200930498 九、發明說明 【發明所屬之技術領域】 本發明係關於化學機械硏磨墊及化學機械硏磨方法。 【先前技術】 近幾年之半導體裝置等的製造中，就可形成具有優異 平坦性表面之硏磨方法而言，廣泛使用化學機械硏磨方法 ❺ (Chemical Mechanical Polishing 1 通常簡稱爲「CMP」）。 該化學機械硏磨方法中，已知隨著化學機械硏磨墊之材質 而硏磨結果有相當大變化，而提出各種化學機械硏磨墊。 例如，特開2002- 1 34445號公報係揭示藉由加入具有 如羧基之親水性官能基之單體之聚合物作爲構成硏磨墊之 成分以提高硏磨墊表面之親水性，藉此提高硏磨速度之技 術。但該技術難以獲得均勻之硏磨墊組成物，有損及被硏 磨面平坦性之問題。 © 另外，特開2004-343099號公報揭示藉由使用摻合交 聯二烯彈性體與酸酐改質之聚合物（接枝聚合物）而成之材 料製造硏磨墊，而提高硏磨速度同時改善被硏磨面之平坦 性之技術。若依據該技術，確認可達到確切之硏磨速度及 被硏磨面之平坦性改善程度之效果。然而該技術由於摻合 材料中之接枝聚合物之使用比例變多會損及硏磨墊之機械 強度，故硏磨墊中之酸酐基含有比例之提高有其界限。其 結果，展現上述效果之程度有一定界限。 -5- 200930498 【發明內容】 本發明係鑑於上述問題而開發者，本發明之目的係提 供一種硏磨速度優異且被硏磨面平坦，亦即被硏磨面之硏 磨量之面內均勻性優異、刮痕少之化學機械硏磨墊及使用 該硏磨墊之化學機械硏磨方法。 '依據本發明，本發明之上述課題第一係藉由提供一種 化學機械硏磨墊而達成，該硏磨墊具有由含有（A)非水溶 ❹ 性基質之前驅物成分及（B)水溶性物質之組成物所形成之 硏磨層， 其特徵爲上述（A)非水溶性基質之前驅物成分以其總 量作爲100質量份時，含有60〜100質量份之（A-1)共聚 物，該共聚物係 (al)選自由不飽和羧酸及不飽和羧酸酐組成之群組之 至少一種不飽和化合物，與 (a2)除上述（a 1)以外之不飽和化合物 〇 之無規共聚物或嵌段共聚物。 本發明之上述課題第二係藉由化學機械硏磨方法而達 成，該方法係使用上述化學機械硏磨墊化學機械硏膜被硏 磨物。 【實施方式】 本發明之化學機械硏磨墊具有由含有（A)非水溶性基 質之前驅物成分及（B)水溶性物質之組成物所形成之硏磨 層。 -6- 200930498 以下，對形成本發明化學機械硏磨墊之硏磨層之組成 物（以下稱爲「硏磨層形成用組成物」）之各成分加以說 明。 <(A)非水溶性基質之前驅物成分> 本發明中所用之（A)非水溶性基質之前驅物成分至少 含有（A-1)共聚物，該共聚物爲： (al)選自由不飽和羧酸及不飽和羧酸酐組成之群組之 Q 至少一種不飽和化合物（以下稱爲「不飽和化合物 (al)」），與 (a2)除上述（al)以外之不飽和化合物之無規共聚物或 嵌段共聚物（以下，該等無規共聚物及嵌段共聚物統稱爲 「共聚物（A-1)」）。共聚物（A-1)中之無規共聚物及嵌段共 聚物分別爲不含接枝聚合物（例如酸酐改質之聚合物）。至 於共聚物（A-1)以不飽和化合物（al)與不飽和化合物（a2)之 無規共聚物較佳。 ❹ 至於上述不飽和化合物（al)可適當的使用例如選自由 不飽和單羧酸、不飽和二羧酸及其酸酐以及二價以上之多 價羧酸之單[(甲基）丙烯醯氧基烷基]酯組成之群組之至少 一種不飽和化合物。該等之具體例可分別列舉如下： 不飽和單羧酸，例如丙烯酸、甲基丙烯酸、巴豆酸、 α-氯丙烯酸、桂皮酸等； 不飽和羧酸或其酸酐’例如馬來酸、馬來酸酐、富馬 酸、衣康酸、衣康酸酐、檸康酸、檸康酸酐、仲康酸等； 二價以上之多價羧酸之單[(甲基）丙烯醯氧基烷基] 200930498 酯，例如琥珀酸單（2-丙烯醯氧基乙酯）、琥珀酸單（2-甲@ 丙烯醯氧基乙酯）、苯二甲酸單（2-丙烯醯氧基乙酯）、苯= 甲酸單（2-甲基丙烯醯氧基乙酯）等。 該等中以不飽和單羧酸較佳，尤其以丙烯酸或甲基丙 烯酸較佳。 上述不飽和化合物（a2)只要可與上述不飽和化合物（al) 共聚合即可而無特別限制，但較佳之例示爲例如選自由芳 0 香族乙烯基化合物、茚及其衍生物、脂肪族共軛二烯及 α -烯烴組成之群組之至少一種不飽和化合物。 該等之具體例可分別列舉爲例如芳香族乙烯基化合 物，例如苯乙烯、α -甲基苯乙烯、鄰-乙烯基甲苯、間一 乙烯基甲苯、對一乙烯基甲苯等； 茚及其衍生物，例如茚、1-甲基茚等； 脂肪族共軛二烯，例如1，3-丁二烯、異戊間二烯等； α -烯烴，例如乙烯、丙烯、1-丁烯、1-己烯等。 〇 該等中以α-烯烴較佳，尤其以乙烯較佳。 共聚合物（Α-1)尤其以使用（甲基）丙烯酸作爲不飽和化 合物（al)，使用乙烯作爲不飽和化合物（a2)所得之（甲基） 丙烯酸與乙烯之無規共聚物或嵌段共聚物較佳，且更好爲 (甲基）丙烯酸與乙烯之無規共聚物。 共聚物（A-1)中之不飽和化合物（al)之共聚合比例較好 爲5〜20質量％，更好爲5〜15質量％，又更好爲7~15質量 %。當不飽和化合物（al)之共聚合比例未達5質量％時， 所得化學機械硏磨墊之硏磨面之表面親水性不足，缺乏於 -8- 200930498 化學機械硏磨時所供給化學機械水性分散體之保持能力， 而有損及硏磨速度且刮痕數增大之情況，且由於硏磨面機 械強度不足導致化學機械硏磨墊缺乏耐久性之狀況故而不 佳。另一方面，當不飽和化合物（al)之共聚合比例超過20 質量％時，由於所得共聚物（A-1)之聚合度降低，而無法獲 得高分子量之共聚物，因此使硏磨墊之機械強度降低，導 致化學機械硏磨墊缺乏耐久性故而較不佳。 0 共聚物（人-1)之重量平均分子量以 1 0,000〜200,000較 佳，更好爲20,000〜150,000。 至於共聚物（A-1)亦可使用市售品。該種市售品可列 舉爲例如Recsparl A210K(日本聚乙烯（股）製造）、Unicrel AN4225C、Unicrel N2030H、Unicrel N5130H、Unicrel N 1 5 60、Unicrel N02 00H(以上爲三井·杜邦聚化學（股）製 造）等。 具有由含有如上述之共聚物（A-1)之前驅物成分製造 〇 之非水溶性基質之化學機械硏磨墊在具有化學機械硏谮步 驟中必要之機械強度（適度之硬度等）之同時，由於與化學 機械硏磨時所供給之化學機械硏磨用水性分散體中之硏磨 顆粒之親合性優異，因此顯示高的硏磨速度，且由於可獲 得具有高度面內均勻性之被硏磨物而較佳。 本發明所用之（A)非水溶性基質之前驅物成分以其總 量作爲100質量份時，含有60〜100質量份之如上述之共 聚物（A-1)，較好含有70〜95質量份，更好含有70〜90質 量份。 -9- 200930498 本發明中所用（A)非水溶性基質之前驅物成分至少含 有如上述之共聚物（A-1)，但除此之外亦可視情況含有（A_ 2)其他聚合物、（A-3)分子內具有兩個以上碳-碳雙鍵之 化合物（以下稱爲「多官能性化合物（A-3)」）等。 上述（A-2)其他聚合物較好爲熱可塑性樹脂、彈性 體、橡膠、硬化樹脂（熱硬化性樹脂、光硬化性樹脂等藉 由熱、光等硬化之樹脂）等。更好爲對大部分化學機械硏 Q 磨用水性分散體所含有之強酸或強鹼安定，且因吸水而軟 化少之熱可塑性樹脂或彈性體更好。 上述熱可塑性彈性體可列舉爲例如1,2-聚丁二烯樹 脂、聚烯烴樹脂、聚苯乙烯樹脂、聚酯樹脂、聚醯胺樹 脂、氟樹脂、聚碳酸酯樹脂、聚乙縮醛樹脂等。分別列舉 之上述聚烯烴樹脂爲例如聚乙烯等，上述氟樹脂爲例如聚 偏氟乙烯等。 至於上述彈性體可列舉爲例如二烯彈性體、聚烯烴彈 〇 性體（TPO)、苯乙烯系彈性體、熱可塑性彈性體、聚矽氧 彈性體、氟彈性體等。至於上述二烯彈性體可列舉爲例如 1,2-聚丁二烯等。上述苯乙烯系彈性體可列舉爲例如苯乙 稀—丁二嫌-苯乙嫌嵌段共聚物（SBS)、其氫化嵌段共聚 物（SEBS)等。至於上述熱可塑性彈性體可列舉爲例如熱可 塑性聚胺基甲酸酯彈性體（TPU)、熱可塑性聚酯彈性體 (TPEE)、聚醯胺彈性體（TPAE)等。 至於上述硬化樹脂可列舉爲例如胺基甲酸酯樹脂、環 氧樹脂、丙烯酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯- -10- 200930498 尿素樹脂、尿素樹脂、矽樹脂、酚樹脂、乙烯酯樹脂等。 該等中最好爲I，2-聚丁二烯樹脂。 該等聚合物（A-2)可僅使用一種，亦可兩種以上倂 用。 (A)非水溶性基質之前驅物成分中（A_2)其他聚合物之 含有比例，以（A)非水溶性基質前驅物成分之總量作爲 1〇〇質量份時，較好爲40質量份以下，更好爲5〜30質量 Q 份，而且以10〜30質量份較佳。 上述多官能性化合物（A- 3 )可列舉爲例如乙二醇二（甲 基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、三乙二醇二 (甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、1，4-丁二 醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基）丙烯酸酯、1,9-壬二醇二（甲基）丙烯酸酯、縮水甘油二（甲基）丙烯酸酯、 聚乙二醇（PEG#200)二（甲基）丙烯酸酯、聚乙二醇 (PEG#400)二（甲基）丙烯酸酯、聚乙二醇（PEG#600)二（甲 〇 基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、季戊四 醇三（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、新 戊二醇二（甲基）丙烯酸酯、苯二甲酸二烯丙酯、四烯丙基 氧基乙烷、異脲氰酸三烯丙酯、N，N’-間-伸苯基雙馬來 醯亞胺、Ν,Ν’-伸甲苯基雙馬來醯亞胺、異脲氰酸三烯丙 酯、異脲氰酸三甲基丙烯基酯 '二乙烯基苯、異脲氰酸三 烯丙酯等。另外，上述中，「PEG#200」、「PEG#400」 及「PEG#600」各爲三洋化成（股）製造之聚乙二醇之商品 名，例如所謂「聚乙二醇（PEG#200)二（甲基）丙烯酸酯」 -11 - 200930498 意指聚乙二醇PEG#200之兩端羥基分別與（甲基）丙烯酸形 成酯鍵之化合物。 該等中，以三羥甲基丙烷三（甲基）丙烯酸酯、異脲氰 酸三烯丙基酯或二乙烯基苯較佳。 (A)非水溶性基質之前驅物成分中之多官能性化合物 (A-3)之含有比例，以（A)非水溶性基質之前驅物成分之總 量作爲100質量份時，較好爲1 〇質量份以下，更好爲 ❹ 1〜1 〇質量份，而且以1〜8質量份較佳。 <(B)水溶性物質> 本發明中使用之（B)水溶性物質爲具有可形成在化學 機械硏磨時可保持因與供給之化學機械硏磨用水性分散體 接觸而自硏磨墊之硏磨面脫離之化學機械硏磨用水性分散 體之空孔（孔隙）功能之物質。自硏磨面脫離時，除溶解於 水中之樣態以外，亦包含藉由與水接觸膨潤或溶膠化而脫 離之樣態。 〇 該（B)水溶性物質較好爲有機水溶性物質、無機水溶 性物質之任一種。 至於有機水溶性物質可列舉爲例如糖類（如澱粉、糊 精及環糊精之多醣類、乳糖、甘露糖醇等）、纖維素類（羥 丙基纖維素、甲基纖維素等）、蛋白質、聚乙烯醇、聚乙 烯基吡咯啶酮、聚丙烯酸、聚環氧乙烷、水溶性之感光性 樹脂、磺化聚異戊間二烯、磺化異戊間二烯共聚物等。 無機水溶性物質可列舉爲例如乙酸鉀、硝酸鉀、碳酸 鉀、碳酸氫鉀、溴化鉀、磷酸鉀、硫酸鉀、硫酸鎂及硝酸 -12- 200930498 鈣等。 (B)水溶性物質可使用上述中之單—種類，亦可混合 兩種以上使用。 (B)水溶性物質就可使所得化學機械硏磨墊之硏磨面 之硬度在適度値之觀點而言，以實心體較佳。 另外’（B)水溶性物質以顆粒狀較佳。其平均粒徑較 好爲0.1〜500μηι，更好爲0.5〜ΙΟΟμπι»藉由使（B)水溶性物 Q 質之平均粒徑在上述範圍內，可獲得顯示高的硏磨速度且 機械強度優異之化學機械硏磨墊。 而且，（Β)水溶性物質較好爲僅於化學機械硏磨墊之 硏磨層中露出於表層之情況下於水等中溶解或膨潤，不會 於硏磨層之內部吸濕，而且不會膨潤。因此（Β)水溶性物 質較好具備有抑制最外部之至少一部分吸濕之外殼。該外 殼可藉由物理性吸著（Β )水溶性物質，亦可與（Β)水溶性物 質化學鍵結，進而亦可藉由該二者而鄰接（Β)水溶性物 〇 質。形成該等外殼之材料可列舉爲例如環氧樹脂、聚醯亞 胺、聚醯胺、聚矽酸鹽、矽烷偶合劑等。該情況下，（Β) 水溶性物質可由具有外殼之水溶性物質與不具有外殼之水 溶性物質所構成，亦可由具有外殼之水溶性物質於其表面 全部均被外殻被覆因此可充分獲得上述效果。 本發明中使用之硏磨層形成用組成物中之（Β)水溶性 物質之使用比例，相對於（Α)非水溶性基質之前驅物成分 100質量份，以1〜3 00質量份較佳，以1~250質量份更 佳，且最好爲3~200質量份。 -13- 200930498 藉由使（B)水溶性物質之含有量在上述範圍內，可獲 得顯示高的硏磨速度且保有適度硬度及機械強度之化學機 械硏磨墊。 <交聯劑> 本發明中使用之硏磨層形成用組成物含有如上述之（A) 非水溶性基質之前驅物成分及（B)水溶性物質作爲必要$ 分，但亦可含有其他交聯劑。 Q 本發明之化學機械硏磨墊之硏磨層較好如後所述般具 有交聯構造，但當硏磨層形成用組成物含有交聯劑時，可 藉由加熱進行交聯構造之形成。 該交聯劑可列舉爲例如有機過氧化物、硫、硫化合物 等。該等之中，以使用有機過氧化物較好（以下將使用有 機過氧化物之交聯構造形成方法稱爲「PO交聯」）。有機 過氧化物可列舉爲例如過氧化二異丙苯、二乙基過氧化 物、二第三丁基過氧化物、二乙醯基過氧化物、二醯基過 © 氧化物等。 交聯劑之使用量，相對於（A)非水溶性基質之前驅物 成分100質量份，較好爲10質量份以下，更好爲0.1〜8 質量份。藉由使用量在該範圍內，可使化學機械硏磨步驟 中刮痕之發生受到抑制，且可獲得硏磨速度高之化學機械 硏磨墊。 <硏磨層形成用組成物之調製方法> 獲得本發明中使用之硏磨層形成用組成物之方法並沒 有特別限制。例如可使用混練機，以習知方法混練上述各 -14- 200930498 成分而獲得。混練機可使用以往習知者。列舉爲例如滾筒 式混練機、捏合混練機、班伯里混練機、押出機（單軸、 多軸）等混練機。混練時之溫度可依據所用成分之種類適 度的調整，但較好爲例如70〜150°C。 <化學機械硏磨墊之硏磨層形成方法> 本發明之化學機械硏磨墊之硏磨層係由如上述之組成 物製造。 0 藉由在適當溫度及壓力下使上述組成物成型成所需形 狀，（A)非水溶性基質之前驅物形成非水溶性基質，可使 (B)水溶性物質分散於其中而獲得硏磨層。 本發明之化學機械硏磨墊之硏磨層較好具有交聯構 造。