1298666 玫、發明說明 【發明所屬之技術領域】1298666 玫,发明说明 [Technical field to which the invention belongs]
此發明使用之具優分散安定性之硏磨劑漿體，無特別 之限制，由半導體製造步驟或靜電夾頭製造步驟爲平坦化 所進行之基板表面之表面硏磨開始，廣泛的被採用於空白 遮光膜、玻璃碟片、光學鏡片等之硏磨面之硏磨之化學機 械硏磨（Chemical Mechanical Polishing ;以下以「CMP 」稱之）用途之適當硏磨劑漿體。 【先前技術】 例如，有關半導體製造步驟所使用之矽基板或靜電夾 頭製造步驟所使用之鋁基板等之基板，要求極高精度之平 坦性，有關其被硏磨面之基板表面平坦化之技術，採用由 硏磨微粒子之機械硏磨及由鈾刻液之化學硏磨組合之 CMP，不損傷基板表面之基板表面高度平坦化之平坦化技 術。 如此使用於該平坦化技術之硏磨劑，一般因應硏磨對 象之基板之種類或平坦化技術要求之加工速度，使用具有 種種大小（平均粒徑）之氧化鈽 （Ce02)、二氧化錳 (Μη02)等之金屬氧化物，沈降氧化矽、煙霧氧化矽、膠 質二氧化矽等之矽氧化物 （Si02)，或煙霧氧化鋁、膠質 氧化鋁等之鋁氧化合物 （ai2o3)等各種類之硏磨微粒子 分散於水等之分散劑中所得之漿體。 但是，此等之硏磨微粒子，依其種類或大小於分散劑 -5- 1298666 中之分散安定性差，例如，氧化鈽粒子時，由於具比較高 的比重，分散氧化鈽粒子於分散劑中調製硏磨劑槳體時， 調製後短時間爲均勻分散，其後於比較短的時間氧化鈽開 始分離，沈降幾乎引起粒子凝集成爲大粒徑，引起粒子分 佈廣之沈降·凝集問題，加工時起經時變化，又，產生基 板表面損傷等之問題。 因此，爲消解向來磨劑漿體有關之沈降·凝集之問題 ，例如硏磨劑漿體於使用前進行攪拌再分散硏磨微粒子之 再分散處理，或過濾分離除去凝集之比指定粒徑大之異常 凝集粒子之分離除去處理等，成爲基板等之平坦化步驟之 大負擔。 向來亦有幾個爲消解此硏磨劑漿體之沈降·凝集問題 之提案。 即，提案以含氧化鈽粒子、丙烯酸銨鹽及丙烯酸甲酯 之共聚物，及水，可高速硏磨不易沈降，不損傷Si〇2絕 緣膜等之被硏磨面之氧化鈽硏磨劑（參閱日本特開2000-17，195號公報）。 又，提案至少選擇含1種由水溶性有機高分子、水溶 性陰離子性界面活性劑、水溶性非離子性界面活性劑及水 溶性胺之化合物，最大沈降速度爲1 # πι / s以下者，沈降 小，可容易由攪拌均勻化，可高速硏磨，不損傷Si02絕 緣膜等之被硏磨面之氧化鈽硏磨劑（參閱日本特開2000-138，195號公報）。 又，提案含氧化鈽粒子，與聚丙烯酸超過全羧基之 -6 - 1298666 9 0%爲氨所中和之聚丙酸亞鹽，及聚丙烯酸超過全羧基之 15〜50%爲氨所中和之聚丙酸次鹽，及水，聚丙烯酸亞鹽 與聚丙烯酸次鹽之合計含量爲〇·15〜1重量％，具良好安 定性，不產生二層分離或凝集沈降固結、粘度變化之氧化 鈽硏磨劑（參閱日本特開2002-3 53,1 75號公報）。 但是，有關此等含分散劑之氧化鈽硏磨劑，難於消解 經1個月或以上之長期沈降·凝集之問題、與維持良好再 分散性，又，相關之製造步驟，發生因已凝集之硏磨劑堵 住裝置內配管等之事例，此諸問題不見得能完全解決之問 題。 又，此任一之氧化鈽硏磨劑亦含較多量 （0.1〜5重 量％)作爲分散劑的水溶性高分子、水溶性陰離子性界面活 性劑、水溶性非離子性界面活性劑、水溶性胺等之有機化 合物，硏磨處理後之廢液中混存氧化鈽粒子之無機物質及 分散劑之有機物質，其廢液處理需費工夫及成本之問題。 加上，有關如此之硏磨劑漿體，由盡可能減低其製造 成本或運輸成本的觀點，製造時盡可能製造高濃度者，使 用時稀釋至指定之濃度使用爲理想，具高濃度者容易產生 沈降·凝集之問題，期望開發更上一層分散安定性之硏磨 劑漿體。 【發明內容】 於此’本發明者等，對有關具優長期分散安定性，又 良好再分散性，盡可能消解沈降·凝集之問題以外，可使 用完全不使用有機分散劑之無分散硏磨劑漿體，經深入硏 1298666 究結果，添加比膠質狀氧化物之硏磨微粒子更具微小平均 粒徑之膠質微粒子，發現可抑制硏磨微粒子之沈降·凝集 ，完成本發明。 因此，本發明之目的爲提供具優長期分散安定性，又 良好再分散性，盡可能消解沈降·凝集之問題以外，可使 用完全不使用有機系分散劑之無分散劑硏磨劑漿體。 又，本發明之其他目的爲提供使用如此之硏磨劑漿體 ，有利於由CMP工業製造使用於半導體製造步驟之矽基 板或使用於靜電夾頭製造步驟之鋁基板等之基板製造方法 〇 即，本發明爲含選擇1種或2種以上之氧化物之硏磨 微粒子，及比上述硏磨微粒子具更小平均粒徑之膠質微粒 子之膠質狀氧化物，與分散此硏磨微粒子及膠質微粒子之 分散劑，具優分散安定性之硏磨劑漿體。 又，含使用此硏磨劑漿體硏磨無機質基板硏磨步驟之 基板之製造方法。 有關本發明作爲硏磨微粒子使用之氧化物，可直接使 用向來作爲此種硏磨微粒子使用者，具體的可列舉如氧化 鈽 （Ce02)、二氧化錳 （Μη02)等之金屬氧化物，沈降氧 化矽、煙霧氧化矽、膠質二氧化矽等之矽氧化物 （Si02) ，或煙霧氧化鋁、膠質氧化鋁等之鋁氧化合物 （ai2o3) 等。此等可僅單獨使用1種，亦可混合2種以上使用。 此等氧化物中，作爲本發明理想使用之硏磨微粒子， 以氧化鈽粒子、氧化鋁粒子等比重較高或平均粒徑較大， -8- 1298666 其自體容易產生沈降·凝集者爲佳，對此種硏磨 別有效。 有關本發明所使用之硏磨微粒子之平均粒箱 無特別限制，又，依種類而異，爲氧化鈽粒子時 100 〜5,000 nm，理想以 500 〜2,000 nm 爲佳， 粒子之種類，平均粒徑 （Dp)低於 100 nm時 不能充分發揮，反之超過5,000 nm時硏磨面容 痕的問題。 又，有關此硏磨微粒子同時使用之膠質微粒 例如膠質氧化鈽、膠質氧化鋁等之膠質狀氧化物 可僅單獨使用1種，亦可混合2種以上使用。 有關此膠質微粒子之平均粒徑 （Dc)，至少 上述硏磨微粒子，依種類而異，含膠質二氧化矽 通常爲10〜300 nm，理想爲20〜200nm，上述 子之平均粒徑 （Dp)與此膠質微粒子之平均粒 之粒徑比 （Dc / Dp)爲10以下，理想以0.01 爲佳。此膠質微粒子之平均粒徑 （Dc)低於10 造時不安定容易凝膠化，反之，超過3 00 nm時 粒徑差異，又，粒徑比（Dc / Dp)超過10時其 微粒子過小不能充分發揮硏磨能力。 又，有關構成硏磨劑漿體之分散劑，可直接 此種硏磨劑漿體所使用之分散劑，無特別限制， 漿體之用途，例如依半導體製造步驟使用之矽基 夾頭製造步驟之鋁基板等基板之平坦化所使用之 微粒子特 ;(Dp)， ，通常爲 依硏磨微 硏磨能力 易產生傷 子，可舉 等，此等 必要小於 較多時， 硏磨微粒 徑（Dc) 〜3程度 nm 時製 容易產生 結果硏磨 使用向來 此硏磨劑 板或靜電 CMP 硏 1298666 磨劑漿體，空白遮光膜、玻璃某片、光學鏡片等之被硏磨 面所使用之CMP硏磨劑漿體，又其他被硏磨面之硏磨所 使用之一般硏磨劑漿體，可適當的選擇。以水爲理想，以 水爲主成分之含甲醇、乙醇、η-丙醇、異丙醇、η-丁醇、 叔-丁醇等之醇類，或酮類、酯類、醚類等水溶性溶劑之 水性分散劑爲合適。又，此等分散劑中，與向來相同，因 應必要於CMP時爲進行化學硏磨而添加蝕刻液。 所以，有關構成本發明硏磨劑漿體之上述硏磨微粒子 之粒子濃度 （Cp)，依硏磨微粒子之種類而異，爲氧化鈽 粒子時，通常爲5〜40重量％，理想爲5〜30重量％，更 理想爲5〜1 0重量％，又，有關膠質微粒子之粒子濃度 (Cc)，含膠質二氧化矽時多數情形，通常爲0.1〜5重量％ ，理想以0.2〜2重量％爲佳，又，上述硏磨微粒子與膠 質微粒子之重量配合比 （Cc / Cp)爲1以下，理想以 0-5以下爲佳。以如此粒子濃度 （Cc)及 （Cp)調製之 硏磨劑漿體，直接以粒子濃度 （Cp)及 （Cc)，或因應必 要以分散劑稀釋至指定之粒子濃度（Cp)及 （Cc)使用 於CMP等之硏磨。硏磨微粒子粒子濃度（Cp)低於5重 量％時硏磨力不足，反之高於40重量％時產生溶解性問題 。又，膠質微粒之粒子濃度 （Cc)低於〇.1重量％時沈降 •凝集之抑制效果降低，反之高於5重量％時反而產生凝 集的問題。又，硏磨微粒子與膠質微粒子之重量配合比 (Cc/Cp)超過1時，容易產生凝集現象。 本發明之硏磨劑漿體，特別是不添加水溶性高分子、 -10- 1298666 水溶性陰離子界面活性劑、水溶性非離子界面活及水溶性 胺等之有機系分散劑亦具有優長期分散安定性，又，再分 散性良好，可消解沈降·凝集的問題。 又，有關本發明，硏磨劑漿體之調製方法，其構成成 分之硏磨微粒子、膠質微粒子及分散劑混合均勻，硏磨微 粒子、膠質微粒子均勻分散於分散劑之漿體者，無特別限 制，可使用通常之攪拌機調製，依必要亦可使用超音波分 散機；均質機、球磨機、振動球磨機、衛星球磨機、媒體 攪拌磨碎機等之濕式分散機。 本發明之硏磨漿體，不僅半導體製造步驟用之矽基板 或靜電夾頭製造用之鋁基板等基板之平坦化，亦使用於配 線板形成具有指定配線之氧化矽絕緣膜等之氧化膜，玻璃 ，氧化砂等之無機絕緣膜，遮光膜·鏡片·菱鏡等之光學 玻璃，ITO等之無機導電膜，玻璃結晶質材料所構成之光 積體電路·光開關元件·光導波路、光纖端面、閃爍器等 光學用單結晶，固體雷射單結晶，藍色雷射用led藍寶 石基板，Sic，GaP，GaAS等之半導體單結晶，磁碟用玻 離基板，磁頭等之硏磨。 