分之平均粒子徑1 50 nm之 PMMA粒子、與作為無機成分之準備平均粒子徑25 nm之二 氧化石夕粒子。樹脂粒子係由PMMA所組成，表面據有官能 團之COOH基。複合型粒子及樹脂粒子係利用上述相同之方 法，準備同樣濃度之原液。 混合複合型粒子之原液與樹脂粒子之原液而以純水稀 釋，使複合型粒子之濃度為2.7重量％，樹脂粒子之濃度為 〇.3重量％。再加入作為氧化劑之過氧化氫水0.1重量％、作 為氧化抑制劑之喹啉酸0.8重量％及添加劑等，利用作為pH 調整劑之KOH將pH調整至10。 又，除了將研磨粒子變更成平均粒徑不同之2種膠態二氧 92915.doc -29- 1252506 化矽外，利用前述相同處方調製比較例之漿液。具體上， 使用平均粒徑40 nm之膠態二氧化矽0.6重量％、與平均粒徑 20 nm之膠態二氧化矽2.4重量％之混合物作為研磨粒子。 使用各漿液，以前述相同條件施行2分鐘研磨，並調查Cu 膜47、TaN膜46與蓋膜44之研磨速度。將研磨時間調整為可 將作為蓋膜44之BD研磨50 nm之時間。其結果，使用本發 明之實施形態之漿液時，Cu膜、TaN膜及蓋膜之研磨速度 分別為 100 nm/min、45 nm/min、及 20 nm/min。相對地，使 用比較例之漿液時，Cu膜之研磨速度為70 nm/min、TaN膜 及蓋膜之研磨速度均為60 nm/min。 如此，使用比較例之漿液時，蓋膜44之研磨速度大到 60 nm/min，故會發生侵飯，使其一部分脫落。Cu膜與蓋膜 44之階差呈現Cu膜方面突出之形狀，侵蝕寬為120 nm。由 於蓋膜44係保護絕緣膜43免於在次一工序受到傷害所必 須，故必須極力避免破裂。對此，使用本發明之實施形態 之漿液時，顯示侵蝕寬只有20 nm之低值，蓋膜44無破裂現 象。由於含有有機材料構成之樹脂粒子，故本發明之實施 形態之漿液在與有機膜之間可產生適切之相互作用。 又，研磨後之Cu膜47表面之窪部被抑制於20 nm以下。另 外，研磨後之Cu膜47上及蓋膜44上之1 cm2之擦傷在使用比 較例時，約10000個；相對地，使用本發明之實施形態之漿 液時，則減少至1 00個以下。利用最適當地選定添加成分， 也可更進一步減少擦傷。 (實施形態3) 92915.doc -30- 1252506 本發明之實施形態之漿液也可適用於STI(Shallow trench isolation :淺溝隔離部）之形成。圖7A及7B係表示STI之形 成處理之工序剖面圖。 首先，如圖7A所示，在設有CMP阻擋膜51之半導體基板 5 0形成溝，將絕緣膜52沉積於其上。在此，可使用SiN作為 CMP阻擋膜51，使用例如SOG等塗敷型絕緣膜作為絕緣膜 52 ° 其次，利用使用本發明之實施形態之漿液之CMP除去絕 緣膜52之不要部分而如圖7B所示露出CMP阻擋膜51表面。 漿液係使用平均粒子徑（1)200 nm之複合型粒子與平均粒 子徑（d2) 1 〇〇 nm之樹脂粒子之粒子混合物作為研磨粒子加 以調製。複合型粒子與樹脂粒子之粒徑比（di/d2)為2。複合 型粒子係包含作為樹脂成分之準備平均粒子徑200 nm之 PST粒子、與作為無機成分之平均粒子徑40 nm之二氧化矽 粒子。在合成此種複合型粒子之際，首先，將苯乙烯92份、 甲基丙烯酸4份、羥甲基丙烯酸乙酯4份、月桂基硫酸銨0.1 份、過硫酸銨0.5份及離子交換水400份收容於容量2公升之 燒瓶中。將此混合物在含氮氣之環境氣體下，一面授拌， 一面升溫至70°C使其聚合6小時。藉此獲得以20重量％之濃 度含有具有羧基之PST粒子之樹脂粒子之原液。又，在PST 粒子之合成之際，添加二乙烯基苯（純度：55%)1份作為交 聯劑。形成COOH以外之官能團時，可使用^比σ定環化合物（氨 基）、續酸鹽（續酸基）等。 在複合化之際，首先，將含PST粒子10重量％之水分散體 92915.doc -31 - 1252506 100伤收谷於谷s 2公升之燒瓶中，並添加甲基三甲氧基矽 烧1份。將此混合物以40t；攪拌2小時，然後，添加硝酸以 便將pHa周整至2，而獲得樹脂成分之水分散體。又，使膠態 二氧化矽（日產化學株式會社製、商品名「snowtex0」）以10 重里/〇之/辰度分散於水中，利用氫氧化鈣將調整至8，而 獲得無機成分之水分散體。其後，將無機成分之水分散體 50份在2小時中徐徐地添加於樹脂成分之水分散體1〇〇份中 加以混合，再攪拌2小時，而獲得聚合物粒？中含有附著二 氧化矽粒子之預備粒子之水分散體。接著，在此水分散體 中添加乙稀基三甲氧基矽烷2份，攪拌丨小時後，添加TE〇s i 份而升溫至6(TC，然後，繼續攪拌3小時，經冷卻而獲得以 10重ΐ %濃度含有複合型粒子之複合型粒子之原液。 混合丽述複合型粒子之原液與樹脂粒子之原液而以純水 稀釋，使複合型粒子之濃度為丨8重量％，樹脂粒子之濃度 為2重量％。在此，係使利用粒子沉降法除去複合型粒子之 原液之上層沉清液而使複合型粒子之濃度成為2〇重量％之 濃縮液、與以上述20重量％之濃度含有交聯劑之樹脂粒子 之原液。再利用作為pH調整劑之ΚΟΗ將pH調整至11。 利用所得之漿液，以下列條件研磨絕緣膜52。 漿液流量：300 cc/min 研磨布·· 1C 1000(羅德尼塔公司製） 研磨負載：300 gf/cm2 游生承載齒輪及轉盤之旋轉數均為1 〇〇 rpm，施行3分鐘 之研磨。 92915.doc -32- 1252506 作為CMP阻撞膜51之材料使用之c或训多半具有疏水 性’ ζ電位為等電點。因此s處於容易發生擦傷之環境。 使用本發明之實施形態之漿液時，研磨後之晶圓表面之 擦傷僅有2個’且侵敍寬被抑制於3〇 以下。如此，確認 在對容易發生擦傷之CMP阻擒膜上之絕緣膜施行cMp之際 也有其效果。 如上所述，依據本發明之形態，可提供可降低窪部及侵 餘，亚可以實狀研磨速度研磨被研磨面之裝〉夜。依據本 發明之另一形態，可提供可降低窪部及侵蝕，並可以實用 ^研磨速度研磨被研磨面之方法。依據本發明之另二形 您，可提供具有高可靠性之半導體裝置之製造方法。 依據本發明，可製造具有新世代所要求之設計法則 0.1 μηι以下之配線之高性能•高速之半導體裝置，具有莫 大工業的價值。 、 有鑑於精通此技藝者可輕易地對本發明加以模仿或變 更，獲取附加利益。因此，從廣義而言，本發明之内容不 應僅限定於上述特殊細節及代表性之實施形態。從而，在 不背離其精神或-般發明概念下，如所附中請專利範圍等 闡述之要旨之範圍内，當然可作種種之變更。 【圖式簡單說明】 圖1係以模式表示複合型粒子及樹脂粒子之概略圖。 圖2Α及2Β係頂環之剖面圖。 圖3 Α及3Β係表示本發明之一實施形態之 製造方法之製程剖面圖。 置之 92915.doc -33- 1252506 圖4係表示CMP之狀態之概略圖。。 圖5係表示W膜之研磨速度與漿液中之樹脂粒子之含量 之關係圖。 圖6A〜6C係表示本發明之另一實施形態之半導體裝置之 製造方法之製程剖面圖。 圖7A及7B係表示本發明之另一實施形態之半導體裝置 之製造方法之製程剖面圖。 【主要元件符號說明】 10 複合型粒 11 樹脂成分 12 無機成分 13 樹脂粒子 20 半導體基板 21 沉積絕緣膜 22 23 TiN膜 24 W膜 30 轉盤 31 研磨布 32 半導體基板 33 頂環 34 喷嘴 35 喷嘴 36 打磨機 doc -34- 漿液 半導體基板 絕緣膜 接觸部 低介電常數膜 蓋膜 溝The slurry ipH of No. 1 to 1 is about 2.5, so that even in the case where the pH is low, the slurry of the embodiment of the present invention can sufficiently ensure a high polishing rate. On the contrary, is it higher than 10? In the eleventh embodiment, the slurry of the embodiment of the present invention can be expected to exhibit the same effect. The conventional slurry