TW200804575A - Metal polishing composition and chemical mechanical polishing method using the same - Google Patents

Metal polishing composition and chemical mechanical polishing method using the same Download PDF

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TW200804575A
TW200804575A TW096114183A TW96114183A TW200804575A TW 200804575 A TW200804575 A TW 200804575A TW 096114183 A TW096114183 A TW 096114183A TW 96114183 A TW96114183 A TW 96114183A TW 200804575 A TW200804575 A TW 200804575A
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honing
acid
metal
composition
group
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TW096114183A
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Chinese (zh)
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Tomoo Kato
Shinichi Sugiyama
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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
    • 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
    • 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
    • C09G1/04—Aqueous dispersions
    • 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
    • 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
    • C09K3/1463—Aqueous liquid suspensions
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

Abstract

The present invention provides a composition for polishing metal that prevents dishing or erosion and has favorable cleaning properties after polishing, and a chemical mechanical polishing method using the composition. The metal polishing composition of the present invention includes: (a) grinding particles of colloidal silica having the surface thereof modified with an aluminate ion or a borate ion; and (b) a heterocyclic aromatic compound having an anionic substituent and three or more nitrogen atoms in the molecule.

Description

200804575 九、發明說明： 【發明所屬之技術領域】 本發明係關於硏磨用組成物，更詳而言，其係關於使用 在製造半導體裝置之配線形成步驟的金屬硏磨用組成物、及 使用它之化學機械硏磨方法。 【先前技術】 在以半導體積體電路（以下適當地簡稱爲「LSI」）所 代表的半導體裝置之開發方面，爲小型化•高速化，近年來 係要求藉由配線的微細化和積層化之高密度化•高積體化 。爲此所需要之技術，一向是採用化學機械硏磨（Chemical Mechanical Polishing，以下適當地簡稱爲「CMP」）等之各 種技術。該CMP係在進行層間絶緣膜等的被加工膜之表面 平坦化、形成插栓（plug)、形成鑲嵌金屬配線等時所必需 之技術，因此，迄今爲止，則使用該技術來施加基板平滑化 或移除在形成配線時的多餘之金屬薄膜（例如，參閱美國發 明專利第4,944,836號說明書）。 CMP之一般方法係在圓形的硏磨平台（platen )上貼附 硏磨墊，然後將硏磨墊表面浸漬硏磨液，並將基板（晶圓） 之表面壓在硏磨墊上，且在由其背面施加特定的壓力（硏磨 壓力）之狀態下，使硏磨平台與基板之兩者相對旋轉，而以 所產生之機械性摩擦將基板表面加以平坦化。 迄今爲止，配線用之金屬係鎢及鋁通用於內連線（ interconnect )結構體。然而，以更進一步的高性能化爲目 的，已開發出使用配線電阻爲低於該等金屬之銅的LSI。用 200804575 於配線該銅之方法係以例如一種揭示於日本發明專利特開 平第2-2 78822號公報之金屬鑲嵌法（damascene )已爲眾人 皆知。另外，也演變成廣泛地採用一種將接觸洞（contact hole )與配線用槽溝同時形成於層間絶緣膜，然後將金屬嵌埋於 該兩者之雙道金屬鑲嵌法（dual damascene)。該銅配線用 之靶材料，已有市售商品級之成份爲五個9( five nine )以 上之高純度銅靶。 然而，近年來，則隨著朝向更加高密度化的配線微細化 而導致需要提高銅配線之導電性或電子特性等，且接著也開 始硏討使用一種經對於高純度銅添加第三成份的銅合金之 方法。同時，要求一種可不致於污染到該等高精細且爲高純 度的材料，能發揮高生產性之高速金屬硏磨方法。關於銅金 屬之硏磨，特別是由於其係屬於軟質之金屬，容易造成僅使 中央部份受到更深的硏磨而產生形似碟盤狀的凹處之現象 (凹陷；dishing )、使複數條配線之金屬面表面形成外形似 碟盤狀的凹部之現象（浸蝕；erosion)，或硏磨傷（刮傷； scratch)。因此，越來越需要高精度之硏磨技術。 並且，最近爲提高生產性，使得製造LSI時的晶圚徑趨 於更大型化。現在是通用直徑爲200毫米以上者，且以300 毫米以上之大小的製造也開始付諸實施。隨著此等之晶圓大 型化，則將容易產生在晶圓中心部與周邊部的硏磨速率差異 。因此，對於在晶圓面內的硏磨均勻性之要求越來越嚴格。 對於銅及銅合金，不採用機械性硏磨方法之化學硏磨方 法，則有一種已揭示於日本發明專利特開昭第49-1 2243 2號 200804575 公報之方法已爲眾人皆知。然而，僅依賴化學性溶解作用的 化學硏磨方法，若與選擇性地將凸部之金屬膜以化學機械方 式實施硏磨的CMP相比較，則由於會造成被削成凹部，亦 即，產生凹陷（dishing)等，以致對於硏磨之平面性尙存在 很大的技術問題。 另一方面，在LSI製造中使用銅配線時，一般則以防止 銅離子對於絶緣材料之擴散爲目的，在配線部與絶緣層之間 設置所謂的「阻障層（barrier layer )」之抗擴散層。阻障 層係由選自 TaN、TaSiN、Ta、TiN、Ti、Nb、W、WN、Co 、Zr、ZrN、Ru和CuTa合金之阻障材料所構成，且以一層 或兩層以上所構成。該等阻障材料，由於其本身即具有導電 性質’爲防止產生浅漏電流寺之誤動作’則必須完全移除絶 緣層上之阻障材料。該移除加工係藉由與金屬配線材料的表 體（bulk)硏磨相同的方法來實施（阻障CMP )。 另外，在銅之表體硏磨，由於特別容易在寬幅之金屬配 線部產生凹陷，爲達成最終的平坦化，則較佳爲能加以調節 在配線部與阻障部所硏磨移除之量。因此，一向是期望著阻 障硏磨用之硏磨液能够具有最適當的銅/阻障金屬之硏磨選 擇性。而且，由於在各層配線層的配線節距或配線密度不相 同，更佳爲能够適當地加以調整硏磨選擇性。 使用於CMP之金屬用硏磨用組成物（金屬用硏磨液） ，一般包含固體硏磨粒（例如，氧化鋁、二氧化矽（silica ))與氧化劑（例如，過氧化氫、過硫酸）。使用此種金屬 用硏磨液的CMP之基本機制，一般認爲係藉由氧化劑來氧 200804575 化金屬表面，然後以硏磨粒移除其氧化皮膜來加以硏磨，例 如已揭示於電化學協會期刊（Journal of Electrochemical Society ) 1991年第138冊第1 1期之第3,460至3,4 64頁中 〇 然而，若使用包含如上所述之固體硏磨粒的金屬用硏磨 液來實施CMP時，則有可能導致會產生刮傷、硏磨面全部 被過度硏磨之現象（薄化；thinning )、硏磨金屬面窪下成 外形似碟盤狀之現象（凹陷）、金屬配線間之絶緣體受到過 度硏磨，再加上複數條配線金屬面窪下成外形似碟盤狀之現 象（浸蝕；erosion)等。並且，在經硏磨後，爲移除殘留於 半導體面的硏磨液所通常實施的洗淨步驟中，因使用含有固 體硏磨粒的硏磨液，其洗淨步驟則將變得更加複雜。並且， 存在著在處理洗淨後的液（廢液）時，必須以沉降法分離出 固體硏磨粒等之成本方面的問題。 解決該等問題之一方法，例如一種藉由組合未含硏磨粒 的硏磨液與乾蝕刻法之金屬表面硏磨方法係已揭示於電化 學協會期刊2000年第147冊第10期之第3,907至3，91 3頁 中。另外，在日本發明專利特開第2001 _ 1270 1 9號公報，則 已揭示一種由過氧化氫/蘋果酸/苯并三唑/聚丙烯酸銨及水 所構成之金屬用硏磨液。若根據此方法時，則半導體基體的 凸部之金屬膜將選擇性地受到CMP，使得金屬膜殘留於凹部 而獲得吾所欲得之導體圖案。其係因爲CMP將以與機械性 遠比傳統的包含固體硏磨粒的硏磨漿（slurry )爲柔軟的硏 磨墊之摩擦而順利進展，使得刮傷之產生已獲得減少。然而 200804575 ，卻有因物理性硏磨力降低，以致有例如不能獲得足夠的硏 磨速率之缺點。 另一方面，包含硏磨粒之硏磨劑，雖然具有能獲得高硏 磨速率之特徵，但是，硏磨液之pH在由中性至酸性時，卻 有因硏磨粒易於凝聚而造成凹陷進行，或造成刮傷之問題。 在由中性至酸性是呈穩定的硏磨粒，在日本發明專利特開第 20 03 - 1 8363 1號公報係已揭示一種使用硼加以表面改質之膠 質二氧化矽（colloidal silica)作爲硏磨粒之硏磨組成物， 在日本發明專利特開第2003- 1 97573號公報係已揭示一種二 氧化矽微粒的表面之一部份或全部係以鋁所被覆的金屬絶 緣膜同時存在之表面硏磨用膠質二氧化矽。該等藉由使用硼 或鋁來加以表面改質所賦予負電荷的硏磨粒係可防止在由 中性至酸性之凝聚。但是，銅等金屬的表面電位在由中性至 酸性領域中係通常帶正電。因此，則將導致由於靜電被吸附 於金屬表面的硏磨粒而產生凹陷或浸鈾，或經硏磨後硏磨粒 將被吸附在金屬表面結果導致洗淨性降低之問題。 【發明內容】 〔所欲解決之技術問題〕 本發明之目的係提供一種經加以抑制凹陷或浸飩，且經 硏磨後的洗淨性爲良好的金屬硏磨用組成物，另外，提供一 種使用該金屬硏磨用組成物之化學機械硏磨方法。 〔解決問題之技術方法〕 有鑑於如上所述之問題，本發明之發明人等經專心硏討 結果發現藉由下列方法能解決問題而達成本發明。 200804575 (1) 一種金屬硏磨用組成物，其特徵爲：包含（a)使用 鋁酸離子或硼酸離子將膠質二氧化矽（colloidal silica)加以表面改質之硏磨粒，及（b)具有陰離 子性取代基且在分子內具有三個以上氮原子之雜芳 香族環（heterocyclic aromatic)化合物。 (2) 如第（1)項所述之金屬硏磨用組成物，其中又包含 (c )在分子內具有三個以上氮原子、且無陰離子性 取代基之雜芳香族環化合物。 (3 ) 如第（1 )項所述之金屬硏磨用組成物，其中該金屬 硏磨用組成物係將如上所述之硏磨粒分散於水溶液 中之硏磨漿。 (4) 如第（1)項所述之金屬硏磨用組成物，其中若該膠 質二氧化矽表面之膠質二氧化矽的表面原子取代率 爲導入鋁原子或硼原子之數目/表面矽原子部位之 數目時，則該取代率爲0.001 %以上、20%以下。 I (5) 如第（1)項所述之金屬硏磨用組成物，其中該膠質 二氧化矽藉由動態光散射法所測得之體積相當直徑 爲3奈米至200奈米。 (6) 如第（1)項所述之金屬硏磨用組成物，其中該金屬 硏磨用組成物之pH爲3至7。 (7) 如第（1)至（6)項中任一項所述之金屬硏磨用組 成物，其中使用該金屬硏磨用組成物實施硏磨時之 被硏磨面是銅或銅合金。 (8) 一種化學機械硏磨方法，其特徵爲：使用包含（a ) -10- 200804575 使用鋁酸鹽離子或硼酸鹽離子將膠質二氧化矽加以 表面改質之硏磨粒，及（b )具有陰離子性取代基、 且在分子內具有三個以上氮原子之雜芳香族環化合 物之金屬硏磨用組成物；且在硏磨壓力爲3 psi( 0.0207 MPa)以下實施硏磨。 (9) 如第（8)項所述之化學機械硏磨方法，其中該金屬 硏磨用組成物又包含（c)在分子內具有三個以上氮 原子、且無陰離子性取代基之雜芳香族環化合物。 ^ ( 1〇) 如第（8)或（9)項所述之化學機械硏磨方法，其 中使用該金屬硏磨用組成物實施硏磨時之被硏磨面 是銅或銅合金。 〔發明之功效〕 若根據本發明，即可提供一種可防止具有負電荷之硏磨 粒對於金屬表面的靜電吸附，抑制凹陷或浸蝕，且經硏磨後 之洗淨性爲良好的金屬硏磨用組成物。 φ 另外，可提供一種使用如上所述的金屬硏磨用組成物之 化學機械硏磨方法。 【實施方式】 〔本發明之最佳實施方式〕 (金屬硏磨用組成物） 本發明之金屬硏磨用組成物，其特徵爲：包含（a)使 用鋁酸鹽離子或硼酸鹽離子將膠質二氧化矽加以表面改質 之硏磨粒，及（b )具有陰離子性取代基、且在分子內具有 三個或以上氮原子之雜芳香族環化合物。 -11- 200804575 另外，必要時也可含有其他化合物。 本發明之金屬硏磨用組成物，通常採取將如上所述之膠 質二氧化矽（硏磨粒）分散於經溶解各成份所構成之水溶液 的硏磨漿之形態。 本發明之金屬硏磨用組成物係適合用作爲在半導體裝 置製造時用於被硏磨物的化學機械硏磨之硏磨用組成物。 另外，本發明之金屬硏磨用組成物之pH較佳爲3至7 ，更佳爲4至7。 若pH爲低於3時，則有可能導致容易凝聚，若pH爲 超過7時，則有可能導致凹陷惡化。 至於用於構成金屬硏磨用組成物之各成份，則將詳加說 明如下，但是各成份係可單獨使用一種、或其兩種以上組合 倂用。 在本發明中，所謂的「金屬硏磨用組成物」（在下文中 ，也稱爲「硏磨用組成物」），除非另有特別加註，其係意 謂不僅是使用於硏磨的組成（濃度）之形態，在使用時則視 需要而加以稀釋後才使用之形態，也統稱爲金屬硏磨用組成 物。濃縮液係在使用於硏磨時，則以水或水溶液等加以稀釋 後使用於硏磨者，且其稀釋倍率係一般爲1至20體積倍。 〈（a )使用鋁酸鹽離子或硼酸鹽離子加以表面改質之膠質 二氧化矽〉 在本發明之硏磨用組成物中，其係包含「（a)使用鋁 酸鹽離子或硼酸鹽離子加以表面改質之膠質二氧化矽」（在 下文則適當地稱爲「特定的膠質二氧化矽」）° -12- 200804575 特定的膠質二氧化矽係在本發明之硏磨用組成物中作 爲硏磨粒而發揮功能者。 在本發明中，所謂的「使用鋁酸鹽離子或硼酸鹽離子加 以表面改質之膠質二氧化矽」係意謂鋁原子或硼原子係存在 於具有配位數爲4的矽原子之部位的膠質二氧化矽表面之狀 態。 例如，也可爲4個氧原子所配位的鋁原子鍵結於該膠質 二氧化矽表面，而形成鋁原子以4配位之狀態下被固定的新 表面之狀態，另外，也可爲存在於表面的矽原子暫時被拉拔 ，而形成與鋁原子調換的新表面之狀態。 · 並且，也可爲4個氧原子所配位的硼原子鍵結於該膠質 二氧化矽表面，而形成硼原子以4配位之狀態下被固定的新 表面之狀態，另外，也可爲存在於表面的矽原子暫時被拉拔 ，而形成與硼原子調換的新表面之狀態。 使用於調製特定的膠質二氧化矽之膠質二氧化矽，更佳 爲在微粒內部並未含鹼金屬等之不純物，且爲經由烷氧基矽 烷之水解所製得之膠質二氧化矽。另外，也可使用由矽酸鹼 性水溶液移除鹼之方法所製造的膠質二氧化矽。但是採取此 方法時，卻有因殘留於微粒內部的鹼金屬將緩慢地析出，以 致影響到硏磨性能之顧慮。從此等觀點來看，則原料更佳爲 以如上所述之經由烷氧基矽烷之水解所製得者。 用作爲原料的膠質二氧化矽之粒徑係根據硏磨粒之使 用目的而適當地加以選擇，但是一般爲約1 〇至200奈米。 -（al)使用鋁酸鹽離子加以表面改質之膠質二氧化矽- -13- 200804575 將如上所述之膠質二氧化矽微粒表面的矽原子取代成 鋁原子，以製造特定的膠質二氧化矽之方法係適合使用例如 一種將鋁酸鈉等之鋁酸化合物添加至膠質二氧化矽的分散 液之方法。該等方法係已詳細揭示於發明專利第3，.463,328 號公報、日本發明專利特開昭第63-123807號公報，其中該 揭示內容係可適用於本發明。 至於其他方法，則有一種將烷氧化鋁添加至膠質二氧化 矽的分散液之方法。 特定的膠質二氧化矽係由於經由4配位的鋁酸鹽離子 與膠質二氧化矽表面的矽烷醇基之反應所形成的鋁矽酸鹽 (alumino silicate)部位將負電荷予以固定，並對微粒賦予 負的大Γ電位（zeta Potential )，而在酸性也具有優越的分 散性。因此，藉由以如上所述之方法所製造之特定的膠質二 氧化矽，重要的是鋁原子應以配位於4個氧原子之狀態存在 〇 此等結構，亦即，在膠質二氧化矽表面產生矽原子與鋁 原子之取代係例如藉由測定硏磨粒的Γ電位即可容易地加 以確認。 若將膠質二氧化矽表面之矽原子取代爲鋁原子之量爲 膠質二氧化矽之「表面原子取代率（導入鋁原子數目/表面 矽原子部位數目）」時，則較佳爲0.00 1 %以上、20%以下， 更佳爲（K01%以上、10%以下，且特佳爲〇·1%以上、5%以下 〇 將膠質二氧化矽表面之矽原子取代爲鋁原子時，對於鋁 -14- *200804575 原子之取代量係藉由控制添加至膠質二氧化矽之分散液的 鋁酸化合物、烷氧化鋁等之添加量（濃度），即可適當地加 以控制。 此時，對於膠質二氧化矽表面的鋁原子之導入量（導入 鋁原子數目/表面矽原子部位數目）係在添加至分散液中的 鋁系化合物之中，從反應後所殘留的未經反應之鋁系化合物 來計算得所消耗的鋁系化合物量，並假定其等係100%參與 反應，然後從藉由膠質二氧化矽直徑所換算之表面積、膠質 ® 二氧化矽之比重2.2、以及每單位表面積的矽烷醇基數（5 至8個/nm2 )，即可加以估計。實際之測定係將所製得之特 定的膠質二氧化矽本身加以元素分析，並假定鋁並不存在於 微粒內部而均勻且薄薄地擴展於表面，然後使用該膠質二氧 化矽之表面積/比重、以及每單位表面積的矽烷醇基數來計 算得。 具體的製法係例如將膠質二氧化矽以1至50重量％之 I 範圍分散於水，並在該分散液加入pH調整劑以將pH調整 成7至1 1，其後則在室溫附近添加鋁酸銨水溶液，並在該溫 度下攪拌1至1 〇小時。其後，以離子交換或超濾法（ ultrafiltration )等移除雜質以製得特定的膠質二氧化矽之方 法。 -（a2)使用硼酸鹽離子加以表面改質之膠質二氧化矽-將如上所述之膠質二氧化矽微粒表面之矽原子取代成 硼原子，以製得特定的膠質二氧化矽之方法，其係包括例如 使用硼酸與矽烷偶合劑將膠質二氧化矽之表面加以改質來 -15- 200804575 製造之方法。該等方法係已詳細揭示於日本發明專利特表第 2003-525 1 9 1號、歐洲發明專利第EP 943648號、歐洲發明 專利第EP 94 1 995號，其中揭示內容係可適用於本發明。 特定的膠質二氧化矽係由於藉由4配位的硼酸鹽離子 與膠質二氧化矽表面的矽烷醇基之反應所形成的部位將負 電荷予以固定，並對微粒賦予負的大Γ電位，而在酸性也具 有優越的分散性。因此，藉由以如上所述之方法所製造之特 定的膠質二氧化矽，重要的是鋁原子應以配位於4個氧原子 A 之狀態存在。 此等結構，亦即，在膠質二氧化矽表面產生矽原子與硼 原子之取代的結構係例如經測定硏磨粒的Γ電位即可容易 地加以確認。 膠質二氧化矽表面之Γ電位係在從PH 3至pH 5時，則 爲0至-1 0 mV，但是經以硼酸鹽離子加以處理，藉此即將降 低爲-10至-20 mV。若在從pH 5至pH 7時，膠質二氧化矽 ^ 表面之Γ電位雖然爲從-10 mV至-2〇 mV，但是經以硼酸鹽 離子加以處理，即可降低爲-20 mV至-40 mV。 將膠質二氧化矽表面之矽原子取代爲硼原子之量，其膠 質二氧化砂之「表面原子取代率（導入硼原子數目/表面矽 原子部位數目）」較佳爲0·001 %以上、20%以下，更佳爲 0.01%以上、10°/。以下，且特佳爲0.1%以上、5%以下。 將膠質二氧化矽表面之矽原子取代爲硼原子時，對於硼 原子之取代量係藉由控制添加至膠質二氧化矽之分散液的 硼酸化合物之添加量（濃度），即可適當地加以控制。 -16- 200804575 關於經以硼酸加以表面改質的膠質二氧化矽之調製，則 將說明如下，但是並不受限於此等方法。 例如，將硼酸粉末（268克）溶解於超純水（5·6公斤 )中，以調製得硼酸溶液。 其次，對該硼酸溶液緩慢地（約以200毫升/分鐘速率 且歷時約1.2小時）加入經使用Η型離子交換樹脂加以脫鹼 的20%膠質二氧化矽溶液（平均粒徑爲20奈米之膠質二氧 化矽），再添加1〇克之四甲氧基矽烷，並邊攪拌混合物、 邊維持溫度在55 °C至60 °C。添加結束後，也邊加熱（約60 °C )混合物、邊攪拌（5.5小時）。 接著，將所製得之溶液經由1微米（1 // m )之陶瓷過濾 器加以過濾以製得經以硼加以表面改質的膠質二氧化矽。 在本發明中，使用如上所述之鋁酸鹽離子或硼酸鹽離子 加以表面改質之膠質二氧化矽，亦即，上述特定的膠質二氧 化矽之大小（體積相當直徑）較佳爲3奈米至200奈米，更 φ 佳爲5奈米至100奈米，特佳爲10奈米至60奈米。另外， 特定的膠質二氧化矽之粒徑（體積相當直徑）係藉由使用動 態光散射法所測定之値。 包含在本發明之硏磨用組成物的硏磨粒中之特定的膠 質二氧化矽之重量比率較佳爲50%以上，#佳爲80%以上。 所含有的硏磨粒也可全部爲特定的膠質二氧化矽。 硏磨用組成物在使用時，硏磨液中之特定的膠質二氧化 矽之含量較佳爲0.001重量％以上、5重量％以下，更佳爲 0.01重量％以上、0.5重量％以下，且特佳爲0.05重量％以上 -17- 200804575 、0.2重量％以下。 在本發明之硏磨用組成物中，除如上所述之特定的膠質 二氧化矽以外，在不至於損及本發明之功效範圍內可又包含 特定的膠質二氧化矽以外之硏磨粒。此時，可使用的特定的 膠質二氧化矽以外之硏磨粒較佳爲煅製二氧化矽（fumed silica)、膠質二氧化政、二氧化鈽（ceria)、氧化錯（alumina )、氧化欽（titania)等，特佳爲膠質二氧化砂。 0 除了如上所述之特定的膠質二氧化矽以外的硏磨粒之 大小，較佳爲與如上所述之特定的膠質二氧化矽爲同等以上 、且兩倍以下。 〈（b)具有陰離子性取代基、且在分子內具有三個或以上 氮原子之雜芳香族環化合物〉 本發明之硏磨用組成物中，其係包含「具有陰離子性取 代基、且在分子內具有三個或以上氮原子之雜芳香族環化合 物」（在下文中也稱爲「（ b )雜芳香族環化合物」）爲必 $ 要成份。 該（b)雜芳香族環化合物係可單獨使用一種、或其兩 種以上組合倂用。 如上所述之「具有陰離子性取代基、且在分子內具有三 個或以上氮原子之雜芳香族環化合物」較佳爲如下所述之四 哩（tetrazole)衍生物、1，2,3-三嗤（l，2,3-triazole)衍生物 、及1，2,4-三唑衍生物。 (四唑衍生物） 其特徵爲：其係在用於形成四唑環的氮原子上並未具 -18- 200804575 有取代基，且在四唑之5位具有陰離子性取代基〔例如，具 有選自由羧基、磺酸基、羥基、胺基、胺甲醯基、羧基醯胺 基、胺磺醯基、及磺醯胺基所構成之族群中之基的取代基； 其中較佳爲羧基、磺酸基，更佳爲羧基〕之四唑衍生物。 (1，2,3-三唑衍生物） 其特徵爲：其係在用於形成1，2,3-三唑環的氮原子上並 未具有取代基，且在1，2,3-三唑之4位和/或5位具有陰離子 性取代基〔例如，具有選自由羧基、磺酸基、羥基、胺基、 0 胺甲醯基、羧基醯胺基、胺磺醯基、及磺醯胺基所構成之族 群中之基的取代基；其中較佳爲羧基、磺酸基、更佳爲羧基 〕之1，2,3-三唑衍生物。 (1，2,4·三唑衍生物） 其特徵爲：其係在用於形成1，2,4-三唑環的氮原子上並 未具有取代基，且在1，2,4-三唑之3位和/或5位具有陰離子 性取代基〔例如，選自由羧基、磺酸基、羥基、胺基、胺甲 ^ 醯基、羧基醯胺基、胺磺醯基、及磺醯胺基所構成之族群中 之基的取代基；其中較佳爲羧基、磺酸基、更佳爲羧基〕之 1，2,4·三唑衍生物。 在本發明中，該「（b)雜芳香族環化合物」，具體而 言係包括如下所例示之化合物（1-2)至（1-4)、（卜6)至 (1-16)，但是並不受限於此等。 -19- ‘200804575[Technical Field] The present invention relates to a composition for honing, and more particularly to a composition for metal honing used in a wiring forming step for manufacturing a semiconductor device, and a use thereof Its chemical mechanical honing method. [Prior Art] In order to reduce the size and speed of semiconductor devices represented by semiconductor integrated circuits (hereinafter referred to as "LSI" as appropriate), in recent years, wiring has been required to be miniaturized and laminated. High density and high integration. For the technology required for this, various techniques such as chemical mechanical polishing (hereinafter referred to as "CMP" as appropriate) have been used. This CMP is a technique necessary for flattening the surface of a film to be processed such as an interlayer insulating film, forming a plug, and forming a damascene wiring. Therefore, the technique has been used to smooth the substrate. Or removing the excess metal film at the time of wiring formation (for example, see U.S. Patent No. 4,944,836). The general method of CMP is to attach a honing pad to a circular platen, then immerse the surface of the honing pad with the honing liquid, and press the surface of the substrate (wafer) against the honing pad. In a state in which a specific pressure (honing pressure) is applied to the back surface, both the honing platform and the substrate are relatively rotated, and the surface of the substrate is flattened by the generated mechanical friction. Heretofore, the metal for wiring and tungsten and aluminum have been used for an interconnect structure. However, for the purpose of further improving the performance, an LSI using a wiring resistance lower than that of the metal has been developed. A method of wiring the copper with 200804575 is known, for example, as a damascene method disclosed in Japanese Laid-Open Patent Publication No. 2-2 78822. Further, it has also been widely used as a dual damascene method in which a contact hole and a wiring trench are simultaneously formed on an interlayer insulating film, and then a metal is embedded in the both. The target material for the copper wiring has a commercially available high-purity copper target of five or more (9) or more. However, in recent years, it is necessary to increase the conductivity or electronic properties of the copper wiring as the wiring is made more dense, and then it is also desired to use a copper which is added with a third component for high-purity copper. The method of alloying. At the same time, there is a need for a high-speed metal honing method that can achieve high productivity without contaminating such high-precision and high-purity materials. Regarding the honing of copper metal, especially since it is a soft metal, it is easy to cause a phenomenon in which a central portion is subjected to deeper honing to produce a dish-like recess (dishing), and a plurality of wirings are made. The metal surface forms a dish-like recess (erosion) or scratch (scratch; scratch). Therefore, there is an increasing need for high precision honing techniques. Further, recently, in order to improve productivity, the crystal diameter of the LSI is becoming larger. It is now a general-purpose diameter of 200 mm or more, and manufacturing of a size of 300 mm or more is also being implemented. As these wafers become larger, the difference in honing rate between the center portion and the peripheral portion of the wafer tends to occur. Therefore, the requirements for honing uniformity in the wafer surface are becoming more and more strict. For copper and copper alloys, a chemical honing method which does not employ a mechanical honing method, a method disclosed in Japanese Laid-Open Patent Publication No. SHO-49-1 2243 No. 200804575 is known. However, the chemical honing method which relies only on the chemical dissolution is compared with the CMP which selectively hones the metal film of the convex portion in a chemical mechanical manner, since it is cut into a concave portion, that is, Dishing, etc., so that there is a great technical problem for the planarity of honing. On the other hand, when copper wiring is used for LSI manufacturing, in general, for the purpose of preventing diffusion of copper ions into an insulating material, a so-called "barrier layer" is provided between the wiring portion and the insulating layer. Floor. The barrier layer is composed of a barrier material selected from the group consisting of TaN, TaSiN, Ta, TiN, Ti, Nb, W, WN, Co, Zr, ZrN, Ru, and CuTa alloy, and is composed of one layer or two or more layers. These barrier materials must completely remove the barrier material on the insulating layer because of its own conductive property 'to prevent the occurrence of malfunction of shallow leakage current temples'. This removal processing is carried out by the same method as the bulk honing of the metal wiring material (barrier CMP). In addition, in the case of honing copper, since it is particularly easy to form a recess in the wide metal wiring portion, in order to achieve final flattening, it is preferable to adjust the wiring portion and the barrier portion to be removed and removed. the amount. Therefore, it has been desired that the honing fluid for barrier honing can have the most appropriate honing selectivity for the copper/barrier metal. Further, since the wiring pitch or the wiring density of each wiring layer is not the same, it is more preferable to appropriately adjust the honing selectivity. A honing composition for metal (CMP honing liquid) for use in CMP, generally comprising solid honing particles (for example, alumina, silica) and an oxidizing agent (for example, hydrogen peroxide, persulfuric acid) . The basic mechanism of CMP using such a metal honing fluid is generally considered to be by oxidizing the oxygen to the surface of the metal, and then removing the oxide film with the honing particles, for example, as disclosed in the Electrochemical Association. Journal of Electrochemical Society, Vol. 138, 1991, No. 1, pp. 460 to 3, 4 64. However, when CMP is performed using a honing liquid containing a solid honing abrasive as described above. , it may cause scratches, honing surfaces are all over-honed (thinning), honing metal surface under the shape of a disc-like phenomenon (recess), insulation of metal wiring The body is over-honed, and a plurality of wiring metal faces are formed into a disc-like shape (erosion). Further, after the honing, in order to remove the honing liquid remaining on the semiconductor surface, the cleaning step is further complicated by the use of the honing liquid containing the solid honing particles. . Further, there is a problem in that it is necessary to separate the solid honing particles by a sedimentation method when the liquid (waste liquid) after washing is treated. One method for solving such problems, for example, a metal surface honing method by combining a honing liquid containing no honing abrasive particles and a dry etching method has been disclosed in the Journal of Electrochemical Association, Vol. 147, No. 10, 2000. 3,907 to 3,91 3 pages. Further, in Japanese Laid-Open Patent Publication No. 2001-127019, a honing liquid for metal composed of hydrogen peroxide/malic acid/benzotriazole/polyammonium acrylate and water has been disclosed. According to this method, the metal film of the convex portion of the semiconductor substrate is selectively subjected to CMP, so that the metal film remains in the concave portion to obtain a conductor pattern which is desired. This is because CMP will progress smoothly with the friction of the abrasive pad which is mechanically farther than the conventional slurries containing solid honing particles, so that the occurrence of scratches has been reduced. However, in 200804575, there is a disadvantage that the physical honing force is lowered, so that, for example, a sufficient honing rate cannot be obtained. On the other hand, the honing agent containing honing particles has the characteristics of being able to obtain a high honing rate, but the pH of the honing liquid is from neutral to acidic, but the granules are easily condensed due to eutectic grains. Carry out or cause scratching problems. A colloidal silica which is surface-modified with boron has been disclosed as a ruthenium in the form of a ruthenium ruthenium which is stabilized from neutral to acidic, and is disclosed in Japanese Laid-Open Patent Publication No. 20 03-18 8 363. The honing composition of the abrasive grains, Japanese Laid-Open Patent Publication No. 2003-179753, discloses that a part or all of the surface of the cerium oxide microparticles is a surface in which a metal insulating film coated with aluminum is simultaneously present. Glue with colloidal cerium oxide. These honing granules which are negatively charged by surface modification using boron or aluminum prevent aggregation from neutral to acidic. However, the surface potential of metals such as copper is generally positively charged from the neutral to acidic domains. Therefore, it causes a sag or immersion of uranium due to static absorbing of the honing particles adsorbed on the metal surface, or the honing of the granules after honing will result in a decrease in detergency. SUMMARY OF THE INVENTION [Technical Problem to be Solved] An object of the present invention is to provide a metal honing composition which is excellent in detergency after being honed by suppressing dents or immersion, and additionally provides a metal honing composition. A chemical mechanical honing method using the metal honing composition. [Technical method for solving the problem] In view of the above-mentioned problems, the inventors of the present invention have found that the present invention can be solved by the following methods. 200804575 (1) A composition for metal honing characterized by comprising (a) a surface-modified cerium particle using colloidal silica using an aluminate ion or a boric acid ion, and (b) having A heterocyclic aromatic compound having an anionic substituent and having three or more nitrogen atoms in the molecule. (2) The metal honing composition according to (1), further comprising (c) a heteroaromatic ring compound having three or more nitrogen atoms in the molecule and having no anionic substituent. (3) The metal honing composition according to Item (1), wherein the metal honing composition is obtained by dispersing the honing particles as described above in a mash slurry in an aqueous solution. (4) The metal honing composition according to Item (1), wherein the surface atomic substitution rate of the colloidal cerium oxide on the surface of the colloidal cerium oxide is a number of aluminum atoms or boron atoms/surface 矽 atoms When the number of parts is the same, the substitution ratio is 0.001% or more and 20% or less. The metal honing composition according to the item (1), wherein the colloidal cerium oxide has a volume equivalent diameter of from 3 nm to 200 nm as measured by dynamic light scattering. (6) The metal honing composition according to Item (1), wherein the metal honing composition has a pH of from 3 to 7. (7) The metal honing composition according to any one of (1) to (6), wherein the surface to be honed using the metal honing composition is copper or a copper alloy . (8) A chemical mechanical honing method characterized by using honing particles comprising (a) -10- 200804575 using aluminate ion or borate ion to surface-modify colloidal ceria, and (b) A metal honing composition having an anionic substituent and a heteroaromatic ring compound having three or more nitrogen atoms in the molecule; and honing is performed at a honing pressure of 3 psi (0.0207 MPa) or less. (9) The chemical mechanical honing method according to Item (8), wherein the metal honing composition further comprises (c) a heteroaromatic having three or more nitrogen atoms in the molecule and having no anionic substituent Group ring compounds. (1) The chemical mechanical honing method according to the item (8) or (9), wherein the surface to be honed using the metal honing composition is copper or a copper alloy. [Effect of the Invention] According to the present invention, it is possible to provide a metal honing which can prevent electrostatic adsorption of a negatively charged honing granule on a metal surface, suppress depression or etch, and have good rinsing property after honing. Use the composition. φ Further, a chemical mechanical honing method using the metal honing composition as described above can be provided. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION (Metal composition for metal honing) The metal honing composition of the present invention is characterized by comprising (a) using an aluminate ion or a borate ion to form a colloid The cerium oxide is surface-modified cerium particles, and (b) a heteroaromatic ring compound having an anionic substituent and having three or more nitrogen atoms in the molecule. -11- 200804575 In addition, other compounds may be contained as necessary. The metal honing composition of the present invention is usually in the form of a pulverized pulp obtained by dispersing the above-mentioned colloidal cerium oxide (cerium granules) in an aqueous solution in which the respective components are dissolved. The metal honing composition of the present invention is suitably used as a honing composition for chemical mechanical honing of a honed object at the time of manufacture of a semiconductor device. Further, the pH of the metal honing composition of the present invention is preferably from 3 to 7, more preferably from 4 to 7. If the pH is less than 3, it may cause aggregation easily, and if the pH exceeds 7, the dent may be deteriorated. As for the components constituting the composition for metal honing, the details are as follows, but each component may be used singly or in combination of two or more kinds thereof. In the present invention, the "metal honing composition" (hereinafter, also referred to as "honing composition"), unless otherwise specifically added, means not only the composition used for honing. The form of (concentration) is used in the form of metal honing, which is used after being diluted as needed. When the concentrate is used for honing, it is diluted with water or an aqueous solution and used in a honing machine, and its dilution ratio is generally 1 to 20 times by volume. <(a) Gluconium cerium oxide surface-modified with aluminate ions or borate ions> In the honing composition of the present invention, it contains "(a) using aluminate ions or borate ions A surface-modified colloidal cerium oxide" (hereinafter referred to as "specific colloidal cerium oxide" as appropriate) ° -12- 200804575 A specific colloidal cerium oxide is used as a cerium in the honing composition of the present invention. Those who play the grain and function. In the present invention, the term "colloidal ceria which is surface-modified with aluminate ions or borate ions" means that an aluminum atom or a boron atom is present in a site having a coordinal atom of 4. The state of the surface of the colloidal cerium oxide. For example, an aluminum atom coordinated to four oxygen atoms may be bonded to the surface of the colloidal ceria to form a new surface in which the aluminum atom is fixed in a state of 4 coordination, or may be present. The germanium atoms on the surface are temporarily pulled out to form a state of a new surface exchanged with aluminum atoms. · In addition, a boron atom coordinated to four oxygen atoms may be bonded to the surface of the colloidal ceria to form a new surface in which the boron atom is fixed in a state of 4 coordination, or may be The germanium atoms present on the surface are temporarily pulled out to form a state of a new surface exchanged with boron atoms. The colloidal cerium oxide used for modulating a specific colloidal cerium oxide is more preferably an impurity which does not contain an alkali metal or the like inside the fine particles, and is a colloidal cerium oxide obtained by hydrolysis of an alkoxy decane. Further, colloidal cerium oxide produced by a method of removing a base from an aqueous alkaline solution of citric acid can also be used. However, when this method is employed, there is a concern that the alkali metal remaining inside the particles will slowly precipitate, which may affect the honing performance. From these viewpoints, the raw material is more preferably obtained by hydrolysis of alkoxysilane as described above. The particle size of the colloidal ceria used as a raw material is appropriately selected depending on the purpose of use of the honing particles, but is generally from about 1 Torr to 200 nm. - (al) a colloidal cerium oxide surface-modified with aluminate ions - 13-200804575 The ruthenium atom on the surface of the colloidal cerium oxide microparticles as described above is substituted with an aluminum atom to produce a specific colloidal cerium oxide. The method is preferably a method of adding, for example, an aluminate compound such as sodium aluminate to a dispersion of colloidal cerium oxide. These methods are disclosed in detail in the Invention Patent No. 3,. 