藉由硏磨墊之硏磨層具有交聯構造，故由上述（A)非 水溶性基質之前驅物成分形成之非水溶性基質具有適度之 彈性回復力，硏磨時可抑制因某滑動應力造成之變位於較 小，又，可有效抑制硏磨時及修整時非水溶性基質過度拉 〇 伸延展造成塑性變形而埋入空隙，或可抑制硏磨層之表面 過度起毛等效果。而且，可實現修整時更有效的形成空 隙，且防止硏磨時漿料保持性降低，且起毛較少之優異硏 磨平坦性故而較佳。 至於交聯構造之形成方法並沒有特別的限制。 本發明中使用之硏磨層形成用組成物不含上述交聯劑 之情況爲可藉由電子束照射之經電子束交聯，含有上述交 聯劑之情況爲除例如電子束交聯以外亦可藉由加熱進行交 聯者。 -15- 200930498 以電子束照射進行交聯構造之形成時’較好在 100〜170°c之溫度及較好5〜50MPa之壓力下使上述組成物 成爲所需形狀之成型體，藉由對其進行電子束照射，可獲 得具有交聯構造之硏磨層。 對上述成型體照射電子束之步驟中，電子束之照射量 以 10〜400kGy(Gy : Grey，J/kg)之範圍較佳，更好爲 25〜300 kGy，又更好爲50~200kGy。當電子束之照射量未 φ 達10kGy時，由於藉由電子束產生之自由基不足，使交 聯度太小而不佳。當超過40OkGy時會造成硏磨層中之分 子被切斷，使所得硏磨層之機械強度下降而較不佳。 對上述成型體照射電子束之步驟中，電子束之加速電 壓較好爲 0.5〜3MV之範圍，更好爲0.7〜2.0MV，又更好 爲0.8〜1.5MV，且最好爲0.9〜1.2MV。當照射電壓未達 0.5 MV時，於成型體表層部分捕獲吸收之電子比例相對較 多，使硏磨層內部之交聯不足故而較不佳，另一方面，當 〇 超過3MV時成型體之發熱過大，使構成成型體之材料發 生變質，引起分子斷裂，造成所得硏磨層之機械強度下降 而不佳。 其中，電子線之加速電壓較好依據對於上述成型體之 透過性而適度設定。電子線之透過程度係與成型體厚度及 電子線之運動能量相依存。依據其照射厚度於厚度方向調 節可均勻透過之電子線之照射條件，可成爲厚度方向之交 聯度均勻之成型體而較佳。另外，依據其照射厚度於厚度 方向調節不均勻透過之電子線之照射條件，可獲得適度厚 -16- 200930498 度方向之交聯度不同之硏磨層。 加速電壓較好爲例如以下槪述般設定。 例如當成型體之比重爲1時，若成型體之厚度未達 2mm，則電子束之加速電壓較好爲0.5MV以上，更好爲 0.8MV以上。若成型體之厚度爲2mm以上未達3mm，則 加速電壓較好爲0.8MV以上，更好爲1MV以上。另外， 當厚度在3 mm以上未達4mm時，加速電壓較好爲1.2MV ❹ 以上，更好爲1.5MV以上。當厚度爲4〜5mm時，加速電 壓較好爲1.7MV以上，更好爲2MV以上。對於成型體厚 度之加速電壓過低時，電子線無法貫通厚度方向而無法期 待足夠之電子線照射效果。對於厚度所需之加速電壓係與 成型品之比重成比例。據此，例如當成型體之比重在〇. 8 時所需之加速電壓爲比重1時之加速電壓之0.8倍。 另一方面，藉由加熱進行交聯構造之形成時，較好在 150〜190。(：之溫度及較好在5~50Pa之壓力下將含有上述交 Q 聯劑之組成物成型爲所需形狀’可獲得具有交聯構造之硏 磨層。 至於如上述般獲得之硏磨層之形狀可爲例如圓盤狀 (圓柱狀）、多角柱狀等，以圓盤狀爲較佳。 至於硏磨層之大小，例如爲圓盤狀時’其硏磨面（圓 柱之一面底面）之直徑可爲例如i50-1，200111111，尤其可爲 500~820 mm。至於硏磨墊厚度可爲例如〇.5~5.〇inm’尤其 是1.0〜3.0 mm，其中較好爲1.5~3.〇mm。 又，上述硏磨層可在其硏磨面或其背面具有適當之凹 -17- 200930498 部。至於凹部之形狀可列舉爲同心圓狀溝槽、放射線狀溝 槽、圓形之凹部及多角型凹部或該等之組合等。 <化學機械硏磨墊> 本發明之化學機械硏磨墊具有如上述般形成之硏磨 層。 本發明之化學機械硏磨墊可爲僅由如上述之硏磨層構 成之單層硏磨墊，或者可爲在如上述之硏磨層背側具備有 q 支撐層之多層型墊。 上述支撐層爲在硏磨面之背側支撐化學機械硏磨墊之 層。該等支撐層之特性並無特別限制，但以比硏磨層更軟 質者較佳。由於具備有更軟質之支撐層，因此當硏磨層之 厚度薄時，可防止硏磨時之硏磨墊上浮，或硏磨層之表面 彎曲等，且可進行穩定之硏磨。 支撐層之平面形狀係與硏磨層之平面形狀相同之平面 形狀，且以相同大小較佳。支撐層之厚度較好爲 〇.l~5mm，更好爲 0.2~2.0mm。 <化學機械硏磨方法> 本發明之化學機械硏磨方法爲使用如上述之本發明化 學機械硏磨墊化學機械硏磨被硏磨物者。 如上述之本發明硏磨墊可安裝在市售化學機械硏磨裝 置上，使用適當之化學機械硏磨用水性分散體，且依據習 知方法供應於化學機械硏磨步驟中。 被硏磨面之構成材料可列舉爲由配線材料之金屬、障 壁金屬及絕緣體以及該等之組合所構成之材料。至於上述 -18- 200930498 配線材料之金屬可列舉爲例如鎢、鋁、銅及含有該等之至 少一種之合金等。上述障壁金屬可列舉爲鉅、氮化钽、 鈮、氮化鈮等。至於上述絕緣體可列舉爲例如Si02、於 Si〇2中添加少量氟及磷而成之氟磷矽酸鹽（BPSG)、於 Si02中摻雜氟之稱爲FSG(摻雜氟之矽酸鹽玻璃）之絕緣 體，及低介電率之氧化矽絕緣體等。至於Si02可列舉爲 例如熱氧化膜、PETEOS(電槳加強之-TEOS)、HDP(高密 © 度電漿加強之-TEOS)、藉由CVD法獲得之Si02等。 實施例 以下藉由實施例更具體說明本發明。 實施例1 以溫度調整至140 °C之雙軸押出機混練作爲（A)非水 溶性基質之前驅物成分之1〇〇質量份之共聚物（A-1)丙烯 〇 酸一乙烯共聚物（商品名「Recsparl A210K」，日本聚乙 烯（股）製造，爲7質量％丙烯酸與93質量％乙烯之無規共 聚物）與38質量份之作爲（B)水溶性物質之；S -環糊精（商品 名「Dexsparl /3-100」，鹽水港精糖（股）製造，平均粒徑 1 5 μιη)，獲得硏磨層形成用組成物之顆粒。 使該顆粒在模具內加熱至140 °C可塑化後，使模具內 之溫度冷卻至30°C固化，藉此製作成直徑840mm，厚度 3.5mm之圓盤狀薄片狀成型體。 接著使該薄片狀成型體以掃描方式之電子束照射裝置 -19- 200930498 (NHV Cooperation(股）製造，型號「EPS-3000」），設定在 常溫、常壓下，電壓1MV，電子束量2 5kGy之條件下， 以8脈衝之電子束照射進行電子束交聯。隨後，使用標準 切削機（Wide Belt Sander)進行經電子束交聯之薄片狀成 型體厚度之調整，使厚度成爲2.5mm。 進而，使用加藤機械（股）製造之溝槽加工機，針對厚 度調整後之薄片狀成型體以切削加工形成寬度〇.5mm，深 0 度1.0mm，間距1.5mm之同心圓狀之溝槽（溝槽之剖面形 狀爲矩形），製作硏磨面上具有溝槽之硏磨層。 使用該硏磨層作爲單層之化學機械硏磨墊，且如下列 般進行化學機械硏磨，並評價其硏磨性能。 [化學機械硏磨] 將上述化學機械硏磨墊之未經加工溝槽之面層合3M 公司製造之膠帶#422後，裝置於Applied Mateial公司製 〇 造之化學機械硏磨裝置「Applied Reflexion」上，以單面 表面上具有Cu膜（膜厚l，500nm)之12吋晶圓作爲被硏磨 物，在下列條件下進行Cu膜之化學機械硏磨。 壓盤轉速：120rpm 硏磨頭轉速：1 OOrpm 硏磨壓力：RP/區域1/區域2/區域3=7.5/6.0/3.0/3.5 [psi] 硏磨機械硏磨用水性分散體：CMS7401、CMS7452 (均爲JSR(股）製造）及水之1:1:6(質量比）混合物 -20- 200930498 水性分散體供給速度：300mL/分鐘. 硏磨時間：1分鐘 [硏磨速度及硏磨量之面內均勻性之評價] 在硏磨後之晶圓被硏磨面之直徑方向自兩端分別去除 5 mm之範圍且均等的設定33點之特定點，且針對該等特 定點測定化學機械硏磨前後之Cu膜之厚度。自該測定結 0 果，以下式計算硏磨速度及硏磨量之面內均勻性。 硏磨量=硏磨前之Cu膜厚-硏磨後之Cu膜厚 硏磨速度=硏磨量之平均値/硏磨時間 硏磨量之面內均勻性（％) =(硏磨量之標準偏差+ 硏磨量之平均値）xl〇〇 [刮痕數之評價] D 使用 KLATencor 公司製造之「Surf Scanning SP1」 ，對硏磨後晶圓之被，硏磨面計算被硏磨面整面之刮痕數。 以上之評價結果列於表2。 實施例2 除使用60質量份之共聚物（A-i)丙烯酸-乙烯無規共 聚物「Recsparl A210K」及40質量份之其他聚合物（A-2) 之1,2·聚丁二烯（熱可塑性樹脂，商品名「RB83 0」， JSR(股）製造）作爲（A)非水溶性基質之前驅物成分以外， -21 - 200930498 其餘如實施例1般製作硏磨層。使用該硏磨層作爲單層之 化學機械硏磨墊，且如實施例1般評價其硏磨性能。評價 結果列於表2。 實施例3 除作爲（A)非水溶性基質之前驅物成分使用之共聚物 (A-1)之種類及量以及（B)水溶性物質之種類及量分別如表 φ 1記載以外，其餘如實施例1同樣製作硏磨層，且評價使 用該等作爲單層之化學機械硏磨墊之硏磨性能。評價結果 列於表2。 實施例4 以溫度調整至14〇°C之雙軸押出機混練作爲（A)非水 溶性基質之前驅物成分之90質量份共聚物（Α·1)丙烯酸-乙稀無規共聚物「Recsparl Α210Κ」及10質量份之多官 〇 能性化合物（A-3)之三烯丙基異脲氰酸酯「TAIC」（日本化 成（股）製造），及1質量份之作爲（B)水溶性物質之沒·環糊 精「Dexsparl /5-100」，藉此獲得硏磨層形成用組成物 顆粒。 除使用該顆粒外’其餘如實施例1般製作硏磨層’且 評價使用該等作爲單層之化學機械硏磨墊之硏磨性能。評 價結果列於表2。 實施例5 -22- 200930498 以加熱至1 20°C之捏合機混練作爲（A)非水溶性基質 之前驅物成分之70質量份共聚物（A-1)之甲基丙烯酸-乙 烯共聚物（商品名「AN4225C」，三井杜邦聚化學（股）製 造，爲5質量％甲基丙烯酸及95質量％乙烯之無規共聚 物）、27質量份之其他聚合物（A-2)之苯乙烯—丁二烯共聚 物（商品名「TR2827」，JSR(股）製造）及3質量份之多官 能性化合物（A-3)之三烯丙基異脲氰酸酯「TAIC」，及8 Q 質量份之作爲（B)水溶性物質之召-環糊精「Dexsparl冷-100」。隨後，添加1質量份（換算成純的過氧化二異丙苯 相當於0.4質量份）之作爲有機過氧化物之「Percumyl D40」（商品名，曰本油脂（股）製造，含有40質量％之過氧 化二異丙苯），再經混練後，在模具內加熱至1 70 °C歷時 18分鐘進行交聯反應（PO交聯）成型，獲得直徑840mm， 厚度3.5mm之圓盤狀薄片狀成型體。 除使用該薄片狀成型體外，其餘如實施例1般製作硏 〇 磨層，且評價使用該等作爲單層之化學機械硏磨墊之硏磨 性能。評價結果列於表2。 實施例6〜7及9~12 除作爲（A)非水溶性基質之前驅物成分使用之各單位 成分之種類及量以及（B)水溶性物質之種類及量分別爲表 1所記載以外，其餘如實施例1般製作硏磨層，且評價使 用該等作爲單層之化學機械硏磨墊之硏磨性能。評價結果 列於表2。 -23- 200930498 另外，實施例9中作爲（B)水溶性物質使用之聚環氧 乙烷係以平均粒徑7μιη之顆粒狀存在於所得之硏磨層 中〇 實施例8、13及14 除作爲（Α)非水溶性基質之前驅物成分使用之各單位 成分之種類及量（Β)水溶性物質之種類及量以及交聯劑之 Q 種類及量分別如表1所記載以外，其餘如實施例5般製作 硏磨層，且評價使用該等作爲單層之化學機械硏磨墊之硏 磨性能。評價結果列於表2。 比較例1 除使用20質量份之作爲非水溶性基質之前驅物成分 之接枝共聚物之馬來酸酐改質之苯乙烯-丁二烯一苯乙烯 嵌段共聚物之氫化物（商品名「Toughtek 1911」，旭化成 ❹ (股）製造，酸價；2mg，CH30Na/g，相當於 2.07mg KOH/g)及80質量份之1，2-聚丁二烯「RB83 0」，38質量 份之作爲水溶性物質之泠-環糊精「Dexsparl々-100」以 外，其餘如實施例5般製作硏磨層，且評價使用該等作爲 單層之化學機械硏磨墊之硏磨性能。評價結果列於表2。 比較例2 除作爲非水溶性基質之前驅物成分使用之各單位成分 之種類及量以及水溶性物質之種類及量分別如表1記載以 -24- 200930498 外，其餘如實施例1般製作硏磨層，且評價使用該等作爲 單層之化學機械硏磨墊之硏磨性能。評價結果列於表2。 比較例3〜5 除作爲非水溶性基質之前驅物成分使用之各單位成分 之種類及量以及水溶性物質之種類及量分別如表1所記載 以外，其餘如實施例5般製作硏磨層，且評價使用該等作 Q 爲單層之化學機械硏磨墊之硏磨性能。