which contains the resin particles or the composite particles as the abrasive particles can be used only in a narrow pH range of about 3 to 7. This is due to the addition of the surfactant to the organic compound 5 in order to improve the interaction between the abrasive particles and the polishing pad. In areas with strong acidity and strength, such additives lose activity and are ineffective. In the embodiment of the present invention, since the composite particles and the resin particles are mixed and used as the polishing particles, a sufficient interaction can be obtained between the polishing particles and the polishing pad, and therefore, in a wide range of pH which is not possible in the past, be usable. 92915.doc -27- 1252506 As shown in Table 1, when a composite particle containing a positive zeta potential and a particle mixture of a resin particle having a negative zeta potential (1^〇6), the viscosity of the slurry is very high, 12 mPas. It is difficult for the slurry having such a high viscosity to drip onto the polishing cloth 31 by the slurry supply nozzle 37, and the cmp cannot be performed. (Embodiment 2) In the metal damascene wiring forming process of Cu, when Cu2nd polishing is performed, it is necessary to polish a different material such as a TaN film or a Si〇2 film in addition to the Cu film. Conventionally, in such a case, the polishing rate is usually set to about 1 to perform non-selective polishing. However, in the case of the organic insulating film, it is affected by physical properties such as hardness and surface hydrophobicity, and when it is polished under the above conditions, large erosion occurs. When the slurry of the embodiment of the present invention is used to perform non-selective polishing at a polishing rate ratio of 1 or more, metal-inlaid wiring can be formed with low etching, and the organic insulating film and film after polishing can be formed. On the surface, almost no scratches will occur. 6A to 6C are cross-sectional views showing the steps of Cu-CMP. First, as shown in Fig. 6A, an insulating film 41 is previously deposited on a semiconductor substrate 4 on which an element (not shown) is formed to form a contact portion 42. LKD51〇9 (manufactured by JSR) 2 〇〇nm which is a low dielectric constant film 43 is deposited on the insulating film ,, and black diamond (manufactured by AMAT, hereinafter referred to as BD) as a cap film 44 is deposited by CVD. . After the trench 45 is formed in the low dielectric constant insulating film 43 and the cap film 44 by RIE (Reactive Ion Etching), the TaN film 46 (20 nm) and the Cu film 47 are deposited by sputtering and plating. 500 nm). Next, the unnecessary portion of the Cu film 47 is removed by CMP under the following conditions, and 92915.doc • 28 - 1252506 The TaN film 46 is exposed as shown in Fig. 6B. Slurry ·· CMS7303/7304 (JSR) Flow: 250 cc/min Grinding cloth: IC1000 (made by Rodena Co.) Load: 300 gf/cm2 The number of rotations of the star-bearing gear and the turntable are 100 rpm, and the execution is 1 Grinding in minutes. In this step, since the polishing is stopped in the TaN film 46, the water-repellent cover film 44 is not exposed. Therefore, it can be ground using a slurry of a commercial product. Thereafter, an unnecessary portion of the TaN film 46 is removed by a trimming process as shown in Fig. 6C. The CMP at this time uses the slurry of the embodiment of the present invention. At the time of preparation of the slurry, a mixture of particles of a composite