463, 328, and the Japanese Patent Application Laid-Open No. 63-123807, the disclosure of which is hereby incorporated herein. As for other methods, there is a method of adding an alkane alumina to a dispersion of colloidal cerium oxide. The specific colloidal cerium oxide is fixed by a negative charge due to the alumino silicate moiety formed by the reaction of the 4-coordinated aluminate ion with the stanol group on the surface of the colloidal cerium oxide, and the particles are fixed. It imparts a negative zeta potential and a superior dispersibility in acidity. Therefore, by the specific colloidal cerium oxide produced by the method as described above, it is important that the aluminum atom is present in a state of being coordinated with four oxygen atoms, that is, on the surface of the colloidal cerium oxide. The substitution which produces a ruthenium atom and an aluminum atom can be easily confirmed, for example, by measuring the zeta potential of the honing particles. When the amount of the argon atom on the surface of the colloidal cerium oxide is substituted with the aluminum atom, the amount of surface atom substitution ratio (the number of introduced aluminum atoms / the number of surface argon atoms) is preferably 0.001% or more. 20% or less, more preferably (K01% or more, 10% or less, and particularly preferably 〇·1% or more, 5% or less, when the ruthenium atom on the surface of the colloidal ruthenium dioxide is substituted with an aluminum atom, for aluminum-14 - *200804575 The atomic substitution amount can be appropriately controlled by controlling the addition amount (concentration) of the aluminate compound, alkane alumina, etc. added to the dispersion of colloidal ceria. At this time, for colloidal oxidation The amount of introduction of aluminum atoms on the surface of the crucible (the number of introduced aluminum atoms / the number of surface germanium atoms) is calculated from the unreacted aluminum compound remaining after the reaction among the aluminum compounds added to the dispersion. The amount of aluminum compound consumed, and assumes that it is 100% involved in the reaction, and then the surface area converted by the diameter of the colloidal ceria, the specific gravity of the colloidal® ceria 2.2, and the surface area per unit area The number of alcohol groups (5 to 8 / nm2) can be estimated. The actual measurement is based on the elemental analysis of the specific colloidal cerium oxide produced, and it is assumed that aluminum is not present inside the particles and is uniform and thin. Extending to the surface, then using the surface area/specific gravity of the colloidal ceria and the number of stanol groups per unit surface area. The specific method is, for example, dispersing colloidal ceria in the range of 1 to 50% by weight of I in water. And adding a pH adjuster to the dispersion to adjust the pH to 7 to 1, and then adding an aqueous solution of ammonium aluminate near the room temperature, and stirring at the temperature for 1 to 1 hour. Thereafter, the ion is used. Exchange or ultrafiltration, etc. to remove specific impurities to produce a specific colloidal ceria. - (a2) Gluconium cerium oxide surface modified with borate ions - colloidal dioxide as described above A method for preparing a specific colloidal cerium oxide by substituting a ruthenium atom on the surface of the ruthenium into a boron atom, which comprises, for example, modifying the surface of the colloidal cerium oxide using a boric acid and a decane coupling agent. - 200804575 Method of manufacture. The methods are disclosed in detail in Japanese Patent Application Laid-Open No. 2003-525 No. 119, European Patent No. EP 943648, and European Patent No. EP 94 1 995, the disclosure of which is incorporated herein by reference. It can be applied to the present invention. The specific colloidal cerium oxide system fixes the negative charge by the reaction of the 4-coordinated borate ion with the stanol group on the surface of the colloidal cerium oxide, and gives a negative to the microparticles. Large zeta potential, and superior dispersibility in acidity. Therefore, by the specific colloidal ceria produced by the method described above, it is important that the aluminum atom be coordinated to four oxygen atoms A. The status exists. Such a structure, i.e., a structure in which a ruthenium atom and a boron atom are substituted on the surface of the colloidal ruthenium dioxide can be easily confirmed by, for example, measuring the zeta potential of the honing particles. The zeta potential of the colloidal cerium oxide surface is from 0 to -10 mV from pH 3 to pH 5, but is treated with borate ions, thereby being lowered to -10 to -20 mV. If the zeta potential of the surface of the colloidal cerium oxide is from -10 mV to -2 〇mV from pH 5 to pH 7, it can be reduced to -20 mV to -40 by treatment with borate ions. mV. The amount of the surface atom substitution rate (the number of introduced boron atoms / the number of surface ruthenium atomic sites) of the colloidal silica is preferably 0.001% or more, 20, in which the ruthenium atom on the surface of the colloidal cerium oxide is substituted with the boron atom. % or less, more preferably 0.01% or more, 10 ° /. Hereinafter, it is particularly preferably 0.1% or more and 5% or less. When the argon atom on the surface of the colloidal cerium oxide is substituted with a boron atom, the substitution amount of the boron atom can be appropriately controlled by controlling the addition amount (concentration) of the boric acid compound added to the dispersion of the colloidal cerium oxide. . -16- 200804575 The preparation of colloidal cerium oxide which has been surface-modified with boric acid will be described below, but is not limited thereto. For example, boric acid powder (268 g) is dissolved in ultrapure water (5.6 kg) to prepare a boric acid solution. Next, the boric acid solution was slowly added (about 200 ml/min at a rate of about 1.2 hours) to a 20% colloidal cerium oxide solution which was de-alkali using a hydrazine-type ion exchange resin (average particle size of 20 nm) Glue ruthenium dioxide), 1 gram of tetramethoxy decane was added, and the mixture was stirred while maintaining the temperature at 55 ° C to 60 ° C. After the end of the addition, the mixture was heated (about 60 ° C) while stirring (5.5 hours). Next, the prepared solution was filtered through a 1 μm (1 // m) ceramic filter to obtain a gelled cerium oxide surface-modified with boron. In the present invention, the colloidal ceria is surface-modified with an aluminate ion or a borate ion as described above, that is, the size (volume equivalent diameter) of the above specific colloidal ceria is preferably 3 From rice to 200 nm, φ is preferably from 5 nm to 100 nm, and particularly preferably from 10 nm to 60 nm. Further, the particle size (volume equivalent diameter) of a specific colloidal ceria is determined by dynamic light scattering. The weight ratio of the specific colloidal cerium oxide contained in the honing granules of the honing composition of the present invention is preferably 50% or more, and more preferably 80% or more. The honing particles contained may also be all specific colloidal cerium oxide. When the composition for honing is used, the content of the specific colloidal cerium oxide in the honing liquid is preferably 0.001% by weight or more and 5% by weight or less, more preferably 0.01% by weight or more and 0.5% by weight or less, and particularly Preferably, it is 0.05% by weight or more and -17-200804575 or 0.2% by weight or less. In the honing composition of the present invention, in addition to the specific colloidal cerium oxide as described above, cerium particles other than the specific colloidal cerium oxide may be contained in the range which does not impair the efficacy of the present invention. At this time, the cerium particles other than the specific colloidal cerium oxide which can be used are preferably fumed silica, colloidal dioxide, ceria, alumina, oxidized chin. (titania), etc., especially good for colloidal silica sand. The size of the honing particles other than the specific colloidal cerium oxide as described above is preferably equal to or more than twice the amount of the specific colloidal cerium oxide as described above. <(b) A heteroaromatic ring compound having an anionic substituent and having three or more nitrogen atoms in the molecule> The honing composition of the present invention contains "an anionic substituent, and A heteroaromatic ring compound having three or more nitrogen atoms in the molecule (hereinafter also referred to as "(b) heteroaromatic ring compound") is a mandatory component. The (b) heteroaromatic ring compound may be used singly or in combination of two or more kinds thereof. The "heteroaromatic ring compound having an anionic substituent and having three or more nitrogen atoms in the molecule" as described above is preferably a tetrazole derivative, 1, 2, 3 as described below. a triterpene (l, 2,3-triazole) derivative and a 1,2,4-triazole derivative. (tetrazole derivative) characterized in that it has no substituent of -18-200804575 on the nitrogen atom used to form the tetrazole ring, and has an anionic substituent at the 5-position of the tetrazole (for example, a substituent selected from a group consisting of a carboxyl group, a sulfonic acid group, a hydroxyl group, an amine group, an amine carbaryl group, a carboxy guanylamino group, an amine sulfonyl group, and a sulfonamide group; wherein a carboxyl group is preferred A tetrazolium derivative of a sulfonic acid group, more preferably a carboxyl group. (1,2,3-triazole derivative) characterized in that it has no substituent on the nitrogen atom used to form the 1,2,3-triazole ring, and is 1,2,3-three The 4-position and/or 5-position of the azole has an anionic substituent (for example, having a selected from the group consisting of a carboxyl group, a sulfonic acid group, a hydroxyl group, an amine group, an amine group, an amino group, a carboxy oxime group, an amine sulfonyl group, and a sulfonium group). A substituent of a group in the group consisting of an amine group; preferably a 1,2,3-triazole derivative of a carboxyl group, a sulfonic acid group, more preferably a carboxyl group. (1,2,4·triazole derivative) characterized in that it has no substituent on the nitrogen atom used to form the 1,2,4-triazole ring, and is 1,2,4-tri The 3-position and/or 5-position of the azole has an anionic substituent (for example, selected from the group consisting of a carboxyl group, a sulfonic acid group, a hydroxyl group, an amine group, an amine group, a carboxy oxime group, an amine sulfonyl group, and a sulfonamide A substituent of a group in the group consisting of a group; wherein a 1,2,4. triazole derivative of a carboxyl group, a sulfonic acid group, or more preferably a carboxyl group is preferred. In the present invention, the "(b) heteroaromatic ring compound" specifically includes the compounds (1-2) to (1-4), (b 6) to (1-16) exemplified below, But it is not limited to this. -19- ‘200804575