評價結果列於表 2 〇 ❹ -25- 200930498200930498 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a chemical mechanical honing pad and a chemical mechanical honing method. [Prior Art] In the manufacture of semiconductor devices and the like in recent years, a honing method for forming a surface having excellent flatness is widely used, and a chemical mechanical honing method ("Chemical Mechanical Polishing 1" is often abbreviated as "CMP") is widely used. . In the chemical mechanical honing method, it is known that the honing result varies considerably with the material of the chemical mechanical honing pad, and various chemical mechanical honing pads are proposed. For example, JP-A-2002-134445 discloses that a polymer having a monomer having a hydrophilic functional group such as a carboxyl group is added as a component constituting a honing pad to improve the hydrophilicity of the surface of the honing pad, thereby improving enthalpy. The technology of grinding speed. However, this technique is difficult to obtain a uniform lining pad composition, which is detrimental to the problem of the flatness of the honed surface. Further, Japanese Laid-Open Patent Publication No. 2004-343099 discloses that a honing pad is produced by using a material obtained by blending a crosslinked diene elastomer and an acid anhydride-modified polymer (graft polymer) to increase the honing speed while A technique to improve the flatness of the honed surface. According to this technique, it is confirmed that the exact honing speed and the degree of improvement in the flatness of the honed surface can be achieved. However, this technique has a limit on the increase in the proportion of the acid anhydride group in the honing pad because the use ratio of the graft polymer in the blending material is increased to impair the mechanical strength of the honing mat. As a result, there is a limit to the extent to which the above effects are exhibited. -5- 200930498 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide an honing speed excellent and flattened by a honing surface, that is, a uniform amount of honing of the honed surface. A chemical mechanical honing pad excellent in properties and scratches, and a chemical mechanical honing method using the honing pad. According to the present invention, the first object of the present invention is achieved by providing a chemical mechanical honing pad having a precursor composition containing (A) a non-aqueous soluble matrix and (B) water-soluble. The honing layer formed by the composition of the substance is characterized in that the (A) water-insoluble matrix precursor component contains 60 to 100 parts by mass of the (A-1) copolymer when the total amount thereof is 100 parts by mass. The copolymer (al) is selected from the group consisting of at least one unsaturated compound composed of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and random copolymer of (a2) an unsaturated compound other than the above (a1) Or block copolymer. The second aspect of the present invention is achieved by a chemical mechanical honing method using the above chemical mechanical honing pad chemical mechanical enamel film honing object. [Embodiment] The chemical mechanical honing pad of the present invention has a honing layer formed of a composition containing (A) a water-insoluble precursor component and (B) a water-soluble substance. -6- 200930498 Hereinafter, each component of the composition of the honing layer forming the chemical mechanical honing pad of the present invention (hereinafter referred to as "the composition for honing layer formation") will be described. <(A) Water-insoluble matrix precursor component> The (A) water-insoluble matrix precursor component used in the present invention contains at least (A-1) copolymer, which is: (al) selected a group of a group consisting of a free unsaturated carboxylic acid and an unsaturated carboxylic anhydride; at least one unsaturated compound (hereinafter referred to as "unsaturated compound (al)"), and (a2) an unsaturated compound other than the above (al) A random copolymer or a block copolymer (hereinafter, these random copolymers and block copolymers are collectively referred to as "copolymer (A-1)"). The random copolymer and the block copolymer in the copolymer (A-1) are each a graft-free polymer (e.g., an acid anhydride-modified polymer). As the copolymer (A-1), a random copolymer of an unsaturated compound (al) and an unsaturated compound (a2) is preferred. ❹ As the above unsaturated compound (al), for example, a mono[(meth)acryloxy group selected from an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an acid anhydride thereof, and a divalent or higher polyvalent carboxylic acid may be suitably used. At least one unsaturated compound of the group consisting of alkyl esters. Specific examples of such may be exemplified as follows: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.; unsaturated carboxylic acids or anhydrides thereof such as maleic acid, Malay Anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, seccoic acid, etc.; mono[(meth)acryloxyalkyl] of a polyvalent carboxylic acid of two or more valences 200930498 Esters, such as succinic acid mono(2-propenyloxyethyl ester), succinic acid mono(2-methyl@ propylene methoxyethyl ester), phthalic acid mono(2-propenyl methoxyethyl ester), benzene = Monocarboxylic acid mono(2-methylpropenyloxyethyl ester) or the like. Among these, an unsaturated monocarboxylic acid is preferred, and especially acrylic acid or methacrylic acid is preferred. The unsaturated compound (a2) is not particularly limited as long as it can be copolymerized with the above unsaturated compound (al), but is preferably exemplified, for example, from an aromatic 0-fragrance vinyl compound, an anthracene and a derivative thereof, and an aliphatic group. At least one unsaturated compound of the group consisting of a conjugated diene and an alpha-olefin. Specific examples of such may be exemplified by aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, etc.; , such as hydrazine, 1-methyl hydrazine, etc.; aliphatic conjugated dienes, such as 1,3-butadiene, isoprene, etc.; α-olefins, such as ethylene, propylene, 1-butene, 1 -hexene and the like. Preferably, the α-olefin is preferred among these, and especially ethylene. The copolymer (Α-1) is a random copolymer or block of (meth)acrylic acid and ethylene obtained by using (meth)acrylic acid as the unsaturated compound (al) and ethylene as the unsaturated compound (a2). The copolymer is preferably, and more preferably a random copolymer of (meth)acrylic acid and ethylene. The copolymerization ratio of the unsaturated compound (al) in the copolymer (A-1) is preferably from 5 to 20% by mass, more preferably from 5 to 15% by mass, still more preferably from 7 to 15% by mass. When the copolymerization ratio of the unsaturated compound (al) is less than 5% by mass, the surface of the honing surface of the obtained chemical mechanical honing pad is insufficient in hydrophilicity, and lacks the chemical mechanical water supply