particle having an average particle diameter of (1) of 200 nm and a resin particle having an average particle diameter (d2) of 100 nm was prepared as an abrasive particle. The particle diameter ratio of the composite particles to the resin particles (1/(12) is 2. The composite particles include PMMA particles having an average particle diameter of 150 nm as a resin component and a prepared average particle diameter of 25 nm as an inorganic component. The oxidized particles are composed of PMMA, and the surface is composed of a COOH group having a functional group. The composite particles and the resin particles are prepared by the same method as described above, and a stock solution of the same concentration is prepared. The stock solution was diluted with pure water so that the concentration of the composite particles was 2.7% by weight, and the concentration of the resin particles was 0.3% by weight. Further, 0.1% by weight of hydrogen peroxide water as an oxidizing agent was added, and quinoline as an oxidation inhibitor was added. 0.8% by weight of an acid, an additive, etc., and the pH was adjusted to 10 by using KOH as a pH adjuster. In addition to changing the abrasive particles into two kinds of colloidal dioxins having different average particle diameters, 92915.doc -29- 1252506 The slurry of the comparative example was prepared by the same prescription as described above. Specifically, 0.6% by weight of colloidal ceria having an average particle diameter of 40 nm and 2.4 g of colloidal ceria having an average particle diameter of 20 nm were used. A mixture of % was used as the polishing particles. Each slurry was polished for 2 minutes under the same conditions as above, and the polishing rates of the Cu film 47, the TaN film 46, and the cap film 44 were examined. The polishing time was adjusted to be a BD which can be used as the cap film 44. The time of polishing was 50 nm. As a result, when the slurry of the embodiment of the present invention was used, the polishing rates of the Cu film, the TaN film, and the cap film were 100 nm/min, 45 nm/min, and 20 nm/min, respectively. When the slurry of the comparative example was used, the polishing rate of the Cu film was 70 nm/min, and the polishing rate of the TaN film and the cover film was 60 nm/min. Thus, when the slurry of the comparative example was used, the polishing speed of the cover film 44 was large. When it reaches 60 nm/min, it will invade the rice and cause a part of it to fall off. The step difference between the Cu film and the cover film 44 is a prominent shape of the Cu film, and the erosion width is 120 nm. Since the cover film 44 protects the insulating film 43 In the next step, damage is necessary, so that cracking must be avoided as much as possible. For this, when the slurry of the embodiment of the present invention is used, it shows that the erosion width is only 20 nm, and the cover film 44 has no cracking phenomenon. Resin particles The slurry of the embodiment of the present invention can have an appropriate interaction with the organic film. Further, the surface of the surface of the Cu film 47 after polishing is suppressed to 20 nm or less. Further, the Cu film 47 and the cover film 44 after polishing are provided. The abrasion of 1 cm2 is about 10,000 when the comparative example is used. In contrast, when the slurry of the embodiment of the present invention is used, the amount is reduced to 100 or less. By appropriately selecting the added component, the abrasion can be further reduced. (Embodiment 3) 92915.doc -30- 1252506 The slurry according to the embodiment of the present invention can also be applied to the formation of STI (Shallow trench isolation). 