在本發明之硏磨用組成物中，該「（b)雜芳香族環化 合物」之添加量，相對於1公斤之硏磨用組成物，較佳爲 φ 0.0001重量％以上、0·005重量％以下，更佳爲0.0005重量％ 以上、0.002重量％以下。 此外，該（b)雜芳香族環化合物係包括苯并三唑-4-甲 酸、苯并三唑-4-磺酸等。 〈（c)在分子內具有三個或以上氮原子、且無陰離子性取 代基之雜芳香族環化合物〉 在本發明之金屬硏磨用組成物中，較佳爲包含「（c) 在分子內具有三個或以上氮原子、且無陰離子性取代基之雜 芳香族環化合物」（在下文中也稱爲「（c)雜芳香族環化 -20- 200804575 合物」）。 藉由含有如上所述之（c)雜芳香族環化合物，即可將 銅表面的鈍態膜（passive film)之負電荷密度加以調整。 在本發明之「（c)在分子內具有三個或以上氮原子、 且無陰離子性取代基之雜芳香族環化合物」係包括在如上所 述之（b )雜芳香族環化合物的芳香族環內，並無如上所述 之陰離子性取代基之雜芳香族環化合物。 0 亦即，其係意謂僅具有雜芳香族環之化合物，而並無鍵 結於該雜芳香族環的取代基者。 在本發明之硏磨用組成物中，該「（ c )雜芳香族環化 合物」之添加量，相對於硏磨用組成物1公斤，較佳爲0.000 1 重量％以上、0.005重量％以下，更佳爲0.0005重量％以上、 0.002重量％以下〇 本發明之硏磨用組成物，除如上所述之成份以外，必要 時，則也可含有下述成份。以下就可適用於本發明之硏磨用 φ 組成物的任意成份加以說明。 〈（d )界面活性劑和/或親水性聚合物〉 在本發明之硏磨用組成物中，其係可含有「（d)界面 活性劑和/或親水性聚合物」。 該界面活性劑和/或親水性聚合物，較佳爲酸型，若使 用鹽結構時，則其係包括銨鹽、鉀鹽、鈉鹽等；該等之中， 較佳爲銨鹽和鉀鹽。 界面活性劑與親水性聚合物係任一者皆具有降低對於 被硏磨面的接觸角之作用，因此具有促進均勻硏磨之作用。 -21- ,200804575 可使用之界面活性劑和/或親水性聚合物較佳爲選自由下列 所組成之族群者。 「陰離子性界面活性劑」係包括：羧酸鹽、磺酸鹽、硫 酸酯鹽、磷酸酯鹽等。此等之中，該「羧酸鹽」係包括：肥 皂、N-醯基胺基酸鹽、聚氧化乙烯或聚氧化丙烯、烷基醚羧 酸鹽、醯化縮氨酸等。該「磺酸鹽」係包括··烷基磺酸鹽、 烷基苯和烷基萘磺酸鹽、萘磺酸鹽、磺基琥珀酸鹽、α-烯 烴磺酸鹽、Ν -醯基磺酸鹽等。該「硫酸酯鹽」係包括：硫酸 ® 化油、烷基硫酸鹽、烷基醚硫酸鹽、聚氧化乙烯或聚氧化丙 烯烷基烯丙基醚硫酸鹽、烷基醯胺硫酸鹽等。該「磷酸酯鹽 」係包括：烷基磷酸鹽、聚氧化乙烯或聚氧化丙烯烷基烯丙 基醚磷酸鹽等。 「陽離子界面活性劑」係包括：脂肪族胺鹽、脂肪族四 級銨鹽、氯化苯甲基烷銨鹽（烷基二甲基苯甲基氯化銨鹽） 、氯化苯甲基乙銨、吡啶鐵鹽、咪唑鑰鹽等。「兩性界面活 ^ 性劑」係包括：羧基甜菜鹼型、磺酸基甜菜鹼型、胺基羧酸 鹽、咪唑鑰甜菜鹼、卵磷脂、氧化烷基胺等。 「非離子界面活性劑」係包括··醚型、醚酯型、酯型、 含氮型等。此等之中，該「醚型」係包括：聚氧化乙烯烷基 及烷基苯基醚、經烷基烯丙基甲醛縮合之聚氧化乙烯醚、聚 氧化乙烯-聚氧化丙烯嵌段聚合物、聚氧化乙烯-聚氧化丙烯 烷基醚等。該「醚酯型」係包括··甘油酯之聚氧化乙烯醚、 山梨糖醇酐酯之聚氧化乙烯醚、山梨醇酯之聚氧化乙燦醚等 。該「酯型」係包括：聚乙二醇脂肪酸酯、甘油酯、聚甘油 -22- 200804575 酯、山梨糖醇酐酯、丙二醇酯、蔗糖酯等。該「含氮型」係 包括：脂肪酸院醇醯胺、聚氧化乙烯脂肪酸醯胺、聚氧化乙 烯烷基醯胺等。 其他也可包含「氟系界面活性劑」、「聚矽氧（silieone )系界面活性劑」等。 「親水性聚合物」係包括：聚乙二醇、聚丙二醇、聚四 亞甲基二醇、聚乙二醇烷基醚、聚乙二醇烯基·酸、聚烷基乙 0 二醇、聚烷基乙二醇烷基醚、聚烷基乙二醇烯基醚、聚烯基 乙二醇、聚烯基乙二醇烷基醚、聚丙二醇烷基醚、聚丙二醇 烯基醚、聚烷基丙二醇、聚烷基丙二醇烷基醚、聚烷基丙二 醇烯基醚、聚烯基丙二醇、聚烷基乙二醇烷基醚及聚烯基丙 二醇烯基醚等之「醚類」；褐藻酸、果膠酸、羧甲基纖維素 、卡德蘭多糖（〇1^(11&amp;11;/5-1，3-葡聚糖）、三聚葡萄糖（ pullulane )等之「多糖類」；甘胺酸銨鹽及甘胺酸鈉鹽等之 「胺基酸鹽」；聚天冬胺酸、聚麩胺酸、聚離胺酸' 聚蘋果 ^ 酸、聚甲基丙烯酸、聚甲基丙烯酸銨鹽、聚甲基丙烯酸鈉鹽 、聚順丁烯二酸、聚伊康酸、聚反丁烯二酸、聚（對-苯乙 嫌甲酸）、聚丙烯酸、聚丙烯醯胺、聚胺基丙烯醯胺、聚丙 烯酸銨鹽、聚丙烯酸鈉鹽、聚醯胺基酸、聚醯胺基酸銨鹽、 聚醯胺基酸鈉鹽及聚乙醛酸等之「聚竣酸及其鹽」；以及聚 乙烯醇、聚乙Μ基吡咯11定酮及聚丙嫌醒等之「乙嫌基系聚合 物」等。 但是，若所使用的基體爲半導體積體電路用之砂基板等 時，由於不希望受到因鹼金屬、鹼土金屬、鹵化物等所造成 -23- 200804575 的污染，因此較佳爲酸型，若採用鹽結構時，則較佳爲銨鹽 。若基體爲玻璃基板等時，則並不受限於此等。在如上所例 示化合物之中，更佳爲聚丙烯酸銨鹽、聚乙烯醇、聚乙烯基 吡咯啶酮、聚乙二醇、聚氧化乙烯-聚氧化丙烯嵌段聚合物 〇 界面活性劑和/或親水性聚合物之添加量，以總量計， 在1公升之使用於硏磨時的硏磨組成物中，則較佳爲設定在 0.001至10克，更佳爲設定在0.01至5克，特佳爲設定在 〇·〇2至3克。亦即，爲獲得足夠的功效，該界面活性劑和/ 或親水性聚合物之添加量較佳爲0.00 1克以上；從防止CMP 速率降低的觀點來看，則較佳爲1 0克以下。至於該等界面 活性劑和/或親水性聚合物之重量平均分子量較佳爲500至 1 0 0，0 0 0，特佳爲 2，0 0 0 至 5 0，0 0 0。 界面活性劑和/或親水性聚合物係可單獨使用一種、或 其兩種以上組合倂用，或也可倂用種類不同的活性劑。 〈（e)在分子內具有至少一個羧基與至少一個胺基之化合 物（胺基酸）&gt; 在本發明之硏磨用組成物中，其係可包含「（ e )在分 子內具有至少一個殘基與至少一個胺基之化合物」。更佳爲 該化合物所含有的胺基中至少一個是二級或三級之胺基。該 化合物也可又具有取代基。 可使用於本發明之在分子內具有至少一個羧基與至少 一個胺基之化合物，較佳爲胺基酸或胺基多元酸，尤其係以 選自由下列所組成之族群者爲適合使用。 -24- 200804575 「胺基酸」係適合使用··甘胺酸、羥基乙基甘胺酸、二 羥基乙基甘胺酸、甘胺醯基甘胺酸、N-甲基甘胺酸、L-丙胺 酸、/3 -丙胺酸、L-2-胺基丁酸、L-降纈胺酸、L·纈胺酸、L-白胺酸、L-降白胺酸、L_異白胺酸、L-別異白胺酸、L-苯基 丙胺酸、L-脯胺酸、肌胺酸、L-鳥胺酸、L-離胺酸、牛磺酸 、L-絲胺酸、L-蘇胺酸、L-別蘇胺酸、L-高升絲胺酸、L-酪 胺酸、3,5-二碘-L-酪胺酸、沒·（ 3,4-二羥基苯基）-L-丙胺 酸、L-甲狀腺素、4-羥基-L-脯胺酸、L-半胱胺酸、L-甲硫胺 酸、L-乙硫胺酸、L-羊毛硫胺酸、L-胱硫醚、L-胱胺酸、L-半胱胺酸、L-天冬胺酸、L-麩胺酸、S-(羧甲基）-L-半胱胺 酸、4-胺基丁酸、L·天冬素（L-天冬醯胺酸）、L-麩醯胺酸 、吖絲胺酸、L-精胺酸、L-刀豆胺酸、L-瓜胺酸、6 ·羥基-L· 離胺酸、肌酸、L-犬尿胺酸、L-組胺酸、1-甲基-L-組胺酸、 3-甲基-L-組胺酸、麥角硫醇、L-色胺酸、放線菌素C1、蜂 毒明肽（apamin )、血管緊縮素I、血管緊縮素π、及抗木 φ 瓜酶等之「胺基酸」。此等之中，較佳爲甘胺酸、L-丙胺酸 、L-組胺酸、L-脯胺酸、L·離胺酸、二羥基乙基甘胺酸。 「胺基多元酸」係包括例如：亞胺基二醋酸、羥基乙基 亞胺基二醋酸、氮川三醋酸、二伸乙基三胺五醋酸、伸乙基 二胺四醋酸、氮川參亞甲基膦酸、伸乙基二胺-N，N，N，，N，· 四亞甲基磺酸、反式環己烷二胺四醋酸、1，2-二胺基丙烷四 醋酸、乙二醇醚二胺四醋酸、伸乙基二胺鄰羥基苯基醋酸、 伸乙基二胺二琥珀酸（SS體）、N- ( 2-羧酸根合乙基）-L-天冬胺酸、/3 -丙胺酸二醋酸、N，N’-雙（2-羥基苯甲基）伸 -25- 200804575 乙基二胺-N，N’-二醋酸等。 可使用於本發明之胺基酸或胺基多元酸，較佳爲胺基酸 或胺基多元羧酸，特佳爲以如下所示之式（1)或式（2)所 代表之化合物。In the honing composition of the present invention, the amount of the "(b) heteroaromatic ring compound" is preferably 0.001 0.0001% by weight or more and 0. 005 by weight based on 1 kg of the composition for honing. % or less is more preferably 0.0005 wt% or more and 0.002 wt% or less. Further, the (b) heteroaromatic ring compound includes benzotriazole-4-carboxylic acid, benzotriazole-4-sulfonic acid and the like. <(c) Heteroaromatic ring compound having three or more nitrogen atoms in the molecule and having no anionic substituent> In the metal honing composition of the present invention, it is preferred to contain "(c) in the molecule A heteroaromatic ring compound having three or more nitrogen atoms and having no anionic substituents (hereinafter also referred to as "(c) heteroaromatic cyclization-20-200804575 compound"). The negative charge density of the passive film on the copper surface can be adjusted by containing the (c) heteroaromatic ring compound as described above. In the present invention, "(c) a heteroaromatic ring compound having three or more nitrogen atoms in the molecule and having no anionic substituent" is included in the aromatic of the (b) heteroaromatic ring compound as described above. A heteroaromatic ring compound having no anionic substituent as described above in the ring. That is, it means a compound having only a heteroaromatic ring and no substituent bonded to the heteroaromatic ring. In the honing composition of the present invention, the amount of the "(c) heteroaromatic ring compound" is preferably 0.0001% by weight or more and 0.005% by weight or less based on 1 kg of the honing composition. More preferably, it is 0.0005 wt% or more and 0.002 wt% or less. The composition for honing of the present invention may contain the following components in addition to the above-mentioned components, if necessary. Hereinafter, any component which can be applied to the honing φ composition of the present invention will be described. <(d) Surfactant and/or hydrophilic polymer> The honing composition of the present invention may contain "(d) surfactant and/or hydrophilic polymer". The surfactant and/or hydrophilic polymer is preferably an acid type, and if a salt structure is used, it includes an ammonium salt, a potassium salt, a sodium salt and the like; among these, an ammonium salt and a potassium salt are preferred. salt. Both the surfactant and the hydrophilic polymer have the effect of lowering the contact angle with respect to the surface to be honed, and thus have the effect of promoting uniform honing. The surfactant and/or hydrophilic polymer which can be used is preferably selected from the group consisting of the following. The "anionic surfactant" includes a carboxylate, a sulfonate, a sulfate, a phosphate, and the like. Among these, the "carboxylate" includes: a fat soap, an N-decylamino acid salt, a polyethylene oxide or a polypropylene oxide, an alkyl ether carboxylate, a hydrazine peptide, and the like. The "sulfonate" includes an alkylsulfonate, an alkylbenzene and an alkylnaphthalenesulfonate, a naphthalenesulfonate, a sulfosuccinate, an alpha-olefinsulfonate, an anthracene-sulfonate. Acid salt, etc. The "sulfate salt" includes: sulfuric acid, oil, alkyl sulfate, alkyl ether sulfate, polyethylene oxide or polyoxypropylene alkyl allyl ether sulfate, alkylguanamine sulfate, and the like. The "phosphate salt" includes alkyl phosphate, polyethylene oxide or polyoxypropylene alkyl allylate phosphate. "Cational surfactant" includes: an aliphatic amine salt, an aliphatic quaternary ammonium salt, a benzyl chloride ammonium chloride salt (alkyl dimethyl benzyl ammonium chloride salt), benzyl chloride chloride Ammonium, pyridinium salt, imidazole key salt, and the like. The "amphoteric surfactant" includes a carboxybetaine type, a sulfobetaine type, an aminocarboxylate, an imidazoline betaine, a lecithin, an alkylamine oxide, and the like. The "nonionic surfactant" includes an ether type, an ether type, an ester type, a nitrogen type, and the like. Among these, the "ether type" includes: a polyoxyethylene alkyl group and an alkylphenyl ether, a polyoxyethylene ether condensed with an alkyl allyl formaldehyde, and a polyoxyethylene-polyoxypropylene block polymer. , polyethylene oxide-polyoxypropylene alkyl ether and the like. The "ether ester type" includes a polyoxyethylene ether of a glyceride, a polyoxyethylene ether of a sorbitan ester, and a polyoxyethylene ether of a sorbitan ester. The "ester type" includes polyethylene glycol fatty acid ester, glycerin ester, polyglycerol-22-200804575 ester, sorbitan ester, propylene glycol ester, sucrose ester and the like. The "nitrogen-containing type" includes: a fatty acid decylamine, a polyoxyethylene fatty acid decylamine, a polyoxyethylene alkyl decylamine, and the like. Others may include "fluorine-based surfactant" and "silieone-based surfactant". The "hydrophilic polymer" includes polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol alkenyl acid, polyalkylene glycol, Polyalkylethylene glycol alkyl ether, polyalkyl ethylene glycol alkenyl ether, polyalkenyl glycol, polyalkenyl glycol alkyl ether, polypropylene glycol alkyl ether, polypropylene glycol alkenyl ether, poly "Ethers" such as alkyl propylene glycol, polyalkyl propylene glycol alkyl ether, polyalkyl propylene glycol alkenyl ether, polyalkenyl propylene glycol, polyalkyl glycol alkyl ether, and polyalkenyl propylene glycol alkenyl ether; "polysaccharides" such as acid, pectic acid, carboxymethyl cellulose, and cadmium polysaccharide (〇1^(11&amp;11;/5-1,3-glucan), pullulane, etc.; "Amino acid salt" such as ammonium glycinate and sodium glycinate; polyaspartic acid, polyglutamic acid, polylysine' poly-adalic acid, polymethacrylic acid, polymethacrylic acid Ammonium salt, sodium polymethacrylate, polymaleic acid, polyisic acid, polyfumaric acid, poly(p-phenylethyl succinic acid), polyacrylic acid, polyacrylamide, polyamine "polydecanoic acid and its salts" such as ceramide, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyacrylic acid acid, polyamidosyl ammonium salt, polyamido acid sodium salt and polyglyoxylic acid And "B-based polymer" such as polyvinyl alcohol, polyethylidene pyrrole 11 ketone, and polyacrylamide. However, if the substrate to be used is a sand substrate for a semiconductor integrated circuit, etc., If it is not desired to be contaminated by an alkali metal, an alkaline earth metal, a halide or the like, it is preferably an acid type, and if a salt structure is used, it is preferably an ammonium salt. If the substrate is a glass substrate or the like, It is not limited thereto. Among the compounds exemplified above, more preferred are ammonium polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyoxyethylene-polyoxypropylene block. The amount of the polymer 〇 surfactant and/or the hydrophilic polymer to be added is preferably 0.001 to 10 g, more preferably 1 to 10 liters of the honing composition used for honing. The optimum setting is 0.01 to 5 grams, and the optimum setting is 2 to 3 grams in 〇·〇. That is, In order to obtain sufficient efficacy, the amount of the surfactant and/or hydrophilic polymer added is preferably 0.001 g or more; from the viewpoint of preventing a decrease in the CMP rate, it is preferably 10 g or less. The weight average molecular weight of the surfactant and/or hydrophilic polymer is preferably from 500 to 1,0 0,0 0, particularly preferably from 2,0 0 to 5,0 0. Surfactant and/or hydrophilic The polymer may be used singly or in combination of two or more kinds thereof, or a different type of active agent may be used. <(e) A compound having at least one carboxyl group and at least one amine group in the molecule (amino group) Acid)&gt; In the honing composition of the present invention, it may contain "(e) a compound having at least one residue and at least one amine group in the molecule". More preferably, at least one of the amine groups contained in the compound is a secondary or tertiary amine group. The compound may also have a substituent. The compound having at least one carboxyl group and at least one amine group in the molecule which can be used in the present invention, preferably an amino acid or an amine polybasic acid, is particularly preferably selected from the group consisting of the following. -24- 200804575 "Amino acid" is suitable for use ··Glycine, hydroxyethylglycine, dihydroxyethylglycine, glycylglycine, N-methylglycine, L - alanine, /3 - alanine, L-2-aminobutyric acid, L-homalic acid, L. valine, L-leucine, L-norreic acid, L-iso-amine Acid, L-isoisoleucine, L-phenylalanine, L-proline, sarcosine, L-ornithine, L-lysine, taurine, L-serine, L -threonine, L-besyluric acid, L-norgosic acid, L-tyrosine, 3,5-diiodo-L-tyrosine, bis(3,4-dihydroxyphenyl) -L-alanine, L-thyroxine, 4-hydroxy-L-proline, L-cysteine, L-methionine, L-ethyl thios, L-lanthione, L - cystathionine, L-cystamine, L-cysteine, L-aspartic acid, L-glutamic acid, S-(carboxymethyl)-L-cysteine, 4-amino group Butyric acid, L. aspartate (L-aspartic acid), L-glutamic acid, lysine, L-arginine, L-cutosin, L-citrulline, 6 ·Hydroxy-L· lysine, creatine, L-kynurenine, L-histidine, 1-methyl-L-histidine, 3-methyl -L-histamine, ergothiol, L-tryptophan, actinomycin C1, bee venom (apamin), angiotensin I, angiotensin π, and anti-wood lucanase Amino acid." Among these, glycine, L-alanine, L-histamine, L-proline, L. lysine, and dihydroxyethylglycine are preferred. "Amine-based polybasic acid" includes, for example, iminodiacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, di-ethyltriamine pentaacetic acid, ethyldiaminetetraacetic acid, and nitric acid Methylene phosphonic acid, ethyl diamine-N, N, N, N, · tetramethylenesulfonic acid, trans cyclohexanediamine tetraacetic acid, 1,2-diaminopropane tetraacetic acid, Glycol ether diamine tetraacetic acid, ethylidene diamine o-hydroxyphenylacetic acid, ethyldiamine disuccinic acid (SS body), N-(2-carboxyethylate)-L-aspartate Acid, /3-alanine diacetic acid, N, N'-bis(2-hydroxybenzyl) extension-25- 200804575 Ethyldiamine-N,N'-diacetic acid, and the like. The amino acid or the amine polybasic acid to be used in the present invention, preferably an amino acid or an amine polycarboxylic acid, is particularly preferably a compound represented by the formula (1) or the formula (2) shown below.