at the time of chemical mechanical honing of -8-200930498 The retention ability of the dispersion is detrimental to the honing speed and the number of scratches is increased, and the chemical mechanical honing pad lacks durability due to insufficient mechanical strength of the honing surface. On the other hand, when the copolymerization ratio of the unsaturated compound (al) exceeds 20% by mass, since the degree of polymerization of the obtained copolymer (A-1) is lowered, a copolymer having a high molecular weight cannot be obtained, so that the honing pad is The decrease in mechanical strength results in a lack of durability of the chemical mechanical honing pad and is therefore less preferred. The weight average molecular weight of the copolymer (human-1) is preferably from 10,000 to 200,000, more preferably from 20,000 to 150,000. As the copolymer (A-1), a commercially available product can also be used. Such a commercially available product can be exemplified by, for example, Recsparl A210K (manufactured by Japan Polyethylene Co., Ltd.), Unicel AN4225C, Unicel N2030H, Unicel N5130H, Unicel N 1 5 60, Unicel N02 00H (above is Mitsui DuPont Poly Chemical Co., Ltd.) Manufacturing) and so on. A chemical mechanical honing pad having a water-insoluble substrate made of a precursor component containing a copolymer (A-1) as described above, having the necessary mechanical strength (appropriate hardness, etc.) in a chemical mechanical enthalpy step Since it has excellent affinity with the honing particles in the chemical mechanical honing aqueous dispersion supplied during chemical mechanical honing, it exhibits a high honing speed, and since a high in-plane uniformity can be obtained It is better to honing things. The (A) water-insoluble matrix precursor component used in the invention contains, as a total amount of 100 parts by mass, 60 to 100 parts by mass of the copolymer (A-1) as described above, preferably 70 to 95 by mass. The portion preferably contains 70 to 90 parts by mass. -9- 200930498 The (A) water-insoluble matrix precursor component used in the present invention contains at least the copolymer (A-1) as described above, but may additionally contain (A-2) other polymers, ( A-3) A compound having two or more carbon-carbon double bonds in the molecule (hereinafter referred to as "polyfunctional compound (A-3)") or the like. The other polymer (A-2) is preferably a thermoplastic resin, an elastomer, a rubber, a cured resin (a resin which is cured by heat or light such as a thermosetting resin or a photocurable resin). It is more preferable to be a thermoplastic resin or an elastomer which is stable to a strong acid or a strong base contained in most of the chemical mechanical 硏 Q water-based dispersion, and which is less softened by water absorption. The thermoplastic elastomer may, for example, be a 1,2-polybutadiene resin, a polyolefin resin, a polystyrene resin, a polyester resin, a polyamide resin, a fluororesin, a polycarbonate resin, or a polyacetal resin. Wait. The polyolefin resin described above is, for example, polyethylene or the like, and the fluororesin is, for example, polyvinylidene fluoride. The above elastomer may, for example, be a diene elastomer, a polyolefin elastomer (TPO), a styrene elastomer, a thermoplastic elastomer, a polyoxyxide elastomer, a fluoroelastomer or the like. The diene elastomer may, for example, be 1,2-polybutadiene or the like. The styrene-based elastomer may, for example, be a styrene-butylene-styrene block copolymer (SBS) or a hydrogenated block copolymer (SEBS). The thermoplastic elastomer may, for example, be a thermoplastic polyurethane elastomer (TPU), a thermoplastic polyester elastomer (TPEE), a polyamine elastomer (TPAE) or the like. The above-mentioned hardening resin may, for example, be urethane resin, epoxy resin, acrylic resin, unsaturated polyester resin, polyurethane - -10-200930498 urea resin, urea resin, enamel resin, phenol resin , vinyl ester resin, and the like. Most preferably, these are I,2-polybutadiene resins. These polymers (A-2) may be used alone or in combination of two or more. (A) The content ratio of (A_2) other polymer in the precursor component of the water-insoluble matrix is preferably 40 parts by mass based on the total amount of the (A) water-insoluble matrix precursor component as 1 part by mass. Hereinafter, it is more preferably 5 to 30 parts by mass of Q parts, and more preferably 10 to 30 parts by mass. The polyfunctional compound (A-3) may, for example, be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, or the like. Ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di Methyl) acrylate, glycidyl di(meth) acrylate, polyethylene glycol (PEG #200) di(meth) acrylate, polyethylene glycol (PEG #400) di(meth) acrylate, Polyethylene glycol (PEG #600) bis(methyl decyl) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Neopentyl glycol di(meth)acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N,N'-m-phenylene醯iimine, hydrazine, Ν'-stretching toluene bismaleimide, triallyl cyanurate, trimethyl propylene sulfonate 'divinyl benzene, isocyanuric acid Allyl. In addition, in the above, "PEG#200", "PEG#400" and "PEG#600" are each trade name of polyethylene glycol manufactured by Sanyo Chemical Co., Ltd., for example, "polyethylene glycol (PEG#200) Di(meth)acrylate" -11 - 200930498 means a compound in which the terminal hydroxyl groups of polyethylene glycol PEG #200 form an ester bond with (meth)acrylic acid, respectively. Among these, trimethylolpropane tri(meth)acrylate, triallyl cyanurate or divinylbenzene is preferred. (A) The content ratio of the polyfunctional compound (A-3) in the precursor component of the water-insoluble matrix is preferably 100 parts by mass based on the total amount of the (A) water-soluble matrix precursor component. 1 parts by mass or less, more preferably 1 to 1 part by mass, and more preferably 1 to 8 parts by mass. <(B) Water-soluble substance> The water-soluble substance (B) used in the present invention has a shape which can be formed in the chemical mechanical honing to maintain self-honing due to contact with the supplied chemical mechanical honing aqueous dispersion. The chemical mechanical honing of the matte surface of the mat honing the pores (porosity) function of the aqueous dispersion. When the honing surface is detached, in addition to the form dissolved in water, it also contains a state of being detached by swelling or solification in contact with water. 