7A and 7B are cross-sectional views showing the steps of forming the STI. First, as shown in Fig. 7A, a trench is formed in the semiconductor substrate 50 provided with the CMP barrier film 51, and the insulating film 52 is deposited thereon. Here, SiN may be used as the CMP barrier film 51, and a coating type insulating film such as SOG may be used as the insulating film 52°. Next, the unnecessary portion of the insulating film 52 is removed by CMP using the slurry of the embodiment of the present invention as shown in FIG. 7B. The surface of the CMP barrier film 51 is exposed. The slurry was prepared by using a mixture of particles of an average particle diameter (1) of 200 nm and a particle mixture of resin particles having an average particle diameter (d2) of 1 〇〇 nm as abrasive particles. The particle diameter ratio (di/d2) of the composite particles to the resin particles was 2. The composite particles include PST particles having a preparation particle diameter of 200 nm as a resin component and cerium oxide particles having an average particle diameter of 40 nm as an inorganic component. In the synthesis of such composite particles, first, 92 parts of styrene, 4 parts of methacrylic acid, 4 parts of ethyl hydroxymethacrylate, 0.1 parts of ammonium lauryl sulfate, 0.5 parts of ammonium persulfate, and ion-exchanged water 400. The contents were contained in a 2 liter flask. This mixture was stirred under a nitrogen-containing atmosphere while being heated to 70 ° C to be polymerized for 6 hours. Thereby, a stock solution of resin particles containing PST particles having a carboxyl group at a concentration of 20% by weight was obtained. Further, in the synthesis of PST particles, 1 part of divinylbenzene (purity: 55%) was added as a crosslinking agent. When a functional group other than COOH is formed, a σ-ring-ring compound (amino group), a repeating acid salt (continued acid group), or the like can be used. At the time of compositing, first, an aqueous dispersion containing 10% by weight of PST particles, 92915.doc -31 - 1252506 100, was taken up in a s 2 liter flask, and 1 part of methyltrimethoxy oxime was added. . This mixture was stirred at 40 t for 2 hours, and then nitric acid was added to adjust the pHa to 2 to obtain an aqueous dispersion of the resin component. In addition, colloidal cerium oxide (manufactured by Nissan Chemical Co., Ltd., trade name "snowtex0") was dispersed in water at 10 liters/min/min, and adjusted to 8 with calcium hydroxide to obtain water dispersion of inorganic components. body. Thereafter, 50 parts of the aqueous dispersion of the inorganic component was gradually added to 1 part of the aqueous dispersion of the resin component in 2 hours, and the mixture was further stirred for 2 hours to obtain polymer particles. An aqueous dispersion containing the preliminary particles to which the cerium oxide particles are attached. Next, 2 parts of ethylene trimethoxy decane was added to the aqueous dispersion, and after stirring for a few hours, TE〇si was added to raise the temperature to 6 (TC, and then stirring was continued for 3 hours, and cooling was carried out to obtain 10 weights. ΐ% concentration contains a stock solution of composite particles of composite particles. The stock solution of the composite particles and the resin