R3 XR5R3 XR5

在通式（1 )中之R1係代表單鍵、伸烷基、或伸苯基。 在通式（1 )中之尺2和&amp;3係各自獨立地代表氫原子、鹵素 原子、羧基、烷基、環烷基、烯基、炔基、或芳基。在通式 (1 )中之R4和R5係各自獨立地代表氫原子、鹵素原子、 羧基、烷基、或醯基。 但是，若R1爲單鍵時，則R4和R5之中至少任一者係 並非爲氧原子。 在通式（1 )中作爲之伸烷基係可爲直鏈狀、分枝狀 、環狀中之任一種，較佳爲碳原子數1至8，例如其係包括 亞甲基、伸乙基。 該伸烷基也可含有之取代基係包括羥基、鹵素原子等。 在通式（1 )中作爲R2和R3之烷基，較佳爲碳原子數 爲1至8，其係包括例如甲基、丙基等。 在通式（1)中作爲R2和R3之環烷基，較佳爲碳原子 數5至1 5，其係包括例如環戊基、環己基、環辛基。 通式（1 )中作爲R2和R3之烯基，較佳爲碳原子數爲2 -26- 200804575 至9，其係包括例如乙烯基、丙烯基、烯丙基。 在通式（1)中作爲R2和R3之炔基，較佳爲碳原子數 爲2至9，其係包括例如乙炔基、丙炔基、丁炔基。 在通式（1 )中作爲R2和R3之芳基，較佳爲碳原子數 爲6至1 5，其係包括例如苯基。 在通式（1 )中作爲R2和R3之各基也可含有之取代基 係包括：羥基、鹵素原子、芳香族環（較佳爲碳原子數爲3 至15)、羧基、胺基等。 ^ 在通式（1 )中作爲R4和R5之烷基，較佳爲碳原子數 爲1至8，其係包括例如甲基、乙基。 醯基，較佳爲碳原子數爲2至9，其係包括例如甲基羰 基。 通式（1)中作爲R4和R5之各基也可具有之取代基係 包括：羥基、胺基、鹵素原子。 在通式（1 )中，較佳爲R4和R5中任一者並非爲氫原 ^ 子。另外，在通式（1 )中，特佳爲R1係單鍵、R2和R4係 氫原子。此時，R3係代表氫原子、鹵素原子、羧基、烷基、 環烷基、烯基、炔基、或芳基；但是，特佳爲氫原子、烷基 。R5係代表氫原子、鹵素原子、羧基、烷基、或醯基；但是 ，特佳爲烷基。作爲R3之烷基也可含有之取代基，較佳爲 羥基、羧基或胺基。作爲R5之烷基也可具有之取代基，較 佳爲羥基或胺基。 在以通式（I )所代表的化合物中之伸烷基鏈中，也可 具有氧原子、硫原子等之雜原子。其中，所謂的「伸烷基鏈 -27- 200804575 」係意謂例如將烷基分割成末端部與鍵結部時，則其鍵結部 爲伸烷基之情形。R1 in the formula (1) represents a single bond, an alkyl group, or a phenyl group. The ruler 2 and the &amp; 3 series in the formula (1) each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an aryl group. R4 and R5 in the formula (1) each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, or a fluorenyl group. However, if R1 is a single bond, at least either of R4 and R5 is not an oxygen atom. The alkylene group in the general formula (1) may be any of a linear chain, a branched chain, and a cyclic group, and preferably has 1 to 8 carbon atoms, for example, it includes a methylene group and a stretching group. base. The substituent which the alkylene group may also contain includes a hydroxyl group, a halogen atom and the like. The alkyl group as R2 and R3 in the formula (1) preferably has 1 to 8 carbon atoms, and includes, for example, a methyl group, a propyl group and the like. The cycloalkyl group as R2 and R3 in the formula (1) preferably has 5 to 15 carbon atoms, and includes, for example, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The alkenyl group as R2 and R3 in the formula (1) preferably has 2 to 26,045,075 to 9, and includes, for example, a vinyl group, a propenyl group, or an allyl group. The alkynyl group as R2 and R3 in the formula (1) preferably has 2 to 9 carbon atoms, and includes, for example, an ethynyl group, a propynyl group, and a butynyl group. The aryl group as R2 and R3 in the formula (1) preferably has 6 to 15 carbon atoms, and includes, for example, a phenyl group. The substituent which may be contained in each of R2 and R3 in the formula (1) includes a hydroxyl group, a halogen atom, an aromatic ring (preferably having 3 to 15 carbon atoms), a carboxyl group, an amine group and the like. The alkyl group as R4 and R5 in the formula (1) preferably has 1 to 8 carbon atoms, and includes, for example, a methyl group or an ethyl group. The fluorenyl group preferably has 2 to 9 carbon atoms, and includes, for example, a methylcarbonyl group. The substituent which may be contained in each of R4 and R5 in the formula (1) may include a hydroxyl group, an amine group, and a halogen atom. In the formula (1), it is preferred that any of R4 and R5 is not a hydrogen atom. Further, in the formula (1), a R1 single bond, R2 and R4 hydrogen atoms are particularly preferred. In this case, R3 represents a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group; however, it is particularly preferably a hydrogen atom or an alkyl group. R5 represents a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group or a fluorenyl group; however, it is particularly preferably an alkyl group. The alkyl group as R3 may also have a substituent, and is preferably a hydroxyl group, a carboxyl group or an amine group. The alkyl group as R5 may have a substituent, and is preferably a hydroxyl group or an amine group. The alkylene chain in the compound represented by the formula (I) may have a hetero atom such as an oxygen atom or a sulfur atom. Here, the "alkylene chain -27-200804575" means a case where, for example, when the alkyl group is divided into a terminal portion and a bonding portion, the bonding portion is an alkyl group.

HOOG-R6—G-N R8 XR10-COOH (2) 在通式（2)中之R6係代表單鍵、伸烷基、或伸苯基。 在通式（2 )中之R7和R8係各自獨立地代表氫原子、鹵素 • 原子、羧基、烷基、環烷基、烯基、炔基、或芳基。在通式 (2 )中之R9係代表氫原子、鹵素原子、羧基、或烷基。在 通式（2)中之R1G係代表伸烷基。但是，若R1G爲一 CH2 — 時，R6則係非爲單鍵，或R9非爲氫原子之兩者中之至少任 在通式（2 )中作爲R6和R1()之伸烷基係可爲直鏈狀、 分枝狀、環狀中之任一者，較佳爲碳原子數爲1至8,其係 包括例如亞甲基、伸乙基。 如上所述之伸烷基和伸苯基也可具有之取代基係包括 經基、鹵素原子等。 在通式（2 )中作爲R7和R8之烷基，較佳爲碳原子數 爲1至8，其係包括例如甲基、丙基等。 在通式（2)中作爲R7和R8之環烷基，較佳爲碳原子 數爲5至1 5，其係包括例如環戊基 '環己基、環辛基。 在通式（2)中作爲R7和R8之烯基，較佳爲碳原子數 爲2至9，其中較佳爲例如乙烯基、丙烯基、烯丙基。 在通式（2 )中作爲R7和R8之炔基，較佳爲碳原子數 -28- 200804575 爲2至9，其係包括例印乙炔基、丙炔基、丁炔基。 在通式（2)中作爲化7和R8之芳基，較佳爲碳原子數 爲6至1 5，其係包括例如苯基。 在通式（2 )中作爲R7和R8之各基也可具有之取代基 係包括例如羥基、鹵素原子、芳香族環（較隹爲碳原子數爲 3至15 )等。 在通式（2)中作爲R9之烷基，較佳爲碳原子數爲1至 8，其係包括例如甲基、乙基。 在通式（2 )中作爲R9之醯基，較佳爲碳原子數爲2至 9，其係包括例如甲基羰基。 在通式（2 )中作爲R9之各基也可具有之取代基係包括 例如羥基、胺基、鹵素原子、羧基。 另外’在通式（2)中’較佳爲R9並非爲氯原子。 在以通式（I)所代表的化合物中之伸烷基鏈中，也可 具有氧原子、硫原子等之雜原子。其中，所謂的「伸烷基鏈 | 」係意謂例如將烷基分割成末端部與鍵結部時’則其鍵結部 爲伸烷基之情形。 在下文中，則將例示以通式（1 )或通式（2 )所代表的 化合物之較佳的具體實例，但是並不受限於此等。 -29- 200804575 表1HOOG-R6-G-N R8 XR10-COOH (2) R6 in the formula (2) represents a single bond, an alkyl group, or a phenyl group. R7 and R8 in the formula (2) each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an aryl group. The R9 in the formula (2) represents a hydrogen atom, a halogen atom, a carboxyl group, or an alkyl group. The R1G system in the formula (2) represents an alkylene group. However, if R1G is a CH2—, R6 is not a single bond, or at least R9 is not a hydrogen atom, and at least any of the alkyl groups of R6 and R1() in the formula (2) may be used. It is preferably a linear one, a branched form or a cyclic form, and preferably has 1 to 8 carbon atoms, and includes, for example, a methylene group and an ethylidene group. The alkyl group and the extended phenyl group as described above may also have a substituent group including a mesogenic group, a halogen atom and the like. The alkyl group as R7 and R8 in the formula (2) preferably has 1 to 8 carbon atoms, and includes, for example, a methyl group, a propyl group and the like. The cycloalkyl group of R7 and R8 in the formula (2) preferably has a carbon number of 5 to 15, and includes, for example, a cyclopentyl 'cyclohexyl group, a cyclooctyl group. The alkenyl group as R7 and R8 in the formula (2) preferably has 2 to 9 carbon atoms, and among them, for example, a vinyl group, a propenyl group or an allyl group is preferable. The alkynyl group as R7 and R8 in the formula (2) preferably has 2 to 9 carbon atoms in the range of -28 to 200804575, and includes ethynyl groups, propynyl groups and butynyl groups. The aryl group of the formula 7 and R8 in the formula (2) preferably has 6 to 15 carbon atoms, and includes, for example, a phenyl group. The substituent which may be contained in each of R7 and R8 in the formula (2) includes, for example, a hydroxyl group, a halogen atom, an aromatic ring (compared to 3 to 15 carbon atoms), and the like. The alkyl group as R9 in the formula (2) preferably has 1 to 8 carbon atoms, and includes, for example, a methyl group or an ethyl group. The fluorenyl group as R9 in the formula (2) preferably has 2 to 9 carbon atoms, and includes, for example, a methylcarbonyl group. The substituent which may be a group of R9 in the formula (2) may include, for example, a hydroxyl group, an amine group, a halogen atom or a carboxyl group. Further, in the formula (2), it is preferred that R9 is not a chlorine atom. The alkylene chain in the compound represented by the formula (I) may have a hetero atom such as an oxygen atom or a sulfur atom. Here, the term "alkylene chain" means a case where, for example, when the alkyl group is divided into a terminal portion and a bonding portion, the bonding portion is an alkylene group. Hereinafter, preferred specific examples of the compound represented by the general formula (1) or the general formula (2) will be exemplified, but are not limited thereto. -29- 200804575 Table 1

R1 R2 R3 R4 R5 A-l - -H -H -H -ch3 A-2 • -H -H -H -CH^OH A-3 - -H -H -ch2oh -GH2OH A-4 - - H -H -H -CHaCHiOH A-5 - -H -H - CH2CHi〇H -CH2CH2OH A-6 • -H -CHS -H -ch2oh A-7 - -H - ch3 «CH2CH2OH -gh2ch2oh A- 8 續 -H -ch2oh -H -CH^OH A-9 - -H -CH(CH3)2 -ch2oh -*ch2oh A-1D - -H -Ph -H -(CH2CH20)2-H A-11 - -H ~CH2X? H -CH2CH2OH -ch2ch2oh A-12 - -H -CH2SCH3 -ch2ch2oh *ch2ch2oh A-13 - -H - H -H _coch2nh2 A-14 - 十 ~ch2oh -H -coch2nh2 A，15 一 -H -H - H -coch3 A-16 -ch2- -CH2CH2OH -CH2CH2OH Α·17 -gh2， -H -H -ch2oh A-18 -CHr -H - H -coch2nh2 A-19 -CH2CHr - H -H -H -H -30- 200804575 表2R1 R2 R3 R4 R5 Al - -H -H -H -ch3 A-2 • -H -H -H -CH^OH A-3 - -H -H -ch2oh -GH2OH A-4 - - H -H - H -CHaCHiOH A-5 - -H -H - CH2CHi〇H -CH2CH2OH A-6 • -H -CHS -H -ch2oh A-7 - -H - ch3 «CH2CH2OH -gh2ch2oh A- 8 Continued -H -ch2oh - H -CH^OH A-9 - -H -CH(CH3)2 -ch2oh -*ch2oh A-1D - -H -Ph -H -(CH2CH20)2-H A-11 - -H ~CH2X? H - CH2CH2OH -ch2ch2oh A-12 - -H -CH2SCH3 -ch2ch2oh *ch2ch2oh A-13 - -H - H -H _coch2nh2 A-14 - 十~ch2oh -H -coch2nh2 A,15 One-H -H - H -coch3 A -16 -ch2- -CH2CH2OH -CH2CH2OH Α·17 -gh2, -H -H -ch2oh A-18 -CHr -H - H -coch2nh2 A-19 -CH2CHr - H -H -H -H -30- 200804575 2