例如，形成電路元件與鋁配線階段之半導體基板，或 形電路元件之半導體基板之階段等之基板上形成氧化矽絕 緣膜之氧化膜之基板，爲消解其氧化膜表面凹凸之平坦化 目的進行CMP時，可使用具備保持基板之夾具與粘貼硏 磨布 （Pad)之回轉盤之一般硏磨裝置，硏磨布以幫浦連 續供給定量本發明之硏磨劑漿體，於指定之回轉數及加壓 -11 - 1298666 下硏磨。 【實施方式】 以下以實施例及比較例爲準，詳細具體的說明本發明 最佳實施形態。 實施例1〜27 [膠質二氧化矽 （20 nm)之調製] 具備餾液出口，液面控制裝置及攪拌器之1 m3夾層 桶槽，投入32 kg甲基矽酸鹽、100 kg甲醇及768 kg 純水，混合成爲A液。 又，具備攪拌器之3 m3之桶槽，投入368kg甲基矽 酸鹽、100 kg甲醇1840 kg純水及12 kg之28wt %氨水 ，混合成爲B液。 其次，A裝之桶槽以蒸氣加熱，餾出甲醇及水之混合 液，A液開始餾出時添加B液以維持A液於一定液面，B 液全部添加終了時，添加純水240 kg維持A液於一定之 液面，反應。 反應終了後，由裝A液之桶槽中取出反應生成物分 析結果，氧化矽爲20重量％平均粒徑爲20 nm之膠質狀 氧化矽生成物（膠質二氧化矽（20 nm))。 [膠質二氧化矽（70 nm)之調製] 具備攪拌器之3 m3之夾層桶槽’投入1721.7 kg甲醇 -12- 1298666 ，3 06.3 kg純水及88.4 kg 之28 wt %氨水，混合後，調 整液溫爲23±1°C，維持液溫於23±1°C，於攪拌下於2〜 1.5小時投入404.4 kg之甲基矽酸鹽反應。 反應終了後，所得之反應混合物之粗製品移至具備餾 液出口，液面控制裝置及攪拌器之1 m3夾層桶槽，桶槽 以蒸氣加熱，餾出甲醇、水及氨之混合液，液體開始餾出 時添加剩餘之反應混合物維持一定液面，反應混合物全部 添加終了時，添加純水至所定之液面，添加純水至桶槽內 之液溫到達l〇〇°C爲止。 液溫到達1 00 °C時停止加熱，冷卻中間製品，液溫成 爲70°C時添加適量之28 wt %氨水，再攪拌混合後，由桶 槽取出反應生成物。 所得之反應生成物氧化矽爲30重量％平均粒徑爲70 nm之膠質狀氧化矽生成物（膠質二氧化矽 （70 nm))。 [膠質二氧化矽（170 nm)之調製] 具備攪拌器之1.8 m3之夾層桶槽，投入8 8 5.1 kg甲 醇，6.31 kg純水及113.25 kg 28 wt %氨水，混合後，調 整液溫爲23±1°C，維持液溫於23±1°C，於攪拌下於3小 時投入171.4kg之甲基矽酸鹽反應。 反應終了後，所得之反應混合物之粗製品移至具備餾 液出口，液面控制裝置及攪拌器之1 m3夾層桶槽，桶槽 以蒸氣加熱，餾出甲醇、水及氨之混合液，液體開始餾出 時添加剩餘之反應混合物維持一定液面，反應混合物全部 -13- 1298666 添加終了時，添加純水至指定之液面，添加純水至桶槽內 之液溫到達100°c爲止。 液溫到達1 0 0 °c時停止加熱，冷卻中間製品，液溫成 爲70 °C時添加適量之28 wt %氨水，再攪拌混合後，由桶 槽取出反應生成物。 所得之反應生成物氧化砂爲2 2重量％平均粒徑爲1 7 〇 nm之膠質狀氧化矽生成物（膠質二氧化矽（17〇 nm))。 [硏磨劑漿體之調製] 使用平均粒徑爲1 . 1 // m及最大粒徑爲8 // m之氧化 鈽粒子作爲硏磨微粒子（日本SEMICHEMICAL公司製商 品名：TE-508)，使用上述所得之3種膠質二氧化矽作爲 膠質微粒子，使用水爲分散劑，以表1所示比例配合，以 攪拌機混均勻，調製各實施例1〜27之硏磨劑漿體。 [沈澱·凝集狀態及再分散性之評價] 有關各實施例1〜27所得之硏磨漿體，其50 ml放 入1 00 ml試驗管內靜止放置1個月之後，以目視觀察沈 澱·凝集狀態。 又，50 ml之硏磨劑漿體放入100 ml PE製容器內靜 止放置1個月，其後以手振動以目視觀察再分散性’同時 橫躺載置於卓上型球磨機（日本入江商會公司製：型式 V-1M)上，以攪拌轉數100 rpm及10分鐘攪拌時間之條 件攪拌，以目視觀察由攪拌機之再分散性。 -14- 1298666 上述沈澱·凝集狀態及再分散性之結果依以下4階段 評價， ◎:沈澱部份全部爲柔軟狀，以手振動可於數秒內再 分散，又，以攪拌機可於5分鐘內再分散。 〇：沈澱部份有固體，以手振動再分散需3 0秒左右 ，又，以攪拌機再分散需1 0分鐘。 △:沈澱部份有固體，以手振動再分散需2分鐘以， 又，以攪拌機再分散需10分鐘。 X :沈澱部份全部固化，以手振動1 0分鐘亦不再分 散，又，以攪拌機再分散需1 0分鐘。 結果如表1所示。 [石英基板硏磨速度] 又，硏磨劑漿體以3倍超純水稀釋，使用具硏磨布之 CMP 硏磨機（日本 NAF-FACTOR 公司製：FACT-200)， 200 rpm回轉數，500 g / Cm2壓力，及1〇 ml / min之速 度供給硏磨劑漿體之條件，硏磨試料（幅3.3 cm X 2.6 cm ’厚度爲1 · 1 5 nm之石英基板）1 〇分鐘，以測微計測 定硏磨前後試料之厚度，由硏磨前後試料之厚度求出對石 英基板（Si02)之硏磨速度（//m/l〇min)。 比較例〜1 5 使用聚乙儲卩比咯院酮（PVP)作爲有機分散劑，與上 述實施例1〜27之情形同樣調製比賽例1〜1 5之硏磨劑 -15- 1298666 漿體，各比較例1〜15所得之硏磨劑，與實施例1〜27 同樣評價，又，求出對石英基板（Si02)之硏磨速度。 結果與上述實施例〜27同列於表1所示。 -16- 1298666 [表l] 實施例No· 1 2 3 4 5 6 7 8 9 硏磨劑組成 (wt %) 氧化铈粒子(Ce02) 5 15 30 5 15 30 5 15 30 膠質二氧化石夕(20nm) 1 1 1 2 2 2 5 5 5 分散劑 沈澱凝固狀態及再分散性評價 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 石英基板硏磨速度 (3 倍稀釋液：//m/10min) 10 10 10 10 10 10 10 10 10 實施例Να 10 11 12 13 14 15 16 17 18 硏磨劑組成 (wt %) 氧化鈽粒子(Ce02) 5 15 30 5 15 30 5 15 30 膠質二氧化矽(70nm) 1 1 1 2 2 2 5 5 5 分散劑 沈澱凝固狀態及再分散性評價 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 石英基板硏磨速度 (3倍稀釋液："m/10min) 10 10 10 10 10 10 10 10 10 實施例No· 19 20 21 22 23 24 25 26 27 硏磨劑組成 (wt %) 氧化鈽粒子(Ce02) 5 15 30 5 15 30 5 15 30 膠質二氧化矽 (170nm) 1 1 1 2 2 2 5 5 5 分散劑 沈澱凝固狀態及再分散性評價 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 石英基板硏磨速度 (3倍稀釋液："m/10min) 10 10 10 10 10 10 10 10 10 比較例No· 1 2 3 4 5 6 7 8 9 硏磨劑組成 (wt %) 氧化鈽粒子(Ce02) 5 15 30 5 15 30 5 15 30 膠質二氧化矽 分散劑 - - 1 1 1 3 3 3 沈澱凝固狀態及再分散性評價 X X X Δ Δ Δ X X X 石英基板硏磨速度 (3倍稀釋液："m/10min) - _ - 10 10 10 10 10 10 實施例No· 10 11 12 13 14 15 硏磨劑組成 (wt %) 氧化鈽粒子(Ce02) 5 15 30 5 15 30 膠質二氧化矽 分散劑 1 1 1 3 3 3 沈澱凝固狀態及再分散性評價 Δ Δ Δ 〇 Δ Δ 石英基板硏磨速度 (3 倍稀釋液：//m/10min) 10 10 10 10 10 10 -17- 1298666 由表1結果可了解，相對於本發明實施例1〜27任 一之硏磨劑黎體發揮優沈降·凝集狀態及再分散性，及對 石英基板硏磨速度’不添加膠質微粒子及分散劑之比較例 1〜3之任一硏磨劑漿體不能再分散，硏磨速度不能測定 ，又，僅添加1重量％及3重量％之分散劑之比較例4〜 1 5之硏磨劑漿體再分散需要更長時間，判明本發明之硏 磨劑漿體具極優沈降·凝集狀態及再分散性。 依本發明可提供經時分散安定性優，又，再分散性良 好，可消解沈降·凝集之問題，又，可使用全不使用有機 分散劑之無分散劑硏磨劑漿體。 又，由使用本發明之硏磨劑漿體，可有利於由CMP 工業製造半導體製造步驟用矽基板或靜電夾頭製造步驟用 鋁基板等之基板。 -18 -The honing agent slurry having excellent dispersion stability used in the invention is not particularly limited, and the surface honing of the substrate surface by the semiconductor manufacturing step or the electrostatic chuck manufacturing step for planarization is widely used. A suitable honing agent slurry for chemical mechanical polishing (hereinafter referred to as "CMP") for honing surfaces such as blank shading films, glass discs, and optical lenses. [Prior Art] For example, a substrate such as an aluminum substrate used in a semiconductor manufacturing step or an electrostatic chuck manufacturing step requires extremely high flatness, and the surface of the substrate on which the surface is honed is flattened. The technique uses a mechanical honing by honing fine particles and a CMP combined with chemical honing of uranium engraving, and a flattening technique that does not damage the surface of the substrate surface to be highly flattened. The honing agent used in the planarization technique generally uses cerium oxide (Ce02) and manganese dioxide having various sizes (average particle diameter) in accordance with the type of the substrate to be honed or the processing speed required for the planarization technique.金属η02) and other metal oxides, such as cerium oxide, cerium oxide, cerium cerium oxide, etc. (SiO 2 ) A slurry obtained by dispersing fine particles in a dispersing agent such as water. However, such honing microparticles have poor dispersion stability in dispersant-5-1298666 depending on the type or size thereof. For example, in the case of cerium oxide particles, dispersed cerium oxide particles are prepared in a dispersing agent due to a relatively high specific gravity. When honing the paddle body, it is uniformly dispersed for a short time after preparation, and then the yttrium oxide starts to separate in a relatively short time, and the sedimentation almost causes the particles to aggregate into a large particle size, causing a problem of sedimentation and agglomeration of a wide particle distribution, from the time of processing. The change over time causes problems such as damage to the surface of the substrate. Therefore, in order to eliminate the problem of sedimentation and agglomeration associated with the slurry of the original abrasive, for example, the honing agent slurry is stirred and dispersed before use, and the granules are re-dispersed, or the separation by filtration is removed to remove the agglomerate. The separation and removal process of the abnormally aggregated particles is a great burden on the planarization step of the substrate or the like. There have also been several proposals to resolve the problem of settling and agglomeration of this honing agent slurry. In other words, it is proposed to use a copolymer containing cerium oxide particles, an ammonium acrylate salt, and a methyl acrylate, and water, to temper the honing agent which is not easily damaged by high-speed honing, and which does not damage the surface of the Si〇2 insulating film ( See JP-A-2000-17, 195). Further, at least one compound containing a water-soluble organic polymer, a water-soluble anionic surfactant, a water-soluble nonionic surfactant, and a water-soluble amine is selected, and the maximum sedimentation rate is 1 #πι / s or less. The sedimentation is small, and it can be easily homogenized by stirring, and can be honed at a high speed without damaging the oxidized honing agent of the honed surface such as the SiO 2 insulating film (refer to Japanese Laid-Open Patent Publication No. 2000-138, No. 195). Further, it is proposed to contain cerium oxide particles, and the polyacrylic acid sulfite which is neutralized by the poly-acrylic acid exceeding -6 - 1298666 90% of the total carboxyl group, and the polyacrylic acid exceeding 15 to 50% of the total carboxyl group is neutralized by ammonia. The polypropionic acid sub-salt, and the water, the polyacrylic acid sub-salt and the polyacrylic acid sub-salt are in a total amount of 〇·15~1% by weight, have good stability, and do not produce two-layer separation or agglomeration sedimentation consolidation, viscosity change of cerium oxide A honing agent (refer to JP-A-2002-3 53,1 75). However, with regard to such oxidizing honing agents containing a dispersing agent, it is difficult to digest the problem of long-term sedimentation and agglutination over one month or more, and to maintain good redispersibility, and the related manufacturing steps are caused by agglomeration. The