particles are diluted with pure water to make the concentration of the composite particles 丨8 wt%, and the concentration of the resin particles is In this case, the supernatant liquid of the stock solution of the composite particles is removed by a particle sedimentation method, and the concentration of the composite particles is 2% by weight, and the concentration is 20% by weight. The raw material of the resin particles of the crosslinking agent was adjusted to pH 11 by using hydrazine as a pH adjusting agent. Using the obtained slurry, the insulating film 52 was ground under the following conditions: slurry flow rate: 300 cc / min Grinding cloth · 1 C 1000 (Ro Grinding load: 300 gf/cm2 The number of rotations of the bearing gear and the turntable is 1 〇〇 rpm, and grinding is performed for 3 minutes. 92915.doc -32- 1252506 As the material of the CMP blocking film 51 use c or training is mostly hydrophobic. The zeta potential is an isoelectric point. Therefore, s is in an environment where abrasion is likely to occur. When the slurry of the embodiment of the present invention is used, only 2 of the surface of the wafer after grinding is invaded. The width is suppressed to 3 Å or less. In this way, it is confirmed that the cMp is applied to the insulating film on the CMP barrier film which is liable to be scratched. As described above, according to the aspect of the present invention, it is possible to provide a lower portion and In the case of the invading, the sub-surface polishing speed can be used to polish the surface to be polished. According to another aspect of the present invention, it is possible to provide a method for reducing the crotch portion and erosion, and polishing the surface to be polished at a practical polishing speed. According to the present invention, it is possible to manufacture a high-performance, high-speed semiconductor device having a wiring design with a design rule of 0.1 μm or less required by the new generation. The value of industry. In view of the fact that those skilled in the art can easily imitate or change the invention to obtain additional benefits. Therefore, in a broad sense, this The content of the invention should not be limited to the specific details and representative embodiments described above. Therefore, it is of course possible to carry out various kinds within the scope of the spirit of the invention and the scope of the invention as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a composite particle and a resin particle in a schematic form. Fig. 2 is a cross-sectional view showing a top ring of a Β and a Β 。. Fig. 3 Α and 3Β show an embodiment of the present invention. A cross-sectional view of the manufacturing process. Fig. 4 is a schematic view showing the state of CMP. Fig. 5 is a graph showing the relationship between the polishing rate of the W film and the content of the resin particles in the slurry. 6A to 6C are process cross-sectional views showing a method of manufacturing a semiconductor device according to another embodiment of the present invention. 7A and 7B are process cross-sectional views showing a method of manufacturing a semiconductor device according to another embodiment of the present invention. [Description of main components] 10 composite pellet 11 resin component 12 inorganic component 13 resin particle 20 semiconductor substrate 21 deposited insulating film 22 23 TiN film 24 W film 30 turntable 31 polishing cloth 32 semiconductor substrate 33 top ring 34 nozzle 35 nozzle 36 sanding Machine doc -34- slurry semiconductor substrate insulating film contact part low dielectric constant film cover film groove