HOO ㈣⑵ ή8 R10-COOH R6 R7 R8 R® R10 B-1 - -H -H -ch3 -CHr B-2 - -H -H -ch2oh -CHr Β·3 - -H -H -ch2ch2oh -CH厂 Β-4 - -H -(CH2CH2O)10-H -ch2- Β-5 • -ch3 -H 9H3 —CH— Β-6 賺 -H -ch2oh -H 9H2OH —CH— Β-7 -ch2- -H -H -H -ch2- Β-8 -CHr -H -H -H -ch2ch2- Β-Β -ch2- -H -H -ch2ch2oh -ch2ch2- Β-10 -ch2- -H -H -CH2C00H -ch2- 以通式（1 )或（2)所代表的化合物之合成方法，並無 特殊限制，可以習知的方法來合成。另外，以通式（1 )或 (2 )所代表之化合物係也可使用市售商品級者。 • 在本發明之硏磨用組成物中，在分子內至少具有一個竣 基及至少具有一個胺基的化合物之添加量，若從將硏磨速率 和平坦性之兩者並存的觀點來看，則較佳爲〇 · 1重量％以上 、5重量％以下，更佳爲0.5重量％以上、2重量％以下。 〈（g)磷酸鹽或亞磷酸鹽〉 在本發明之硏磨用組成物中，若含有硏磨粒以外之無機 成份時，則較佳爲含有（g)磷酸鹽或亞磷酸鹽。 在本發明之硏磨用組成物中，較佳爲以因對於硏磨面的 反應性或吸附性、硏磨金屬之溶解性、被硏磨面之電化學性 -31- 200804575 質、化合物官能基之解離狀態、作爲液應有之穩定性等適當 地設定如上所述之成份的種類、添加量、或pH。 在本發明之硏磨用組成物中的pH爲如上所述者。 〈（h )氧化劑〉 本發明之硏磨用組成物，較佳爲含有能將適合的硏磨對 象之金屬加以氧化的化合物（氧化劑）。 「氧化劑」係包括例如：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。 鐵（III)鹽係除例如硝酸鐵（III )、氯化鐵（III )、 硫酸鐵（III )、溴化鐵（III )等無機之鐵（III)鹽以外， 適合使用鐵（III)之有機錯合鹽。 使用鐵（III )之有機錯合鹽時，用於構成鐵（III )錯 合鹽之錯合物形成化合物係例如：除了醋酸、檸檬酸、草酸 、柳酸、二乙基二硫胺甲酸、琥珀酸、酒石酸、乙醇酸、甘 攀 胺酸、丙胺酸、天冬胺酸、硫乙醇酸、伸乙基二胺、伸丙基 二胺、二伸乙甘醇、三伸乙甘醇、1，2-乙二醇、丙二酸、戊 二酸、3-羥基丁酸、丙酸、鄰苯二甲酸、間苯二甲酸、3-羥 基柳酸、3,5-二羥基柳酸、五倍子酸、苯甲酸、順丁烯二酸 等或該等之鹽以外，也包括胺基多元羧酸及其鹽。 「胺基多元羧酸及其鹽」係包括：伸乙基二胺 -冰扎1^’，：^’-四醋酸、二伸乙基三胺五醋酸、1，3-二胺基丙烷 -氷冰&gt;1’，&gt;1’-四醋酸、1，2-二胺基丙烷-&gt;1，：^，：^’，：^’-四醋酸、伸 -32- 200804575 乙基二胺-N，N’-二琥珀酸（外消旋體）、伸乙基二胺二琥珀 酸（SS體）、N- ( 2-羧酸根合乙基）-L·天冬胺酸、N·(羧 基甲基）天冬胺酸、/3-丙胺酸二醋酸、甲基亞胺基二醋 酸、氮川三醋酸、環己烷二胺四醋酸、亞胺基二醋酸、乙二 醇醚二胺四醋酸、伸乙基二胺1-N，N’-二醋酸、伸乙基二胺 鄰羥基苯基醋酸、N，N-雙（2-羥基苯甲基）伸乙基二胺·ν，Ν-二醋酸等及其鹽。相對鹽之種類較佳爲鹼金屬鹽及銨鹽，特 佳爲銨鹽。 此等之中，較佳爲過氧化氫、碘酸鹽、次氯酸鹽、氯酸 鹽、過硫酸鹽、鐵（ΠΙ)之有機錯合鹽，若使用鐵（m) 之有機錯合鹽時，其較佳的錯合物形成化合物係包括：檸檬 酸、酒石酸、胺基多元羧酸〔具體而言，其係包括：伸乙基 二胺-N，N，N’，N’-四醋酸、二伸乙基三胺五醋酸、1，3-二胺基 丙烷-N，N，N’，N’-四醋酸、伸乙基二胺-N，N’-二琥珀酸（外消 旋體）、伸乙基二胺二琥珀酸（SS體）、N-(2-羧酸根合乙 基）-L-天冬胺酸、N-(羧基甲基）-L-天冬胺酸、/3 -丙胺酸 二醋酸、甲基亞胺基二醋酸、氮川三醋酸、亞胺基二醋酸〕 〇 在該等氧化劑中，最佳爲過氧化氫、過硫酸鹽、以及鐵 (III )之伸乙基二胺-N，N，N’，N’-四醋酸、1，3-二胺基丙烷 -N，N，N’，N’-四醋酸及伸乙基二胺二琥珀酸（SS體）之錯合 氧化劑之添加量，相對於每1公升之使用於硏磨時的硏 磨用組成物，較佳爲設定在0.003莫耳至8莫耳，更佳爲設 -33- 200804575 定在0·03莫耳至6莫耳，特佳爲設定在〇1莫耳至$莫耳。 亦即，氧化劑之添加量，從確保充分的金屬氧化且高CMP 速率的觀點來看，則較佳爲0·003莫耳以上；從防止硏磨面 變粗糙的觀點來看，則較佳爲8莫耳以下。 〔配線金屬原材料〕 在本發明中，屬於硏磨對象的半導體，較佳爲具有由銅 金屬和/或銅合金所構成之配線的LSI，特佳爲銅合金。並且 ’在銅合金之中，較佳爲含銀的銅合金。包含在銅合金中之 銀含量較佳爲40重量％以下，特佳爲1〇重量％以下，進一 步更佳爲1重量％以下，且在0.00001至O.i重量％之範圍的 銅合金是最能發揮優異功效。 〔配線之大小〕 在本發明中，硏磨對象的半導體，例如若爲屬於DRAM (動態隨機存取記憶體）裝置系列時，以半線寬（half pitch )計則較佳爲Ο . 1 5 // m以下，特佳爲Ο · 1 Ο μ m以下，進一步 更佳爲0.0 8 /z m以下，若爲屬於MPU (微處理單元）裝置系 列時，則較佳爲具有〇·12/ζ m以下，特佳爲0.09/z m以下， 進一步更佳爲0.07/zm以下之配線的LSI。對於此等之LSI ，本發明之硏磨液將可發揮特別優異的功效。 〔阻障金屬〕 在本發明中，半導體較佳爲在由銅金屬和/或銅合金所 構成之配線與層間絶緣膜之間’設置用於防止銅的擴散之阻 障層。阻障層較佳爲使用低電阻之金屬材料，特佳爲cJiN、 TiW、Ta、TaN、W、WN、Ru，其中，特佳爲 Ta、TaN。 -34- •200804575 〔硏磨方法〕 本發明之硏磨用組成物，使用時可採用屬於濃縮液，而 在使用時則予以加水稀釋以作爲使用液之方法，各成份係以 容後所述之水溶液形態予以混合該等，必要時則加水稀釋以 作爲使用液之方法，或已經調製成爲使用液之方法等。 使用本發明之硏磨用組成物的硏磨方法，對於如上所述 之任何方法都可適用，將硏磨液供應至硏磨平台上之硏磨墊 0 ，將其與被硏磨面接觸並使被硏磨面與硏磨墊相對運動以實 施硏磨之硏磨方法。 用於硏磨之裝置，可使用包括用於保持具有被硏磨面的 半導體基板等之保持器，與貼附硏磨墊（且搭配可改變轉速 的馬達等）的硏磨平台之一般硏磨裝置。 「硏磨墊之材料」並無特殊限制，可使用一般性的不織 布、發泡聚胺基甲酸酯、多孔質氟樹脂等。 硏磨條件雖然並無特殊限制，但是硏磨平台之旋轉速度 φ 較佳爲200 rpm以下之低轉速，以使基扳不至於被拋出。 具有被硏磨面（被硏磨膜）的半導體基板對於硏磨墊的 加壓壓力，較佳爲3 psi ( 0.0207 MPa)以下，更佳爲〇.1至 2 psi ( 0.00069 MPa至0.0138 MPa)，爲符合硏磨速率之晶 圓面內均勻性及圖案平坦性之條件，則更佳爲0.5至1.5 psi (0.00345 MPa 至 0.0104 MPa) ° 在進行硏磨之期間，對於硏磨墊應連續地以泵等來供應 硏磨用組成物。該供應量雖然並無特殊限制，但是較佳爲能 使硏磨墊表面經常爲硏磨用組成物所覆蓋。 -35- 200804575 硏磨結束後之半導體基板，則在流水中充分地加以洗淨 後，使用自旋乾燥機等來拂落附著於半導體基板上的水滴後 ，將其乾燥。若使用本發明之硏磨用組成物時，硏磨後的洗 淨性則將變得良好。其係可推測爲硏磨粒和配線金屬的靜電 互相排斥作用所造成。 在本發明之硏磨方法中，用於稀釋的水溶液係與如下所 述之水溶液相同。 水溶液係以預先含有氧化劑、酸、添加劑、界面活性劑 中之至少一種以上的水，予以稀釋成能使得水溶液中所含有 的成份和供稀釋的硏磨用組成物的成份之總成份成爲在使 用硏磨用組成物來進行硏磨時之成份。在以水溶液稀釋後使 用之情況，則可將不易溶解之成份以水溶液之形態來混合， 以調製成更濃縮之硏磨用組成物。 對於經濃縮之硏磨用組成物以加水來稀釋之方法，則有 一種將用於供應經濃縮之硏磨用組成物的配管與用於供應 水的配管，在途中將其合流加以混合，然後將經混合稀釋的 硏磨用組成物供應至硏磨墊之方法。 混合係可採用慣用之方法，亦即，在賦予壓力之狀態下 通過狹窄通路以使液彼此衝突混合之方法、在配管中裝入玻 璃管等之塡充物以使液體之流動反複進行分流分離、合流之 方法、以及在配管中設置以動力旋轉的翼片之方法等。 硏磨用組成物之供應速率較佳爲10至1，000毫升/分鐘 ，若欲符合硏磨速率之晶圓面內均勻性及圖案平坦性之條件 時，則更佳爲170至8 00毫升/分鐘。 -36- 200804575 經濃縮之硏磨用組成物以水溶液等加以稀釋以硏磨之 方法，其係獨立地設置用於供應硏磨用組成物之配管與用於 供應水或水溶液之配管，並分別對硏磨墊供應特定量之液， 而藉由硏磨墊與被硏磨面的相對運動來邊混合邊硏磨之方 法。 另外，也有一種在一個容器裝入特定量的經濃縮之硏磨 用組成物與水並加以混合後，對硏磨墊供應該經混合之硏磨 用組成物，以硏磨之方法。 本發明之另一種硏磨方法，其係將硏磨用組成物所應含 有之成份至少分成爲兩種構成成份，並在使用該等時，則予 以加水稀釋後供應至硏磨平台上之硏磨墊，將其與被硏磨面 接觸，並使被硏磨面與硏磨墊相對運動，以硏磨之方法。 例如，若氧化劑爲一構成成份（A )，而酸、添加劑、 界面活性劑及水爲另一構成成份（B )，在使用其等時，則 以水將構成成份（A)與構成成份（B)加以稀釋來使用。 另外，將溶解度低的添加劑分成爲兩種構成成份（A) 與（B )，將氧化劑、添加劑及界面活性劑爲一構成成份（A )，將酸、添加劑、界面活性劑及水爲另一構成成份（B ) ，在使用其等時，則加入水以將構成成份（A )與構成成份 (B )加以稀釋來使用。 在該實例之情況時，則需要分別供應構成成份（A )與 構成成份（B)與水之三種配管。稀釋混合之方法，則有將 三種配管連結於供應至硏磨墊之一配管，而在其配管內加以 混合之方法。此種情形下，也可採取先連結兩種配管後再連 -37- 200804575 結其他之一配管之方法。 例如，可採取先混合含有不易溶解的添加劑之構成成份 與其他構成成份，並延長混合路徑以確保溶解時間後，再連 結水配管之方法。 其他之混合方法，則可如上所述直接將三個配管分別引 導至硏磨墊，而以硏磨墊與被硏磨面之相對運動加以混合之 方法、在一個容器混合三種構成成份，並由其將經稀釋之硏 磨用組成物供應至硏磨墊之方法等。 在如上所述之硏磨方法中，也可採取將含有氧化劑之一 構成成份設定爲40°C以下，將其他構成成份由室溫加溫至 lOOt之範圍，且在一構成成份與其他構成成份或加水稀釋 來使用時，則在經混合後設定爲40°C以下之方法。 由於溫度一旦升高，溶解度將增加，因此在提高硏磨用 組成物之低溶解度原料的溶解度上是適合使用之方法。 將未含氧化劑的其他成份以由室溫至1 〇〇°C之範圍加溫 而將其溶解之原料，由於溫度一旦降低，則將會析出至溶液 中，因此若使用溫度已降低的該成份時，則必須預先將加溫 所析出者加以溶解。 其可採取輸送經加溫溶解的構成成份液之方法’與預先 攪拌含析出物之液，然後送液並將配管加溫以將其溶解之方 經加溫之成份，若將含氧化劑的一構成成份之溫度提高 至40°C以上時，則有可能導致氧化劑發生分解之顧慮。因此 ，在經加溫之構成成份，與含有用於冷卻該經加溫之構成成 -38- 200804575 份之氧化劑的一構成成份進行混合之情形下，則必須設定爲 40°C以下。 在本發明中，如上所述可將硏磨用組成物之成份分成兩 種以上來供應至硏磨面。此時，較佳爲分成爲含氧化物的成 份與含酸的成份來供應。另外，也可採取將硏磨用組成物作 成爲濃縮液，稀釋水則分開供應至硏磨面之方式。 〔墊〕 「硏磨用之墊（pad)」可爲無發泡結構之墊或發泡結 ^ 構之墊。前者係如塑膠板以硬質合成樹脂整體材料用作爲墊 者。另外，後者則有獨立發泡體（乾式發泡系列）、連續發 泡體（濕式發泡系列）、兩層複合體（積層系列）之三種， 特佳爲兩層複合體（積層系列）。發泡係可爲均勻或不均勻 〇 並且，也可爲含有使用於「硏磨之硏磨粒」（例如，二 氧化鈽、二氧化矽、氧化鋁、樹脂等）者。另外，各自可分 φ 成爲硬度爲軟質與硬質者，但是任一種皆可用。積層系列之 墊，較佳爲各層使用不同硬度者。 「墊之材質」較佳爲不織布、人工皮革、聚醯胺、聚胺 基甲酸酯、聚酯、聚碳酸酯等。 另外，對於硏磨面與墊相接觸之面，也可施加格子槽溝 /洞穴/同心槽溝/螺旋狀槽溝等之加工。 〔晶圓〕 使用本發明之硏磨用組成物來實施CMP之對象晶圓的 直徑較佳爲爲200毫米以上，特佳爲300毫米以上。若在300 -39- 200804575 毫米以上時，則特別是本發明之硏磨用組成物可發揮顯著的 功效。 《實施例》 以下以實施例說明本發明。但是本發明並不受限於此等 實施例。 (使用鋁酸鹽離子加以表面改質的膠質二氧化矽（A-1 )之 調製） 對於1，000克之經水解四乙氧基矽烷所製得平均硏磨粒 Φ 大小（平均一次粒徑）爲3 5奈米之膠質二氧化矽（製品名 :Quotron PL-3，製造廠商：扶桑化學公司）之20重量％水 分散物，加入氨水以調整pH爲9.0。其後，則在室溫攪拌下 ，在數分鐘內將15.9克之 Al2〇3濃度爲 3.6重量％、HOO (4)(2) ή8 R10-COOH R6 R7 R8 R® R10 B-1 - -H -H -ch3 -CHr B-2 - -H -H -ch2oh -CHr Β·3 - -H -H -ch2ch2oh -CH Factory -4 - -H -(CH2CH2O)10-H -ch2- Β-5 • -ch3 -H 9H3 -CH- Β-6 earn -H -ch2oh -H 9H2OH -CH- Β-7 -ch2- -H - H -H -ch2- Β-8 -CHr -H -H -H -ch2ch2- Β-Β -ch2- -H -H -ch2ch2oh -ch2ch2- Β-10 -ch2- -H -H -CH2C00H -ch2- The method for synthesizing the compound represented by the formula (1) or (2) is not particularly limited and can be synthesized by a conventional method. Further, a commercially available product grade can also be used as the compound represented by the formula (1) or (2). In the honing composition of the present invention, the amount of the compound having at least one thiol group and at least one amine group in the molecule is from the viewpoint of coexisting both the honing rate and the flatness. It is preferably 重量·1% by weight or more and 5% by weight or less, more preferably 0.5% by weight or more and 2% by weight or less. <(g) Phosphate or phosphite> When the inorganic component other than the honing particles is contained in the honing composition of the present invention, it is preferred to contain (g) a phosphate or a phosphite. In the honing composition of the present invention, it is preferred that the reactivity or the adsorption property to the honing surface, the solubility of the honed metal, and the electrochemical property of the honed surface - 31-200804575, compound function The type of the component, the amount of addition, or the pH as described above is appropriately set in the dissociation state of the substrate, the stability as the liquid, and the like. The pH in the honing composition of the present invention is as described above. <(h) oxidizing agent> The honing composition of the present invention preferably contains a compound (oxidizing agent) capable of oxidizing a metal of a suitable honing object. "Oxidant" includes, for example, hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate , dichromate, permanganate, ozone water and silver (II) salt, iron (III) salt. The iron (III) salt is preferably iron (III) except for an inorganic iron (III) salt such as iron (III) nitrate, iron (III) chloride, iron (III) sulfate or iron (III). Organically mixed salt. When an organic complex salt of iron (III) is used, a complex forming compound for constituting an iron (III) complex salt is, for example, in addition to acetic acid, citric acid, oxalic acid, salicylic acid, diethyldithiocarbamic acid, Succinic acid, tartaric acid, glycolic acid, glycoside, alanine, aspartic acid, thioglycolic acid, ethyl diamine, propyl diamine, diethylene glycol, triethylene glycol, 1 , 2-ethylene glycol, malonic acid, glutaric acid, 3-hydroxybutyric acid, propionic acid, phthalic acid, isophthalic acid, 3-hydroxysalic acid, 3,5-dihydroxysalic acid, gallnut Acids, benzoic acid, maleic acid, etc., or the like, also include amine-based polycarboxylic acids and salts thereof. "Amine-based polycarboxylic acid and its salt" include: ethylidene diamine-ice slag 1^', :^'-tetraacetic acid, di-extended ethyltriamine pentaacetic acid, 1,3-diaminopropane- Ice Ice &gt;1',&gt;1'-tetraacetic acid, 1,2-diaminopropane-&gt;1,:^,:^',:^'-tetraacetic acid, extension-32-200804575 ethyl Amine-N,N'-disuccinic acid (racemate), ethyldiamine disuccinic acid (SS body), N-(2-carboxyethylate)-L-aspartic acid, N ·(carboxymethyl)aspartic acid, /3-alanine diacetate, methylimidodiacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol ether Diamine tetraacetic acid, ethyldiamine 1-N,N'-diacetic acid, ethyldiamine o-hydroxyphenylacetic acid, N,N-bis(2-hydroxybenzyl)ethylidene diamine ν, Ν-diacetic acid and the like and salts thereof. The type of the relative salt is preferably an alkali metal salt or an ammonium salt, and particularly preferably an ammonium salt. Among them, preferred are organically-substituted salts of hydrogen peroxide, iodate, hypochlorite, chlorate, persulfate, and iron, and if an organic complex salt of iron (m) is used. In the preferred embodiment, the complex complex forming compound includes: citric acid, tartaric acid, and an amine-based polycarboxylic acid (specifically, the system includes: ethylene diamine-N, N, N', N'-four Acetic acid, di-ethyltriamine pentaacetic acid, 1,3-diaminopropane-N,N,N',N'-tetraacetic acid, ethylidene diamine-N,N'-disuccinic acid Spiral), ethyldiamine disuccinic acid (SS body), N-(2-carboxyethylate)-L-aspartic acid, N-(carboxymethyl)-L-aspartic acid , /3 - alanine diacetic acid, methyl iminodiacetic acid, nitrilotriacetic acid, iminodiacetic acid] 〇 among these oxidizing agents, preferably hydrogen peroxide, persulfate, and iron (III Ethyldiamine-N,N,N',N'-tetraacetic acid, 1,3-diaminopropane-N,N,N',N'-tetraacetic acid and ethyldiaminediamide The amount of the wrong oxidizing agent of the acid (SS body) is used for honing per 1 liter. The composition for honing is preferably set at 0.003 m to 8 m, more preferably -33-200804575 at 0. 