case where the honing agent blocks the piping in the apparatus and the like, these problems are not necessarily completely solved. Further, any of the oxidative honing agents also contains a relatively large amount (0.1 to 5% by weight) of a water-soluble polymer as a dispersing agent, a water-soluble anionic surfactant, a water-soluble nonionic surfactant, and water solubility. An organic compound such as an amine, an organic substance in which cerium oxide particles are mixed and a organic substance of a dispersing agent are mixed in a waste liquid after honing, and the waste liquid treatment requires labor and cost. In addition, with regard to such a honing agent slurry, it is desirable to manufacture a high concentration as much as possible from the viewpoint of minimizing its manufacturing cost or transportation cost, and it is preferable to use it at a concentration diluted to a specified concentration during use, and it is easy to have a high concentration. There is a problem of sedimentation and agglomeration, and it is desired to develop a further stratified slurry of dispersion stability. SUMMARY OF THE INVENTION The present inventors have used a non-dispersive honing agent which does not use an organic dispersing agent in addition to the problem of good long-term dispersion stability, good redispersibility, and resolution of aggregation and aggregation as much as possible. As a result of the in-depth study of 1298666, a colloidal fine particle having a smaller average particle diameter than the pulverized fine particles of the colloidal oxide was added, and it was found that the sedimentation and aggregation of the honed fine particles were suppressed, and the present invention was completed. Accordingly, an object of the present invention is to provide a dispersant-free honing agent slurry which does not use an organic dispersant at all, in addition to the problem of good long-term dispersion stability and good redispersibility, as far as possible to eliminate the problem of sedimentation and aggregation. Further, another object of the present invention is to provide a substrate manufacturing method using the above-described honing agent slurry, which is advantageous for manufacturing a substrate for use in a semiconductor manufacturing step by a CMP industry or an aluminum substrate or the like for use in an electrostatic chuck manufacturing step. The present invention is a colloidal oxide containing a selected one or more oxides, and a colloidal oxide having a smaller average particle diameter than the above-mentioned honed microparticles, and dispersing the honed microparticles and colloidal microparticles The dispersant is a honing agent slurry with excellent dispersion stability. Further, a method of producing a substrate comprising the honing step of honing an inorganic substrate using the honing agent slurry. The oxide used in the present invention as a honing microparticle can be used as a user of such honing microparticles, and specific examples thereof include metal oxides such as cerium oxide (Ce02) and manganese dioxide (?? Antimony oxides (SiO 2 ) such as antimony, smog samarium oxide, colloidal cerium oxide, or aluminum oxide compounds (ai2o3) such as smog alumina and colloidal alumina. These may be used alone or in combination of two or more. Among these oxides, as the honing fine particles which are preferably used in the present invention, it is preferable that the cerium oxide particles and the alumina particles have a high specific gravity or a large average particle diameter, and it is preferable that the -8- 1298666 itself is likely to cause sedimentation and agglomeration. This kind of honing is not effective. The average particle size of the honing microparticles used in the present invention is not particularly limited, and varies depending on the type, and is preferably 5,000 to 5,000 nm for cerium oxide particles, preferably 500 to 2,000 nm, and the kind and average particle diameter of the particles. (Dp) can not be fully utilized when it is lower than 100 nm, and vice versa when it exceeds 