TaN膜 Cu膜 半導體基板 CMP阻擋膜 絕緣膜 半導體基板 保持環 研磨布 框體 空氣供應管 夾定板 氣囊 頂環 頂環 襯墊膜 -35-TaN film Cu film Semiconductor substrate CMP barrier film Insulation film Semiconductor substrate Retaining ring Abrasive cloth Frame Air supply tube Clamping plate Airbag Top ring Top ring Liner film -35-

Claims (1)

125^^2543號專利申請案 中文申請專利範圍替換本(94年1〇月） 十、申請專利範圍：Patent application No. 125^^2543 Chinese patent application scope replacement (94 years 1 month) X. Patent application scope: —種CMP用漿液，其係包含：含複合化之 機成分之複合型粒子、及樹脂粒子；且 树脂成分與無 剞述CMP漿液之黏度低於1〇 mPas者。 2. 如請求項1之CMP用製液’其中前述複合型粒 脂粒子係同極性者。 建才对 3·如請求们之⑽用聚液，其中前述複合型粒子及前 脂粒子中之任一係等電點者。 对 4·如W求項1之CMM 3至液，其中前述複合型粒子之平均粒 徑d】與前述樹脂粒子之平均粒徑t之粒徑比率⑷ 在2以上者。 2)n 5·如請求項t液，其中前述樹脂粒子之含量係前 述複合型粒子與前述樹脂粒子之總量之10重量％以上90 重量％以下者。 S東員1之CMP用漿液，其中前述樹脂成分係選擇自聚 甲基丙烯酸甲酯及聚苯乙烯所成群者。 士明求項1之CMP用漿液，其中前述樹脂成分係表面具有 親水性基者。 8·種研磨方法，其係包含使具有被研磨面之半導體基板 頂接於貼附在轉盤上之研磨布之步驟；及 將幻述CMP用漿液滴在前述研磨布上而研磨前述被研 f面=步驟；前述CMP用漿液之黏度低於1〇mPas，且包 含：含複合化之樹脂成分與無機成分之複合型粒子、及 樹脂粒子。 92915-941018.doc 1252506 月长項8之研磨方法，其中前、 人刑叔7 川水，從r之别述複 口 i叔子及前述樹脂粒子係同極性者。 1 〇 ·如睛求項8之研磨方， 1 人 /、中剧述CMP用衆液中之前述複 ί叔子及前述樹脂粒子中之任—係等電點者。 之研磨方法’其中前述CMp用漿液中之前述複 之千均粒徑山與前述樹脂粒子之 粒徑比率（di/d2)係在2以上者。 2之 ::求項8之研磨方法’其中前述cMp用聚液中之前述樹 月曰粒子之含量係前述複合型粒子與前述樹脂粒子之總量 之重量。/〇以上90重量❹/。以下者。 ^求項8之研磨方法’其中前述半導體基板係被保持於 保持環，前述被研磨面係位於前述保持環之上方者。 士。月求項8之研磨方法’其中前述複合型粒子及前述樹脂 粒子係在研磨前述被研磨面之前，被固定於前述研 者。 15· —種半導體裝置之製造方法，其係包含： 在半導體基板上形成絕緣膜之步驟； 在前述絕緣膜形成凹部之步驟，· 將導電性材料沉積於前述凹部之内部及前述絕緣膜 上’以形成具有導電性之層者；及 ^由使用CMP用漿液之CMp除去沉積於前述絕緣膜上 之前述導電性材料而露出前述絕緣膜之表面，將前述導 電性材料留置於前述凹部之步驟；前述CMp用装液之黏 度低於1 0 mPas，且向合·本銪入儿> 〇：^92915-941〇18doc 匕^ ;吕禝合化之樹脂成分與無機成 1252506 16 17 18. 19. 20. 分之複合型粒子、及樹脂粒子。 — 士明求項15之半導體裝置之製造方法，其中前述用 - 漿液中之前述複合型粒子與前述樹脂粒子係同極性者。 ，如請求们5之半導體裝置之製造方法，其中前述⑽用 漿液中之前述複合型粒子及前述樹脂粒子中之任一係等 電點者。 ” 如請求項15之半導體裝置之製造方法，其中前述cMp用 漿液中之複合型粒子之平均粒徑di與前述樹脂粒子之平 均粒徑旬之粒徑比率（A/D係在2以上者。 如請求項15之半導體裝置之製造方法’其中前述cMp用 漿液中之前述樹脂粒子之含量係前述複合型料與前述 樹脂粒子之總量之1〇重量％以上9〇重量％以下者。 如請求項15之半導體裝置之製造方法，其中前述導電性 材料係包含介著TaN膜被沉積之Cii膜者。 O:\92\929I5-941018.doc 3- 1252506 十一、圖式： 第093112543號專利申請案 中文圖式替換本(94年10月）A CMP slurry comprising: composite particles containing a composite component; and resin particles; and a resin component having a viscosity of less than 1 〇 mPas with no CMP slurry described above. 2. The liquid preparation for CMP according to claim 1 wherein the composite type lipid particles are of the same polarity. According to the request (10), a liquid is used, wherein any one of the composite particles and the pre-lipid particles is an isoelectric point. In the case of the CMM 3 to the liquid of the first aspect, the particle diameter ratio (4) of the average particle diameter d of the composite particles to the average particle diameter t of the resin particles is 2 or more. 2) n 5 The liquid of the request item, wherein the content of the resin particles is 10% by weight or more and 90% by weight or less based on the total of the composite particles and the resin particles. The slurry for CMP of S Dongjin 1, wherein the resin component is selected from the group consisting of polymethyl methacrylate and polystyrene. The slurry for CMP according to Item 1, wherein the resin component has a hydrophilic base on its surface. 8. A polishing method comprising the steps of: abutting a semiconductor substrate having a surface to be polished on a polishing cloth attached to a turntable; and grinding the CMP slurry onto the polishing cloth to grind the ground Surface = step; the viscosity of the slurry for CMP is less than 1 〇 mPas, and includes composite particles containing a composite resin component and an inorganic component, and resin particles. 