03 m to 6 m, especially preferably at 〇1 m to $mear. That is, the amount of the oxidizing agent added is preferably from 0.003 mol or more from the viewpoint of ensuring sufficient metal oxidation and a high CMP rate, and from the viewpoint of preventing roughening of the honing surface, it is preferably 8 moles below. [Wiring metal material] In the present invention, the semiconductor to be honed is preferably an LSI having a wiring composed of a copper metal and/or a copper alloy, and particularly preferably a copper alloy. Further, among the copper alloys, a copper alloy containing silver is preferred. The content of silver contained in the copper alloy is preferably 40% by weight or less, particularly preferably 1% by weight or less, still more preferably 1% by weight or less, and the copper alloy in the range of 0.00001 to 0% by weight is most effective. Excellent efficacy. [Size of Wiring] In the present invention, when the semiconductor to be honed is, for example, a DRAM (Dynamic Random Access Memory) device series, it is preferable to use a half pitch (Ο). / / m or less, particularly preferably Ο · 1 Ο μ m or less, further preferably 0.0 8 /zm or less, and if it is an MPU (Micro Processing Unit) device series, it is preferably 〇·12/ζ m In the following, an LSI having a wiring of 0.09/zm or less, and more preferably 0.07/zm or less is particularly preferable. For these LSIs, the honing fluid of the present invention will exert particularly excellent effects. [Barrier Metal] In the present invention, the semiconductor preferably has a barrier layer for preventing diffusion of copper between the wiring composed of copper metal and/or copper alloy and the interlayer insulating film. The barrier layer is preferably a metal material having a low electrical resistance, and particularly preferably cJiN, TiW, Ta, TaN, W, WN, Ru, and particularly preferably Ta or TaN. -34- •200804575 [Horse method] The composition for honing of the present invention can be used as a concentrated liquid when it is used, and diluted with water to be used as a use liquid, and each component is described later. The aqueous solution form is mixed, and if necessary, diluted with water to be used as a liquid, or a method of preparing a liquid to be used. The honing method using the honing composition of the present invention is applicable to any of the methods described above, and the honing liquid is supplied to the honing pad 0 on the honing table to be in contact with the honed surface. A honing method in which the honed surface is moved relative to the honing pad to perform honing. For honing, a honing platform including a semiconductor substrate for holding a honed surface, and a honing platform to which a honing pad is attached (and a motor that can change the rotational speed, etc.) can be used. Device. The "material of the honing pad" is not particularly limited, and a general non-woven fabric, a foamed polyurethane, a porous fluororesin or the like can be used. Although the honing condition is not particularly limited, the rotational speed φ of the honing platform is preferably a low rotational speed of 200 rpm or less so that the base plate is not thrown. The pressing pressure of the semiconductor substrate having the honed surface (the honed film) for the honing pad is preferably 3 psi (0.0207 MPa) or less, more preferably 〇1 to 2 psi (0.00069 MPa to 0.0138 MPa). It is preferably 0.5 to 1.5 psi (0.00345 MPa to 0.0104 MPa) for the in-plane uniformity and pattern flatness of the honing rate. During the honing, the honing pad should be continuously The honing composition is supplied by a pump or the like. Although the supply amount is not particularly limited, it is preferable that the surface of the honing pad is often covered by the honing composition. -35- 200804575 The semiconductor substrate after completion of the honing is sufficiently washed in running water, and then the water droplets adhering to the semiconductor substrate are dropped by a spin dryer or the like, and then dried. When the composition for honing of the present invention is used, the rinsing property after honing becomes good. It can be presumed to be caused by the mutual repelling of static electricity between the honing particles and the wiring metal. In the honing method of the present invention, the aqueous solution used for dilution is the same as the aqueous solution described below. The aqueous solution is diluted with water containing at least one of an oxidizing agent, an acid, an additive, and a surfactant in advance so that the total component of the component contained in the aqueous solution and the component of the honing composition to be diluted is used. The ingredients used for honing with the composition. In the case of being diluted with an aqueous solution, the less soluble components can be mixed in the form of an aqueous solution to prepare a more concentrated honing composition. For the method of diluting the concentrated honing composition by adding water, there is a pipe for supplying the concentrated honing composition and a pipe for supplying water, which are combined and mixed on the way, and then A method of supplying a mixed-diluted honing composition to a honing pad. The mixing method may be a conventional method in which a liquid is passed through a narrow passage in a state where pressure is applied to cause a liquid to collide with each other, and a filler such as a glass tube is placed in a pipe to repeatedly perform split separation of the flow of the liquid. , a method of joining, and a method of providing a power-rotating fin in a pipe. The supply rate of the honing composition is preferably from 10 to 1,000 ml/min, and more preferably 170 to 800 ml if the wafer in-plane uniformity and pattern flatness are to be met. /minute. -36- 200804575 The concentrated honing composition is diluted with an aqueous solution or the like to be honed, and the piping for supplying the honing composition and the piping for supplying water or the aqueous solution are separately provided, and respectively A method of supplying a specific amount of liquid to the honing pad while mixing and honing by the relative movement of the honing pad and the surface to be honed. Further, there is also a method of supplying the mixed honing composition to a honing pad after a specific amount of the concentrated honing composition and water are mixed in a container. Another honing method according to the present invention is characterized in that at least the components to be contained in the honing composition are divided into two constituent components, and when used, they are diluted with water and supplied to the honing platform. Grinding the pad, contacting it with the honed surface, and moving the honed surface against the honing pad to honing. For example, if the oxidizing agent is a constituent component (A) and the acid, the additive, the surfactant, and the water are the other constituent component (B), when the composition or the like is used, the constituent component (A) and the constituent component are represented by water ( B) Use diluted to use. In addition, the low solubility additive is divided into two components (A) and (B), the oxidizing agent, the additive and the surfactant are a constituent (A), and the acid, the additive, the surfactant and the water are the other. When the component (B) is used, water is added to dilute the component (A) and the component (B) to be used. In the case of this example, it is necessary to supply three kinds of pipes of the constituent component (A) and the constituent component (B) and water, respectively. In the method of diluting and mixing, there are a method in which three kinds of pipes are connected to a pipe supplied to one of the honing pads and mixed in the pipes. In this case, it is also possible to connect the two types of piping and then connect the other one of the -37-200804575. For example, a method of mixing a constituent component containing a non-dissolving additive with other constituent components and extending the mixing path to ensure a dissolution time and then connecting the water piping can be employed. In other mixing methods, the three pipes can be directly guided to the honing pad as described above, and the three components can be mixed in one container by mixing the honing pad with the relative movement of the honing surface. It is a method of supplying a diluted honing composition to a honing pad or the like. In the honing method as described above, it is also possible to set one of the constituent components containing the oxidizing agent to 40 ° C or less, and to heat the other constituent components from room temperature to 100 °, and in a constituent component and other constituent components. When it is diluted with water, it is set to 40 ° C or less after mixing. Since the solubility increases as the temperature rises, it is a suitable method for increasing the solubility of the low solubility raw material of the honing composition. The raw material which does not contain the oxidizing agent and is heated by heating from room temperature to 1 〇〇 ° C, will be precipitated into the solution as the temperature is lowered, so if the temperature is lowered, the component is lowered. At the time, the precipitated person must be dissolved in advance. The method may be a method of conveying a component liquid which is dissolved by heating and a liquid which preliminarily agitates the liquid containing the precipitate, and then the liquid is supplied and the pipe is heated to dissolve it, if the oxidizing agent is used When the temperature of the constituent component is raised to 40 ° C or higher, there is a concern that the oxidizing agent may be decomposed. Therefore, in the case where the component to be heated is mixed with a constituent component containing an oxidizing agent for cooling the heated composition of -38 to 200804575, it is necessary to set it to 40 ° C or lower. In the present invention, as described above, the components of the honing composition can be divided into two or more kinds to be supplied to the honing surface. In this case, it is preferred to supply the oxide-containing component and the acid-containing component. Further, it is also possible to adopt a method in which the honing composition is used as a concentrate, and the dilution water is separately supplied to the honing surface. [Pad] The "pad for honing" may be a mat for a non-foamed structure or a mat for a foamed structure. The former is used as a plastic sheet with a hard synthetic resin as a whole material. In addition, the latter has three types of independent foam (dry foaming series), continuous foam (wet foaming series), and two-layer composite (layered series), especially two-layer composite (layered series) . The foaming system may be uniform or non-uniform, and may also be used in the "honing abrasive grains" (for example, cerium oxide, cerium oxide, aluminum oxide, resin, etc.). In addition, each of them can be divided into φ to be soft and hard, but any one can be used. The pads of the laminated series are preferably those having different hardnesses for each layer. The "material of the mat" is preferably a non-woven fabric, an artificial leather, a polyamide, a polyurethane, a polyester, a polycarbonate or the like. In addition, the processing of the lattice groove/cavity/concentric groove/spiral groove may be applied to the surface where the honing surface is in contact with the mat. [Wafer] The diameter of the target wafer on which CMP is applied by using the honing composition of the present invention is preferably 200 mm or more, and particularly preferably 300 mm or more. When it is at least 300 - 39 - 200804575 mm, the honing composition of the present invention can exert remarkable effects. <<Embodiment>> Hereinafter, the present invention will be described by way of examples. However, the invention is not limited to the embodiments. (Preparation of colloidal cerium oxide (A-1) which is surface-modified with aluminate ions) Average honing grain Φ size (average primary particle diameter) obtained for 1,000 g of hydrolyzed tetraethoxy decane A 20 wt% aqueous dispersion of 35 nm of colloidal cerium oxide (product name: Quotron PL-3, manufacturer: Fuso Chemical Co., Ltd.) was added with ammonia water to adjust the pH to 9.0. Thereafter, 15.9 g of Al2〇3 concentration was 3.6% by weight in a few minutes under stirring at room temperature.