〇 The (B) water-soluble substance is preferably any of an organic water-soluble substance and an inorganic water-soluble substance. Examples of the organic water-soluble substance include saccharides (such as starch, polysaccharides of dextrin and cyclodextrin, lactose, mannitol, etc.), celluloses (hydroxypropylcellulose, methylcellulose, etc.), Protein, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyethylene oxide, water-soluble photosensitive resin, sulfonated polyisoprene, sulfonated isoprene copolymer, and the like. The inorganic water-soluble substance may, for example, be potassium acetate, potassium nitrate, potassium carbonate, potassium hydrogencarbonate, potassium bromide, potassium phosphate, potassium sulfate, magnesium sulfate or nitric acid -12-200930498 calcium. (B) The water-soluble substance may be used alone or in combination of two or more. (B) The water-soluble substance is preferably a solid body from the viewpoint of moderate hardness of the honing surface of the obtained chemical mechanical honing pad. Further, the (B) water-soluble substance is preferably in the form of particles. The average particle diameter is preferably from 0.1 to 500 μm, more preferably from 0.5 to ΙΟΟμπι», by making the average particle diameter of the (B) water-soluble substance Q in the above range, and exhibiting a high honing speed and excellent mechanical strength. Chemical mechanical honing pad. Further, the (Β) water-soluble substance is preferably dissolved or swollen in water or the like only when exposed to the surface layer in the honing layer of the chemical mechanical honing pad, and does not absorb moisture inside the honing layer, and does not Will swell. Therefore, the (Β) water-soluble substance preferably has an outer casing which suppresses at least a part of the outermost moisture absorption. The outer shell can be chemically adsorbed (Β) with a water-soluble substance, or chemically bonded to the (Β) water-soluble substance, and further, the water-soluble substance can be adjacent to each other. The material forming the outer casing may, for example, be an epoxy resin, a polyimide, a polyamine, a polyphthalate, a decane coupling agent or the like. In this case, the (Β) water-soluble substance may be composed of a water-soluble substance having a shell and a water-soluble substance having no outer shell, or may be covered with a water-soluble substance having a shell on the entire surface thereof, so that the above-mentioned can be sufficiently obtained. effect. The use ratio of the (Β) water-soluble substance in the composition for forming a honing layer to be used in the present invention is preferably from 1 to 30,000 parts by mass based on 100 parts by mass of the precursor component of the water-insoluble substrate. It is preferably 1 to 250 parts by mass, and more preferably 3 to 200 parts by mass. -13- 200930498 By setting the content of the (B) water-soluble substance within the above range, a chemical mechanical honing pad which exhibits a high honing speed and maintains moderate hardness and mechanical strength can be obtained. <Crosslinking agent> The composition for forming a honing layer to be used in the present invention contains (A) the water-insoluble matrix precursor component and (B) the water-soluble substance as described above, but may also contain Other crosslinkers. Q The honing layer of the chemical mechanical honing pad of the present invention preferably has a crosslinked structure as described later, but when the honing layer forming composition contains a crosslinking agent, the crosslinked structure can be formed by heating. . The crosslinking agent may, for example, be an organic peroxide, sulfur, a sulfur compound or the like. Among these, it is preferred to use an organic peroxide (hereinafter, a method of forming a crosslinked structure using an organic peroxide is referred to as "PO crosslinking"). The organic peroxide may, for example, be dicumyl peroxide, diethyl peroxide, di-tert-butyl peroxide, diethyl hydrazine peroxide, di- fluorenyl peroxide or the like. The amount of the crosslinking agent to be used is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the (A) water-insoluble matrix precursor component. By using the amount within this range, the occurrence of scratches in the chemical mechanical honing step can be suppressed, and a chemical mechanical honing pad having a high honing speed can be obtained. <Preparation method of composition for honing layer formation> The method of obtaining the composition for honing layer formation used in the present invention is not particularly limited. For example, it can be obtained by kneading the above-mentioned respective components of -14 to 200930498 by a conventional method using a kneading machine. The kneading machine can be used by conventional practitioners. For example, it is a kneading machine such as a drum type kneader, a kneading kneader, a Banbury kneader, and an extruder (single-axis, multi-axis). The temperature at the time of kneading can be appropriately adjusted depending on the kind of the components to be used, but is preferably, for example, 70 to 150 °C. <Method of Forming Honing Layer of Chemical Mechanical Honing Pad> The honing layer of the chemical mechanical honing pad of the present invention is produced from the composition as described above. 