92915-941018.doc 1252506 The grinding method of the term 8 of the month, in which the former and the human being uncle 7 Sichuan water, the other from the r, and the above-mentioned resin particles are the same polarity. 1 〇 · As for the grinding of the item 8, one person /, the middle of the CMP liquid in the above-mentioned nucleus and any of the above-mentioned resin particles. In the polishing method, the particle size ratio (di/d2) of the plurality of thousand-average particle diameter mountains and the resin particles in the slurry for CMp is 2 or more. 2: The polishing method of the item 8 wherein the content of the above-mentioned tree ruthenium particles in the liquid for cMp is the weight of the total amount of the composite particles and the resin particles. /〇 above 90 weight ❹ /. The following. The polishing method of claim 8 wherein the semiconductor substrate is held by a retaining ring, and the surface to be polished is positioned above the retaining ring. Shi. In the polishing method of the ninth aspect, the composite particles and the resin particles are fixed to the above-mentioned researchers before polishing the surface to be polished. A method of manufacturing a semiconductor device, comprising: forming an insulating film on a semiconductor substrate; and forming a concave portion in the insulating film, depositing a conductive material on the inside of the concave portion and the insulating film' And forming a layer having conductivity; and removing the surface of the insulating film by removing the conductive material deposited on the insulating film by CMp using a slurry for CMP, and leaving the conductive material in the concave portion; The viscosity of the above-mentioned liquid for CMp is less than 10 mPas, and the combination of · 铕 铕 & & ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂. Composite particles and resin particles. The method for producing a semiconductor device according to the item 15, wherein the composite particles in the slurry are the same as the resin particles. The method of manufacturing a semiconductor device according to claim 5, wherein the composite particle of the slurry (10) and the isoelectric point of any one of the resin particles are used. The method for producing a semiconductor device according to claim 15, wherein the ratio of the average particle diameter di of the composite particles in the cMp slurry to the average particle diameter of the resin particles is (A/D is 2 or more). The method for producing a semiconductor device according to claim 15 wherein the content of the resin particles in the cMp slurry is 1% by weight or more and 9% by weight or less based on the total amount of the composite material and the resin particles. The method of manufacturing a semiconductor device according to Item 15, wherein the conductive material comprises a Cii film deposited via a TaN film. O:\92\929I5-941018.doc 3- 1252506 XI. Drawing: Patent No. 093112543 Application Chinese pattern replacement (October 94) 6868 92915.doc 62 125250692915.doc 62 1252506 92915.doc 2- 125250692915.doc 2- 1252506 樹脂粒子之比率（重量％) 92915.doc 471252506Resin particle ratio (% by weight) 92915.doc 471252506 46 44 43 41 4046 44 43 41 40 44 43 41 40 42 眷 92915.doc 125250644 43 41 40 42 眷 92915.doc 1252506 5252 圖7 92915.docFigure 7 92915.doc
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