Na2〇/Al2〇3莫耳比爲1 ·50之鋁酸鈉水溶液緩慢地添加入， 並再攪拌〇·5小時。所製得之溶膠（sol )，則裝入SUS (不 銹鋼）製高壓釜裝置，在1 30°C加熱4小時後，以空間速率 ^ 爲1 h_1，在室溫通液於經塡充氫型強酸性陽離子性交換樹A sodium aluminate solution having a Na2?/Al2?3 molar ratio of 1.50 was slowly added thereto, and stirred for another 5 hours. The prepared sol (sol) was placed in an autoclave apparatus made of SUS (stainless steel), and after heating at 1300 ° C for 4 hours, the space velocity was 1 h_1, and the solution was passed through a liquid-filled hydrogen type at room temperature. Strongly acidic cationic exchange tree

W 脂（Amberlite IR-12 0B )之管柱，與經塡充羥基型強鹼性陰 離子性交換樹脂（Amberlite IRA-410)之管柱，並移除其初 餾物。 所製得之使用鋁酸鹽離子加以表面改質的膠質二氧化 石夕（A -1 )之體積平均粒徑爲4 0奈米’且以如前所述之方法 所計算得之鋁被覆量爲1 %。另外，使用鋁酸鹽離子加以表 面改質的膠質二氧化矽（A-1 )，並未觀察到調製後之增黏 、凝膠化。 -40- •200804575 (使用硼酸鹽離子加以表面改質的膠質二氧化矽（Ad)之 調製） 將26 8克之硼酸粉末溶解於5.6公斤之超純水中，以調 製硼酸溶液。 其次，對該硼酸溶液，以約200毫升/分鐘之速率、歷 時約1.2小時緩慢地加入1 5,000克之經水解四乙氧基矽烷所 製得之平均硏磨粒大小（平均一次粒徑）爲3 5奈米之膠質 二氧化矽（製品名：Quotron PL-3，製造廠商：扶桑化學公 司）之20重量％水分散物，然後再添加1 0克之四甲氧基矽 烷。在添加時，混合物係在攪拌下，其溫度維持在55°C至 6 0°C。添加結束後，也在攪拌下將混合物加熱至約60 °C歷時 5.5小時。 接著，將所製得之溶液經由1微米（1 V m)之陶瓷過濾 器加以過濾，以獲得使用硼酸鹽離子加以表面改質的膠質二 氧化砍（A - 2 )。 φ (硏磨用組成物之調製） 將藉由如上所述所製得之鋁酸鹽離子加以表面改質的 膠質二氧化矽（A-1 )作爲硏磨粒，並以如下所示之組成調 製實施例1之硏磨用組成物。另外，組成物之pH調製係使 用氨和硝酸來實施。 〔實施例1〕 一硏磨用組成物一 • ( a)硏磨粒（膠質二氧化矽（人-1 50克/公升 -41- 200804575 • ( b)雜芳香族環化合物（1，2,3_ 50毫克/公升 三唑-4,5-二甲酸） • (e)胺基酸（甘胺酸） 10克/公升 • ( h )氧化劑（30%過氧化氫） 15克/公升 〔實施例2〕 在實施例1中，除取代^2,3-三唑_4,5_二甲酸，而添加 1，2,3，4-四唑-5-醋酸，並將硏磨粒取代爲膠質二氧化矽（A-2 )以外，其餘則以與實施例1相同的方式來調製實施例2之 硏磨用組成物。 〔實施例3〕 除在實施例1中，再添加1，2，3 -三唑作爲（c )雜芳香 族環化合物以外，其餘則以與實施例1相同的方式調製實施 例3之硏磨用組成物。 〔比較例1〕 在實施例1中，除取代1，2,3-三唑-4,5-二甲酸，而添加 1，2,3-三唑作爲（c)雜芳香族環化合物以外，其餘則以與實 施例1相同的方式調製比較用之硏磨用組成物。 〔比較例2〕 在實施例1中，除取代1，2,3-三唑-4,5·二甲酸而添加 1，2,3,4-四唑以作爲（c )雜芳香族環化合物’並將硏磨粒取 代爲膠質二氧化矽（Α-2 )以外，其餘則以與實施例1相同 的方式調製比較用之硏磨用組成物。 將在實施例1至3、比較例1及2所調製之硏磨用組成 物（硏磨液）加以調液後，在室溫下保管6個月後’以如下 -42- 200804575 所示之硏磨方法進行硏磨，並評估硏磨性能（凹陷、浸蝕） 。其評估結果係展示於表3。 (硏磨試驗） 硏磨裝置係使用Lapmaster公司製造之裝置「LGP-6 12 」，以如下所述之條件邊供應硏磨漿、邊硏磨設於各晶圓上 之膜。 • 基板： (1 ) 8英寸之附有銅膜之矽晶圓 (2) 浸蝕評估用；200毫米直徑之銅配線晶圓（圖案 晶圓）（圖罩圖案（mask pattern) 754 CMP ( ATDF 公 司）） • 平台（table )轉速：64 rpm • 硏磨頭（h e a d )轉速：6 5 r p m (加工線速率 =1·〇公尺/秒鐘） • 硏磨壓力：140 hPa • 硏磨墊：R〇hm&amp;Haas公司製造，型號1(：-1400 (〖一 grv ) + ( A2 1 ) • 硏磨漿供應速率：200毫升/分鐘 • 硏磨速率之測定：以硏磨前後之電阻來換算膜壓。具體 而言，其係以硏磨速率（奈米/分鐘）=(硏磨前之銅膜 厚度一硏磨後之銅膜厚度）/硏磨時間所測得。 〈評估〉 1. 凹陷評估 凹陷評估用基板係藉由將矽氧化膜以微影照像步驟與 -43 - 200804575 反應性離子蝕刻步驟加以圖案化，以形成寬度爲0 _0 9至10 0 # m、深度爲600奈米之配線用槽溝與連接洞，再以濺鍍法 形成厚度爲20奈米之Ta膜，接著以濺鍍法形成厚度爲50 奈米之銅膜，其後則以電鍍法形成總厚度爲1，〇〇〇奈米之銅 膜所製得之晶圓，加以裁切成6 X 6公分所製得。 將此基板以如上所述之條件，邊將硏磨漿供應至硏磨裝 置的硏磨平台之硏磨布上，以實施直至非配線部之銅完全受 到硏磨之時間，再加上相當於其時間之3 0%份的過硏磨（以 30%之過硏磨），然後使用觸針式高低落差儀來測定線寬與 間距（1 i n e a n d s p a c e )部（線寬爲1 0 0 // m、間距爲1 〇 〇 μ m )之高低落差，以評估凹陷。 2. 浸蝕評估 對於與上述凹陷之圖案晶圓相同之基板，施加直至非配 線部之銅完全受到硏磨之時間再加上相當於其時間之20% 份的過硏磨（以20%之過硏磨），然後以接觸式高低落差儀 Dektak V3 201 ( Veeco公司製造）測定線寬與間距部（線寬 爲100//m、間距爲ΙΟΟμιη)之高低落差。 3 . 洗淨功效評估 用於偵測晶圓上的異物之裝置係一種光散射式異物測 定裝置（例如，KLA Tencor公司製造之SP1-TB1等）。該 方式之裝置，其偵測晶圓上的異物之方法，並非爲將雷射光 入射於晶圓表面以檢測該雷射光的正反射光，而係藉由以預 先配置於指定方向的光檢測器來偵測所散射的雷射光之光 強度，以偵測晶圓上的異物。雷射光將依序掃描晶圓面，若 • 44- 200804575 異物等之不均勻部份存在於晶圓面時，則散射強度將產生變 化。該裝置係藉由將該散射光強度，與預先以標準微粒加以 修正的散射光強度進行對照，即可顯示以標準微粒換算散射 光強度的異物之大小及其位置。 .殘留於硏磨洗淨乾燥後之表面的麈埃之數量評估，係經 硏磨後，加以水洗乾燥，並使用KLA-TENCOR公司製造之 SP1-TB1來測定缺陷數目。並且，以SEM (掃描型電子顯微 鏡）觀察表面以調查每單位面積的矽微粒數目，結果該微粒 ^ 移除性係可加以分類成如下所述之三種。另外，SEM係使用 日本電子公司製造之JSMT22 0A。 A :幾乎並無殘留硏磨粒（低於100個/晶圓） B ： 有殘留硏磨粒（100以上至低於1，〇〇〇個/晶圓） C ：殘留硏磨粒多（1，000個以上/晶圓） -45- 200804575The column of W grease (Amberlite IR-12 0B) was packed with a column of hydroxy-type strongly basic anion exchange resin (Amberlite IRA-410) and its initial product was removed. The volume average particle diameter of the colloidal silica dioxide (A -1 ) prepared by using aluminate ions to be surface-modified is 40 nm and the amount of aluminum coating calculated by the method described above is obtained. It is 1%. Further, colloidal cerium oxide (A-1) which was surface-modified with aluminate ions was not observed to have viscosity-increasing or gelation after preparation. -40- •200804575 (Preparation of colloidal cerium oxide (Ad) modified with borate ions) 268 g of boric acid powder was dissolved in 5.6 kg of ultrapure water to prepare a boric acid solution. Next, the average honing particle size (average primary particle diameter) of the boric acid solution prepared by slowly adding 15,000 g of hydrolyzed tetraethoxy decane at a rate of about 200 ml/min for about 1.2 hours was 3. A 20 wt% aqueous dispersion of 5 nm colloidal cerium oxide (product name: Quotron PL-3, manufacturer: Fuso Chemical Co., Ltd.), and then 10 g of tetramethoxy decane was further added. When added, the mixture was stirred and maintained at a temperature between 55 ° C and 60 ° C. After the end of the addition, the mixture was also heated to about 60 ° C for 5.5 hours with stirring. Next, the prepared solution was filtered through a 1 μm (1 V m) ceramic filter to obtain a colloidal oxidized chopped (A - 2 ) surface-modified with borate ions. φ (modulation of honing composition) Gluconium cerium oxide (A-1) surface-modified by aluminate ions prepared as described above is used as honing particles, and is composed as follows The composition for honing of Example 1 was prepared. Further, the pH modulation of the composition was carried out using ammonia and nitric acid. [Example 1] A composition for honing - (a) honing particles (colloidal cerium oxide (human-1 50 g / liter - 41 - 200804575 • (b) heteroaromatic ring compound (1, 2, 3_ 50 mg / liter of triazole-4,5-dicarboxylic acid) • (e) Amino acid (glycine) 10 g / liter • ( h ) oxidant (30% hydrogen peroxide) 15 g / liter [Examples 2] In Example 1, except for the substitution of 2,3-triazole-4,5-dicarboxylic acid, 1,2,3,4-tetrazole-5-acetic acid was added, and the honing particles were substituted for colloid. The honing composition of Example 2 was prepared in the same manner as in Example 1 except for the cerium oxide (A-2). [Example 3] In addition to Example 1, 1, 2 was further added. The honing composition of Example 3 was prepared in the same manner as in Example 1 except that the 3-triazole was used as the (c) heteroaromatic ring compound. [Comparative Example 1] In Example 1, except for the substitution 1 2,3-triazole-4,5-dicarboxylic acid, and 1,2,3-triazole was added as the (c) heteroaromatic ring compound, and the others were prepared and used in the same manner as in Example 1. The composition for honing. [Comparative Example 2] In Example 1, 1,2,3,4-tetrazole was added as a (c) heteroaromatic ring compound in addition to 1,2,3-triazole-4,5-dicarboxylic acid, and the granules were replaced. The honing composition for comparison was prepared in the same manner as in Example 1 except for the colloidal cerium oxide (Α-2). The honing prepared in Examples 1 to 3 and Comparative Examples 1 and 2 After the liquid was adjusted with the composition (honing liquid), it was stored at room temperature for 6 months, and then honed by the honing method shown in the following -42-200804575, and the honing performance (depression, etching) was evaluated. The results of the evaluation are shown in Table 3. (Horse test) The honing device was equipped with a device "LGP-6 12" manufactured by Lapmaster Co., Ltd., and supplied with 硏 硏, 硏 硏 设Film on the circle. • Substrate: (1) 8-inch copper wafer with copper film (2) for evaluation of etching; 200 mm diameter copper wiring wafer (pattern wafer) (mask pattern) 754 CMP (ATDF)) • Table speed: 64 rpm • Head speed: 6 5 rpm (processing line rate = 1 〇 ft) / sec) • Honing pressure: 140 hPa • Honing pad: manufactured by R〇hm &amp; Haas, model 1 (:-1400 (〖grv) + (A2 1) • 硏 refining supply rate: 200 ml / Minutes • Determination of honing rate: The membrane pressure is converted by the resistance before and after honing. Specifically, it is the honing rate (nano/min) = (the thickness of the copper film before honing is a honed copper) Film thickness) / honing time measured. <Evaluation> 1. The evaluation substrate for the evaluation of the depression is patterned by a photolithography step and a reactive ion etching step of -43 - 200804575 to form a width of 0 _0 9 to 10 0 # m a trench with a depth of 600 nm and a connection hole, and then a Ta film having a thickness of 20 nm is formed by sputtering, and then a copper film having a thickness of 50 nm is formed by sputtering, and then plating is performed. The method is to form a wafer made of a copper film having a total thickness of 1, 〇〇〇 nanometer, which is cut into 6 x 6 cm. The substrate is supplied to the honing cloth of the honing platform of the honing device under the conditions as described above, and the time until the copper of the non-wiring portion is completely honed is performed, and the equivalent is added. 30% of the time has been honed (by 30% honing), and then the stylus type height and low drop meter is used to measure the line width and spacing (1 ineandspace) (line width is 1 0 0 // m The height difference of 1 〇〇μ m is used to evaluate the depression. 2. Erosion evaluation For the same substrate as the recessed pattern wafer, the time until the non-wiring portion of the copper is completely honed plus 20% of the time is over-grinded (by 20%) After honing, the height difference and the pitch portion (line width of 100//m, pitch ΙΟΟμιη) were measured by a contact type high and low drop meter Dektak V3 201 (manufactured by Veeco Co., Ltd.). 3. Cleaning efficacy evaluation The device for detecting foreign matter on the wafer is a light scattering foreign matter measuring device (for example, SP1-TB1 manufactured by KLA Tencor Co., Ltd.). The device of the method for detecting foreign matter on the wafer is not for injecting laser light onto the surface of the wafer to detect the regular reflection of the laser light, but by using a photodetector pre-configured in a specified direction. To detect the intensity of the scattered laser light to detect foreign matter on the wafer. The laser light will scan the wafer surface in sequence, and if the uneven portion of foreign matter such as 44-200804575 exists on the wafer surface, the scattering intensity will change. By comparing the intensity of the scattered light with the intensity of the scattered light corrected in advance by the standard particles, the apparatus can display the size and position of the foreign matter in terms of the intensity of the scattered light in the standard particle. The amount of ruthenium remaining on the surface after honing and drying was evaluated by honing, washed with water, and SP1-TB1 manufactured by KLA-TENCOR Co., Ltd. was used to determine the number of defects. Further, the surface was observed by SEM (Scanning Electron Microscope) to investigate the number of ruthenium particles per unit area, and as a result, the particle removal property can be classified into three types as described below. In addition, the SEM system used JSMT22 0A manufactured by JEOL. A : There are almost no residual honing particles (less than 100 / wafer) B : There are residual honing particles (100 or more to less than 1, one / wafer) C : Residual honing particles (1 , more than 000 / wafer) -45- 200804575

ε撇 洗淨 功效 &lt; U &lt; u &lt; 浸蝕 (奈米） 〇 (N 1—Η ο m ο a账 00 m oo ON OO Ό (Ν (〇雜芳香族環化合物 1 1，2,3-三唑 1 1，2,3,4-四唑 1，2,3·三唑 (b)雜芳香族環化合物 1，2,3-三唑-4,5-二甲酸 1 1，2,3,4-四唑-5-醋酸 1 1，2,3-三卩坐-4,5-二甲酸 硏磨粒 種類 r-H 1 &lt; &lt; (Ν &lt; (N &lt; &lt; 寸 寸 卜 卜 寸 硏磨用組成物 (硏磨漿） CO &lt;Ν CO cn cA m 1實施例1 比較例1 實施例2 比較例2 實施例3 -9寸| 200804575 如表3所示，在實施例1至3中，係使用包含：（a) 使用鋁酸鹽離子或硼酸鹽離子將膠質二氧化矽加以表面改 質之硏磨粒，及（b )具有陰離子性取代基、且在分子內具 有三個或以上氮原子之雜芳香族環化合物之硏磨用組成物 ，其係在任何情况下皆可顯示優越的功效。 並且，在實施例3中，係使用又包含（c)在分子內具 有三個或以上氮原子、且無陰離子性取代基之雜芳香族環化 合物之硏磨用組成物，其凹陷評估係具有26奈米之優異功撇 撇 功效 &&lt; U &lt; u &lt; etch (nano) 〇 (N 1 - Η ο m ο a account 00 m oo ON OO Ό (Ν (noisy aromatic ring compound 1, 1, 2, 3 -triazole 1, 1,2,3,4-tetrazole 1,2,3 · triazole (b) heteroaromatic ring compound 1,2,3-triazole-4,5-dicarboxylic acid 1,2, 3,4-tetrazole-5-acetic acid 1, 1,2,3-triterpene-4,5-dicarboxylic acid 硏 abrasive grain type rH 1 &lt;&lt; (Ν &lt; (N &lt;&lt; Inch honing composition (硏磨浆) CO &lt;Ν CO cn cA m 1 Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 -9 inch | 200804575 As shown in Table 3, in Example 1 Up to 3, the use of: (a) the use of aluminate ions or borate ions to modify the surface of the colloidal cerium oxide particles, and (b) has an anionic substituent, and has three in the molecule The honing composition of the heteroaromatic ring compound of one or more nitrogen atoms can exhibit superior efficacy in any case. Moreover, in Example 3, the use further comprises (c) having in the molecule Three or more nitrogen atoms and no anionic substituents A composition for honing of an aromatic cyclic compound, the evaluation of the depression has an excellent work of 26 nm.

Claims (1)

« 200804575 十、申請專利範圍· 1 .一種金屬硏磨用組成物，其特徵爲：包含（a )使用鋁酸 離子或硼酸離子將膠質二氧化矽加以表面改質之硏磨粒 ，及（b )具有陰離子性取代基、且在分子內具有三個或 以上氮原子之雜芳香族環化合物。 2.如申請專利範圍第1項所述之金屬硏磨用組成物，其中又 包含（c)在分子內具有三個以上氮原子、且無陰離子性 取代基之雜芳香族環化合物。 • 3 .如申請專利範圍第1項所述之金屬硏磨用組成物，其中該 金屬硏磨用組成物係將該硏磨粒分散於水溶液中之硏磨 漿。 4.如申請專利範圍第1項所述之金屬硏磨用組成物，其中若 在該膠質二氧化矽表面之膠質二氧化矽的表面原子取代 率爲導入鋁原子或硼原子之數目/表面矽原子部位之數目 時，則該取代率爲0.001%以上、20%以下。 5 ·如申請專利範圍第1項所述之金屬硏磨用組成物，其中該 ® 膠質二氧化矽藉由使用動態光散射法所測得之體積相當 直徑爲3奈米至2 0 0奈米。 6·如申請專利範圍第1項所述之金屬硏磨用組成物，其中該 金屬硏磨用組成物之pH爲3至7。 7. 如申請專利範圍第1至6項中任一項所述之金屬硏磨用組 成物，其中使用該金屬硏磨用組成物實施硏磨時之被硏 磨面是銅或銅合金。 8. —種化學機械硏磨方法，其特徵爲：使用包含（a)使用 -48- 200804575 鋁酸鹽離子或硼酸鹽離子將膠質二氧化矽加以表面改質 之硏磨粒，及（b)具有陰離子性取代基、且在分子內具 有三個以上氮原子之雜芳香族環化合物之金屬硏磨用組 成物；且在硏磨壓力爲3 psi ( 0.0207 MPa)以下實施硏 磨。 9.如申請專利範圍第8項所述之化學機械硏磨方法，其中該 金屬硏磨用組成物又包含（c)在分子內具有三個以上氮 原子.、且無陰離子性取代基之雜芳香族環化合物。 Φ 1 0.如申請專利範圍第8或9項所述之化學機械硏磨方法， 其中使用該金屬硏磨用組成物實施硏磨時之被硏磨面是 銅或銅合金。« 200804575 X. Patent application scope 1. A composition for metal honing, characterized in that it comprises (a) honing particles which are surface-modified with colloidal cerium oxide using aluminate ions or boric acid ions, and (b) A heteroaromatic ring compound having an anionic substituent and having three or more nitrogen atoms in the molecule. 2. The metal honing composition according to claim 1, which further comprises (c) a heteroaromatic ring compound having three or more nitrogen atoms in the molecule and having no anionic substituent. The metal honing composition according to claim 1, wherein the metal honing composition is a honing slurry in which the honing particles are dispersed in an aqueous solution. 4. The metal honing composition according to claim 1, wherein if the surface atomic substitution rate of the colloidal cerium oxide on the surface of the colloidal cerium oxide is a number of aluminum atoms or boron atoms/surface 矽When the number of atomic sites is the same, the substitution ratio is 0.001% or more and 20% or less. 5. The metal honing composition according to claim 1, wherein the colloidal cerium oxide has a volume equivalent to a diameter of from 3 nm to 200 nm as measured by dynamic light scattering. . The metal honing composition according to the above aspect of the invention, wherein the metal honing composition has a pH of from 3 to 7. 7. The metal honing composition according to any one of claims 1 to 6, wherein the surface to be honed using the metal honing composition is copper or a copper alloy. 8. A chemical mechanical honing method, characterized in that: (a) a granule comprising (a) a surface modification of colloidal cerium oxide using -48-200804575 aluminate ion or borate ion, and (b) A metal honing composition having an anionic substituent and a heteroaromatic ring compound having three or more nitrogen atoms in the molecule; and honing at a honing pressure of 3 psi (0.0207 MPa) or less. 9. The chemical mechanical honing method according to claim 8, wherein the metal honing composition further comprises (c) a compound having three or more nitrogen atoms in the molecule, and having no anionic substituent. Aromatic ring compounds. Φ 1 0. The chemical mechanical honing method according to claim 8 or 9, wherein the honed surface when the metal honing composition is used for honing is copper or a copper alloy. -49- 200804575 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： Μ 〇 j\\\ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：-49- 200804575 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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JP7375515B2 (en) 2019-12-11 2023-11-08 Jsr株式会社 Chemical mechanical polishing composition and chemical mechanical polishing method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4206233B2 (en) * 2002-07-22 2009-01-07 旭硝子株式会社 Abrasive and polishing method
US20050079803A1 (en) * 2003-10-10 2005-04-14 Siddiqui Junaid Ahmed Chemical-mechanical planarization composition having PVNO and associated method for use
JP2005340755A (en) * 2003-11-14 2005-12-08 Showa Denko Kk Abrasive compound and polishing method

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US11001732B2 (en) 2016-05-19 2021-05-11 Dongjin Semichem Co., Ltd. Polishing slurry composition
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