0 By forming the above composition into a desired shape at an appropriate temperature and pressure, (A) a water-insoluble matrix precursor forms a water-insoluble matrix, and (B) a water-soluble substance is dispersed therein to obtain a honing Floor. The honing layer of the chemical mechanical honing pad of the present invention preferably has a crosslinked structure. Since the honing layer of the honing pad has a crosslinked structure, the water-insoluble matrix formed by the precursor component of the above (A) water-insoluble matrix has a moderate elastic restoring force, and can suppress a certain sliding stress during honing The variation is small, and it can effectively inhibit the excessive stretching of the water-insoluble matrix during honing and trimming, thereby causing plastic deformation and embedding in the void, or suppressing the excessive fuzzing of the surface of the honing layer. Further, it is preferable to form the void more effectively at the time of trimming, and to prevent the slurry retainability from being lowered during honing and to have excellent honing flatness with less fluffing. There is no particular limitation on the method of forming the crosslinked structure. The composition for forming a honing layer used in the present invention does not contain the above-mentioned crosslinking agent, and can be cross-linked by electron beam irradiation by an electron beam, and the above-mentioned crosslinking agent is contained in addition to, for example, electron beam crosslinking. The crosslinker can be carried out by heating. -15- 200930498 When forming a crosslinked structure by electron beam irradiation, it is preferable to form the above-mentioned composition into a molded body of a desired shape at a temperature of 100 to 170 ° C and a pressure of preferably 5 to 50 MPa. By performing electron beam irradiation, a honing layer having a crosslinked structure can be obtained. In the step of irradiating the above-mentioned molded body with an electron beam, the irradiation amount of the electron beam is preferably in the range of 10 to 400 kGy (Gy: Grey, J/kg), more preferably 25 to 300 kGy, still more preferably 50 to 200 kGy. When the irradiation amount of the electron beam is not φ of 10 kGy, the degree of crosslinking is too small because the radical generated by the electron beam is insufficient. When it exceeds 40 OkGy, the molecules in the honing layer are cut, which lowers the mechanical strength of the resulting honing layer. In the step of irradiating the above-mentioned molded body with an electron beam, the acceleration voltage of the electron beam is preferably in the range of 0.5 to 3 MV, more preferably 0.7 to 2.0 MV, still more preferably 0.8 to 1.5 MV, and most preferably 0.9 to 1.2 MV. . When the irradiation voltage is less than 0.5 MV, the proportion of electrons trapped in the surface layer of the molded body is relatively large, which makes the internal crosslinking of the honing layer insufficient, and on the other hand, when the enthalpy exceeds 3 MV, the heat of the molded body is low. If it is too large, the material constituting the molded body is deteriorated, causing molecular breakage, resulting in a decrease in the mechanical strength of the obtained honing layer. Among them, the accelerating voltage of the electron beam is preferably set appropriately in accordance with the permeability to the molded body. The degree of transmission of the electron line depends on the thickness of the molded body and the kinetic energy of the electron beam. It is preferable to adjust the irradiation condition of the electron beam which can be uniformly transmitted in the thickness direction in accordance with the thickness of the irradiation, and it is preferable to form a molded body having a uniform degree of crosslinking in the thickness direction. Further, depending on the irradiation conditions in which the thickness of the electron beam which is unevenly transmitted is adjusted in the thickness direction, a honing layer having a moderately thick cross-linking degree in the direction of -16 to 200930498 can be obtained. The acceleration voltage is preferably set as described below, for example. For example, when the specific gravity of the molded body is 1, if the thickness of the molded body is less than 2 mm, the acceleration voltage of the electron beam is preferably 0.5 MV or more, more preferably 0.8 MV or more. When the thickness of the molded body is 2 mm or more and less than 3 mm, the acceleration voltage is preferably 0.8 MV or more, more preferably 1 MV or more. Further, when the thickness is less than 3 mm and not more than 4 mm, the acceleration voltage is preferably 1.2 MV ❹ or more, more preferably 1.5 MV or more. When the thickness is 4 to 5 mm, the acceleration voltage is preferably 1.7 MV or more, more preferably 2 MV or more. When the accelerating voltage of the thickness of the molded body is too low, the electron beam cannot penetrate the thickness direction and the sufficient electron beam irradiation effect cannot be expected. The accelerating voltage required for the thickness is proportional to the specific gravity of the molded article. Accordingly, for example, when the specific gravity of the molded body is 〇8, the acceleration voltage required is 0.8 times the acceleration voltage at a specific gravity of 1. On the other hand, when the crosslinked structure is formed by heating, it is preferably from 150 to 190. (The temperature and preferably the composition containing the above-mentioned cross-linking agent is molded into a desired shape at a pressure of 5 to 50 Pa to obtain a honing layer having a crosslinked structure. As for the honing layer obtained as described above The shape may be, for example, a disk shape (cylindrical shape), a polygonal column shape, or the like, and is preferably a disk shape. As for the size of the honing layer, for example, a disk shape, the honing surface (the bottom surface of the cylinder) The diameter may be, for example, i50-1, 200111111, especially 500 to 820 mm. The thickness of the honing pad may be, for example, 〇.5~5. 