5,000 nm. Further, the colloidal oxide such as colloidal cerium oxide or colloidal alumina may be used alone or in combination of two or more. Regarding the average particle diameter (Dc) of the colloidal microparticles, at least the above-mentioned honed microparticles vary depending on the type, and the colloidal cerium oxide is usually 10 to 300 nm, preferably 20 to 200 nm, and the average particle diameter (Dp) of the above particles. The particle diameter ratio (Dc / Dp) of the average particles to the colloidal particles is preferably 10 or less, and preferably 0.01. The average particle size (Dc) of the colloidal microparticles is less than 10, and it is easy to gel when it is unstable. On the contrary, when the particle size ratio exceeds 10 00 nm, the particle size is too small to exceed the particle size ratio (Dc / Dp). Give full play to the ability to ponder. Further, as the dispersing agent constituting the honing agent slurry, the dispersing agent used in the honing agent slurry may be directly used without particular limitation, and the use of the slurry, for example, the ruthenium chuck manufacturing step used in accordance with the semiconductor manufacturing step. The fine particles used for the flattening of the substrate such as the aluminum substrate; (Dp), usually, the honing ability is easy to cause the wound, and the like, and the like, if necessary, the honing micro-grain (Dc) ~3 degree nm is easy to produce results. Use this honing agent plate or electrostatic CMP 硏1298666 abrasive paste, blank mask, glass, optical lens, etc. The CMP honing agent slurry and other general honing agent slurry used for honing of the honing surface can be appropriately selected. Water-based, water-based alcohols containing methanol, ethanol, η-propanol, isopropanol, η-butanol, tert-butanol, or ketones, esters, ethers, etc. Aqueous dispersants for the solvent are suitable. Further, in these dispersants, as in the case of the prior art, it is necessary to add an etching liquid for chemical honing at the time of CMP. Therefore, the particle concentration (Cp) of the honing microparticles constituting the honing agent slurry of the present invention varies depending on the type of the pulverized microparticles, and is usually 5 to 40% by weight, preferably 5 to 5% by weight of the cerium oxide particles. 30% by weight, more desirably 5 to 10% by weight, and further, the particle concentration (Cc) of the colloidal fine particles, in the case of containing colloidal ceria, usually 0.1 to 5% by weight, desirably 0.2 to 2% by weight Preferably, the weight ratio (Cc / Cp) of the honed fine particles to the colloidal fine particles is 1 or less, and preferably 0-5 or less. The honing agent slurry prepared with such particle concentrations (Cc) and (Cp) is directly diluted to the specified particle concentration (Cp) and (Cc) by particle concentration (Cp) and (Cc), or as necessary, with a dispersing agent. Used for honing of CMP, etc. When the concentration of the fine particle particles (Cp) is less than 5% by weight, the honing force is insufficient, and if it is higher than 40% by weight, the solubility problem occurs. Further, when the particle concentration (Cc) of the colloidal particles is less than 0.1% by weight, the sedimentation effect is suppressed. On the other hand, when the concentration is higher than 5% by weight, the problem of aggregation is caused. Further, when the weight ratio (Cc/Cp) of the honed particles to the colloidal particles exceeds 1, aggregation tends to occur. The honing agent slurry of the invention, especially the organic dispersing agent without adding water-soluble polymer, -10- 1298666 water-soluble anionic surfactant, water-soluble nonionic interface active and water-soluble amine, also has excellent long-term dispersion Stability, and good redispersibility, can solve the problem of sedimentation and agglutination. Further, in the method for preparing a honing agent slurry, the pulverized fine particles, the colloidal fine particles and the dispersing agent of the constituent components are