〇inm', especially 1.0~3.0 mm, preferably 1.5~3. Further, the honing layer may have a suitable concave portion -17-200930498 on the honing surface or the back surface thereof. The shape of the concave portion may be a concentric circular groove, a radial groove, or a circular shape. a concave portion and a polygonal recess or a combination thereof, etc. <Chemical Mechanical Honing Pad> The chemical mechanical honing pad of the present invention has the honing layer formed as described above. The chemical mechanical honing pad of the present invention may be only a single-layer honing pad composed of a honing layer as described above, or may be a honing layer as described above The side is provided with a multi-layer mat having a q-support layer. The support layer is a layer supporting a chemical mechanical honing pad on the back side of the honing surface. The characteristics of the support layers are not particularly limited, but are softer than the honing layer. Preferably, because of the softer support layer, when the thickness of the honing layer is thin, the honing pad can be prevented from floating up during honing, or the surface of the honing layer can be bent, and stable honing can be performed. The planar shape of the support layer is the same as the planar shape of the honing layer, and is preferably the same size. The thickness of the support layer is preferably 〇.l~5mm, more preferably 0.2~2.0mm. Mechanical Honing Method> The chemical mechanical honing method of the present invention is a chemical mechanical honing of a honed object using the chemical mechanical honing pad of the present invention as described above. The honing pad of the present invention as described above can be installed in commercially available chemistry. The mechanical honing device uses an appropriate chemical mechanical honing aqueous dispersion and is supplied to the chemical mechanical honing step according to a conventional method. The constituent material of the honing surface can be exemplified by the metal of the wiring material and the barrier metal. And insulator And the metal of the wiring material of the above-mentioned -18-200930498, for example, tungsten, aluminum, copper, and an alloy containing at least one of the above, etc. The barrier metal can be exemplified by giant nitriding.钽, 铌, tantalum nitride, etc. As the above insulator, for example, SiO 2 , fluorophosphonium silicate (BPSG) obtained by adding a small amount of fluorine and phosphorus to Si 〇 2, and fluorine doped in SiO 2 are called FSG. Insulators (doped with fluorine bismuth silicate glass), ruthenium oxide insulators with low dielectric constant, etc. As for SiO 2 , for example, thermal oxide film, PETEOS (TEOS enhanced), HDP (high density © kWh) Pulp-reinforced TEOS), SiO 2 obtained by CVD, and the like. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. Example 1 As a (A) water-soluble matrix precursor component, a copolymer of (A-1) a acrylic acid-ethylene copolymer (a) was mixed with a biaxial extruder having a temperature adjusted to 140 °C. The product name "Recsparl A210K", manufactured by Japan Polyethylene Co., Ltd., is a random copolymer of 7 mass% of acrylic acid and 93 mass% of ethylene) and 38 parts by mass of (B) water-soluble substance; S-cyclodextrin (Product name "Dexsparl / 3-100", manufactured by Saline Port Refined Sugar Co., Ltd., having an average particle diameter of 15 μm), and obtained particles of a composition for forming a honing layer. The pellet was heated in a mold to 140 ° C to be plasticized, and then the temperature in the mold was cooled to 30 ° C to be solidified, whereby a disk-shaped sheet-like molded body having a diameter of 840 mm and a thickness of 3.5 mm was produced. Then, the sheet-shaped molded body is subjected to scanning electron beam irradiation apparatus -19-200930498 (manufactured by NHV Cooperation, model "EPS-3000"), and is set at normal temperature and normal pressure, voltage 1 MV, electron beam amount 2 Under the condition of 5 kGy, electron beam crosslinking was carried out by electron beam irradiation of 8 pulses. Subsequently, the thickness of the sheet-shaped molded body which was cross-linked by electron beam was adjusted using a standard cutting machine (Wide Belt Sander) to have a thickness of 2.5 mm. Further, a groove-shaped machine manufactured by Kato Machinery Co., Ltd. was used to form a concentric groove having a width of 〇.5 mm, a depth of 0 degree of 1.0 mm, and a pitch of 1.5 mm for the sheet-shaped molded body after thickness adjustment. The cross-sectional shape of the groove is rectangular), and a honing layer having a groove on the honing surface is produced. This honing layer was used as a single layer of chemical mechanical honing pad, and chemical mechanical honing was performed as follows, and the honing performance was evaluated. [Chemical Mechanical Honing] After the surface of the unprocessed groove of the above chemical mechanical honing pad was laminated to the tape #422 manufactured by 3M Company, the chemical mechanical honing device "Applied Reflexion" manufactured by Applied Mateial Co., Ltd. was installed. On the other hand, a 12-inch wafer having a Cu film (film thickness of 1,500 nm) on a single-sided surface was used as a honed object, and chemical mechanical honing of the Cu film was performed under the following conditions. Platen speed: 120 rpm Honing head speed: 1 OO rpm Honing pressure: RP / Zone 1 / Zone 2 / Zone 3 = 7.5 / 6.0 / 3.0 / 3.5 [psi] Honing mechanical honing water dispersion: CMS7401, CMS7452 (all manufactured by JSR) and water 1:1:6 (mass ratio) mixture -20- 200930498 Aqueous dispersion supply speed: 300mL/min. Honing time: 1 minute [honing speed and honing amount Evaluation of the in-plane uniformity] The wafer after the honing is removed from the both ends by the diameter direction of the honing surface by 5 mm, and the specific points of 33 points are equally set, and the chemical machine is measured for the specific points. The thickness of the Cu film before and after honing. From the results of the measurement, the following equation calculates the in-plane uniformity of the honing speed and the amount of honing. Honing amount = Cu film thickness before honing - Cu film thickness after honing honing speed = average honing amount / honing time in-plane uniformity of honing amount (%) = (honing amount) Standard deviation + average of honing amount) xl 〇〇 [Evaluation of the number of scratches] D Using "Surf Scanning SP1" manufactured by KLATencor, the honing surface is calculated for the honed surface. The number of scratches on the face. The above evaluation results are shown in Table 2. Example 2 In addition to using 60 parts by mass of the copolymer (Ai) acrylic-ethylene random copolymer "Recsparl A210K" and 40 parts by mass of other polymer (A-2) 1,2·polybutadiene (thermoplasticity) Resin, trade name "RB83 0", manufactured by JSR (share)) As the (A) water-insoluble