uniformly mixed, and the pulverized fine particles and the colloidal fine particles are uniformly dispersed in the slurry of the dispersing agent, and there is no particular limitation. It can be prepared by using a usual mixer, and if necessary, an ultrasonic disperser; a homogenizer, a ball mill, a vibrating ball mill, a satellite ball mill, a media agitating mill, etc., can be used. The honing slurry of the present invention is not only flattened by a substrate such as a ruthenium substrate used for a semiconductor manufacturing step or an aluminum substrate for manufacturing an electrostatic chuck, but also used for forming an oxide film such as a ruthenium oxide insulating film having a predetermined wiring on a wiring board. Inorganic insulating film such as glass, oxidized sand, optical glass such as light-shielding film, lens, and magenta, inorganic conductive film such as ITO, optical composite circuit composed of glass crystalline material, optical switching element, optical waveguide, and fiber end face , single crystal for optical use such as scintillator, solid laser single crystal, blue sapphire substrate for blue laser, semiconductor single crystal for Sic, GaP, GaAS, etc., plasmon for magnetic disk, glass substrate, etc. For example, a substrate in which an oxide film of a ruthenium oxide insulating film is formed on a substrate such as a semiconductor substrate in a circuit stage and an aluminum wiring stage, or a semiconductor substrate in a circuit stage, or the like, and CMP is performed for the purpose of flattening the unevenness of the surface of the oxide film. In the case of using a general honing device having a jig for holding the substrate and a rotary disk to which a draped cloth (Pad) is attached, the honing cloth continuously supplies the honing agent slurry of the present invention to the pump, at a specified number of revolutions and Pressurized -11 - 1298666 under honing. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be described in detail with reference to the embodiments and comparative examples. Examples 1 to 27 [Preparation of colloidal cerium oxide (20 nm)] 1 m3 sandwich tank with liquid outlet, liquid level control device and stirrer, 32 kg methyl silicate, 100 kg methanol and 768 Kg pure water, mixed into liquid A. Further, a 3 m3 tank having a stirrer was charged, and 368 kg of methyl phthalate, 100 kg of methanol 1840 kg of pure water, and 12 kg of 28 wt% of ammonia water were charged and mixed to form a liquid B. Secondly, the tank tank installed in A is heated by steam, and the mixture of methanol and water is distilled off. When liquid A starts to be distilled, B liquid is added to maintain liquid A in a certain liquid level. When all the liquids B are added, 240 kg of pure water is added. Maintain liquid A in a certain liquid level and react. After the completion of the reaction, the reaction product was taken out from the tank containing the liquid A, and the cerium oxide was 20% by weight of a colloidal cerium oxide product having an average particle diameter of 20 nm (colloidal cerium oxide (20 nm)). [Preparation of colloidal cerium oxide (70 nm)] 3 m3 of mezzanine tank with agitator 'input 1721.7 kg methanol-12- 1298666, 3 06.3 kg pure water and 88.4 kg of 28 wt% ammonia water, after mixing, adjust The liquid temperature was 23 ± 1 ° C, the liquid temperature was maintained at 23 ± 1 ° C, and 404.4 kg of methyl citrate was reacted under stirring for 2 to 1.5 hours. After the reaction is completed, the crude product of the obtained reaction mixture is transferred to a 1 m3 sandwich tank tank having a liquid outlet, a liquid level control device and a stirrer, and the tank is heated by steam to distill off a mixture of methanol, water and ammonia. When the distillation is started, the remaining reaction mixture is added to maintain a certain liquid level. When the reaction mixture is completely added, pure water is added to the predetermined liquid surface, and pure water is added until the liquid temperature in the tank reaches l〇〇°C. When the liquid temperature reached 100 ° C, the heating was stopped, and the intermediate product was cooled. When the liquid temperature was 70 ° C, an appropriate amount of 28 wt% aqueous ammonia was added, and after stirring and mixing, the reaction product was taken out from the tank. The obtained reaction product cerium oxide was 30% by weight of a colloidal cerium oxide product (colloidal cerium oxide (70 nm)) having an average particle diameter of 70 nm. [Preparation of colloidal cerium oxide (170 nm)] A 1.8 m3 sandwich tank with a stirrer, 8 8 5.1 kg methanol, 6.31 kg pure water and 113.25 kg 28 wt% ammonia water. After mixing, adjust the liquid temperature to 23 At ±1 ° C, the liquid temperature was maintained at 23 ± 1 ° C, and 171.4 kg of methyl citrate was reacted under stirring for 3 hours. After the reaction is completed, the crude product of the obtained reaction mixture is transferred to a 1 m3 sandwich tank tank having a liquid outlet, a liquid level control device and a stirrer, and the tank is heated by steam to distill off a mixture of methanol, water and ammonia. When the distillation is started, the remaining reaction mixture is added to maintain a certain liquid level. When the reaction mixture is all -13-298666, the pure water is added to the specified liquid level, and pure water is added until the liquid temperature in the tank reaches 100 °C. When the liquid temperature reaches 10 °C, the heating is stopped, and the intermediate product is cooled. When the liquid temperature is 70 °C, an appropriate amount of 28 wt% ammonia water is added, and after stirring and mixing, the reaction product is taken out from the tank. The obtained reaction product oxide sand was 22% by weight of a colloidal cerium oxide product having an average particle diameter of 17 〇 nm (colloidal cerium oxide (17 〇 nm)). [Preparation of honing agent slurry] cerium oxide particles having an average particle diameter of 1.1 gram and a maximum particle diameter of 8 // m are used as honing particles (trade name: TE-508, manufactured by SEMICHEMICAL, Japan). Three types of colloidal cerium oxide obtained above were used as colloidal fine particles, and water was used as a dispersing agent, and the mixture was mixed in a ratio shown in Table 1, and uniformly mixed by a stirrer to prepare a honing agent slurry of each of Examples 1 to 27. [Evaluation of Precipitation, Aggregation State, and Redispersibility] The honing slurry obtained in each of Examples 1 to 27 was placed in a test tube at 100 ml for 1 month, and visually observed for precipitation and agglutination. status. In addition, 50 ml of the honing agent slurry was placed in a 100 ml PE container for one month, and then vibrated by hand to visually observe the redispersibility while being placed horizontally on the Zhuo Shang type ball mill (Japan Jinjiang Chamber of Commerce) The system: Model V-1M) was stirred under stirring conditions of 100 rpm and a stirring time of 10 minutes to visually observe the redispersibility of the mixer. -14- 1298666 The results of the above precipitation, agglomeration state and redispersibility are evaluated in the following four stages. ◎: The precipitated parts are all soft, can be redispersed in a few seconds by hand vibration, and can be dispersed in 5 minutes with a stirrer. Redisperse. 〇: The precipitated part has a solid, it takes about 30 seconds to re-disperse by hand vibration, and it takes 10 minutes to re-disperse with a mixer. △: The precipitated portion had a solid, which was re-dispersed by hand for 2 minutes, and further dispersed by a stirrer for 10 minutes. X: The precipitated part was completely cured, and it was no longer dispersed by shaking for 10 minutes with the hand, and it took 10 minutes to re-disperse with a mixer. The results are shown in Table 1. [Quartz substrate honing speed] Further, the honing agent slurry was diluted with 3 times of ultrapure water, and a CMP honing machine (made by Japan NAF-FACTOR Co., Ltd.: FACT-200) with a honing cloth was used, and the number of revolutions was 200 rpm. 500 g / Cm2 pressure, and a speed of 1 〇 ml / min for the honing agent slurry, honing the sample (3.3 cm X 2.6 cm 'thickness of 1 · 15 5 nm quartz substrate) 1 , minutes to The thickness of the sample before and after honing was measured by a micrometer, and the honing speed (//m/l 〇 min) of the quartz substrate (SiO 2 ) was determined from the thickness of the sample before and after honing. Comparative Example ~1 5 Using polyethyl hydrazine quinone ketone (PVP) as an organic dispersant, the honing agent-15-1298666 slurry of the competition examples 1 to 15 was prepared in the same manner as in the above Examples 1 to 27, The honing agents obtained in each of Comparative Examples 1 to 15 were evaluated in the same manner as in Examples 1 to 27, and the honing speed for the quartz substrate (SiO 2 ) was determined. The results are shown in Table 1 in the same manner as in the above Examples-27. -16- 1298666 [Table 1] Example No. 1 2 3 4 5 6 7 8 9 honing agent composition (wt%) cerium oxide particles (Ce02) 5 15 30 5 15 30 5 15 30 colloidal silica dioxide eve ( 20 nm) 1 1 1 2 2 2 5 5 5 Evaluation of solidification state and redispersibility of dispersant precipitation ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ honing speed of quartz substrate (3 times dilution liquid: m m/10 min) 10 10 10 10 10 10 10 10 10 EXAMPLES Να 10 11 12 13 14 15 16 17 18 honing agent composition (wt%) cerium oxide particles (Ce02) 5 15 30 5 15 30 5 15 30 colloidal cerium oxide (70 nm) 1 1 1 2 2 2 5 5 5 Evaluation of solidification state and redispersibility of dispersant precipitation ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ honing speed of quartz substrate (3 times dilution: "m/10min) 10 10 10 10 10 10 10 10 10 Example No. 19 20 21 22 23 24 25 26 27 honing agent composition (wt %) cerium oxide particles (Ce02) 5 15 30 5 15 30 5 15 30 colloidal cerium oxide (170 nm) 1 1 1 2 2 2 5 5 5 Evaluation of solidification state and redispersibility of dispersant precipitation ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ honing speed of quartz substrate (3 times dilution: "m/10min) 1 0 10 10 10 10 10 10 10 10 Comparative Example No. 1 2 3 4 5 6 7 8 9 Composition of honing agent (wt %) Cerium oxide particles (Ce02) 5 15 30 5 15 30 5 15 30 Dispersion of colloidal cerium oxide Agent - - 1 1 1 3 3 3 Precipitation solidification state and redispersibility evaluation XXX Δ Δ Δ XXX Quartz substrate honing speed (3 times dilution: "m/10min) - _ - 10 10 10 10 10 10 Example No· 10 11 12 13 14 15 honing agent composition (wt %) cerium oxide particles (Ce02) 5 15 30 5 15 30 colloidal cerium oxide dispersing agent 1 1 1 3 3 3 precipitation solidification state and redispersibility evaluation Δ Δ Δ 〇 Δ Δ Quartz substrate honing speed (3 times dilution liquid: m/10 min) 10 10 10 10 10 10 -17 - 1298666 It can be understood from the results of Table 1 that it is relative to any of Embodiments 1 to 27 of the present invention. The honing agent has excellent sedimentation, agglutination state and redispersibility, and the honing speed of the quartz substrate is not added to the colloidal particles and the dispersing agent. No honing agent slurry can be redispersed. The grinding speed could not be measured, and only the honing agent slurry of Comparative Examples 4 to 15 in which only 1% by weight and 3% by weight of the dispersing agent were added was added. It took a longer time to disperse, and it was found that the abrasive slurry of the present invention has excellent sedimentation, agglomeration state and redispersibility. According to the present invention, the dispersion stability over time can be provided, and the redispersibility is good, the problem of sedimentation and agglomeration can be eliminated, and a dispersant-free honing agent slurry which does not use an organic dispersant can be used. Further, by using the honing agent slurry of the present invention, it is possible to manufacture a substrate for an aluminum substrate or the like for a semiconductor substrate manufacturing step or a semiconductor chuck manufacturing step for the semiconductor manufacturing step by the CMP industry. -18 -