matrix precursor component, -21 - 200930498, the honing layer was produced as in Example 1. This honing layer was used as a single layer chemical mechanical honing pad, and the honing performance was evaluated as in Example 1. The results of the evaluation are shown in Table 2. Example 3 The type and amount of the copolymer (A-1) used as the precursor component of the (A) water-insoluble substrate and (B) the type and amount of the water-soluble substance are as described in Table φ 1, respectively. In Example 1, a honing layer was also prepared, and the honing performance using these chemical mechanical honing pads as a single layer was evaluated. The evaluation results are shown in Table 2. Example 4 Mixing with a biaxial extruder at a temperature adjusted to 14 ° C as 90 parts by mass of a (A) water-insoluble matrix precursor component (Α·1) acrylic-ethylene random copolymer "Recsparl Α210Κ" and 10 parts by mass of the trially-functional compound (A-3) triallyl isocyanurate "TAIC" (manufactured by Nippon Kasei Co., Ltd.), and 1 part by mass of (B) water-soluble A non-volatile substance, cyclodextrin "Dexsparl /5-100", thereby obtaining particles of a composition for honing layer formation. The honing layer was prepared as in Example 1 except that the particles were used, and the honing performance using these chemical mechanical honing pads as a single layer was evaluated. The evaluation results are shown in Table 2. Example 5 -22- 200930498 A methacrylic-ethylene copolymer of 70 parts by mass of the copolymer (A-1) as a precursor component of the (A) water-insoluble matrix was kneaded by a kneader heated to 1200 °C ( The trade name "AN4225C", manufactured by Mitsui DuPont Poly Chemical Co., Ltd., is a random copolymer of 5% by mass of methacrylic acid and 95% by mass of ethylene), and 27 parts by mass of other polymers (A-2) of styrene. Butadiene copolymer (trade name "TR2827", manufactured by JSR) and 3 parts by mass of triallyl isocyanurate "TAIC" of polyfunctional compound (A-3), and 8 Q mass (B) Water-soluble substance call-cyclodextrin "Dexsparl cold-100". Subsequently, 1 part by mass (converted to pure dicumyl peroxide equivalent to 0.4 parts by mass) was added as "organic peroxide" "Percumyl D40" (trade name, 曰本油(股), containing 40% by mass The dicumyl peroxide was pulverized and then kneaded in a mold to 190 ° C for 18 minutes for crosslinking reaction (PO cross-linking) molding to obtain a disk-like flaky shape having a diameter of 840 mm and a thickness of 3.5 mm. Molded body. A ruthenium-polished layer was prepared as in Example 1 except that the sheet-like molded body was used, and the honing performance using these chemical mechanical honing pads as a single layer was evaluated. The evaluation results are shown in Table 2. Examples 6 to 7 and 9 to 12, except that the type and amount of each unit component used as the (A) water-insoluble matrix precursor component and (B) the type and amount of the water-soluble substance are respectively as shown in Table 1, The honing layer was prepared as in Example 1, and the honing performance using these chemical mechanical honing pads as a single layer was evaluated. The evaluation results are shown in Table 2. -23- 200930498 In addition, the polyethylene oxide used as the (B) water-soluble substance in Example 9 is present in the obtained honing layer in the form of particles having an average particle diameter of 7 μm. Examples 8, 13, and 14 The type and amount of each unit component used as the precursor component of the (Α) water-insoluble matrix, and the type and amount of the water-soluble substance and the Q type and amount of the crosslinking agent are as described in Table 1, respectively. The honing layer was prepared in the same manner as in Example 5, and the honing performance using these chemical mechanical honing pads as a single layer was evaluated. The evaluation results are shown in Table 2. Comparative Example 1 A hydride of a maleic anhydride-modified styrene-butadiene-styrene block copolymer (trade name "20 parts by mass of a graft copolymer as a precursor component of a water-insoluble matrix Toughtek 1911", manufactured by Asahi Kasei Co., Ltd., acid value; 2 mg, CH30Na/g, equivalent to 2.07 mg KOH/g) and 80 parts by mass of 1,2-polybutadiene "RB83 0", 38 parts by mass A honing layer was produced as in Example 5 except for the hydrazine-cyclodextrin "Dexsparl(R)-100" which is a water-soluble substance, and the honing performance using these chemical mechanical honing pads as a single layer was evaluated. The evaluation results are shown in Table 2. Comparative Example 2 The type and amount of each unit component used as the precursor component of the water-insoluble substrate, and the type and amount of the water-soluble substance were prepared as in Example 1 except that the amount of the water-soluble substance and the amount of the water-soluble substance were as shown in Table 1 except for -24 to 200930498. The layers were ground and evaluated for the honing performance of these chemical mechanical honing pads as a single layer. The evaluation results are shown in Table 2. Comparative Examples 3 to 5 A honing layer was produced as in Example 5 except that the type and amount of each unit component used as the water-repellent substrate precursor component and the type and amount of the water-soluble substance were as described in Table 1, respectively. And evaluate the honing performance of these chemical mechanical honing pads using Q as a single layer. The results of the evaluation are shown in Table 2 〇 ❹ -25- 200930498
1« 交聯構造形成方法 電子束 電子束 電子束 電子束 〇 (X 電子束 電子束 o 電子束 電子束 電子束 電子束 O Ph O CL, O Oh 電子束 o a. o P-. o cu 交聯劑 量(質量份） 〇 〇 〇 〇 〇 〇 ο 对 o Ο Ο ο ο 寸 O ίΝ 〇 o 寸 o 寸· 对 d & 1 1 1 1 PQD40 1 1 PQD40 1 1 1 1 PQD40 PQD40 PQD40 1 PQD40 PQD40 PQD40 (B冰溶性物質 量(質量份） 00 m 00 〇〇 00 00 Ο 卜 225 m 286 00 m 00 卜 o 00 m 種類 石-CD 召-CD /3-CD 冷-CD /3-CD β-CO β-CO β-CO ΡΕΟ K2S04 β-CO K2S04 K2S04 β-CO β-CD β-CO β-CO 1 /3-CD (A)非水溶性基質前驅物成分 多官能性化合物(A-3) 量(質量份） 〇 〇 〇 〇 〇 in ο ^Τ) o O cn o o 種類 1 1 1 TAIC TAIC TAIC TMP TAIC 1 TAIC TAIC TAIC TAIC 1 1 TAIC 1 TAIC 1 其他聚合物(A-2) 量(質量份） 〇 〇 〇 〇 ο o m W-ί (N o o CN 00 >〇 o o 種類 1 RB830 1 1 TR2827 1 1 RB830 RB830 TR2827 RB830 RB830 1 RB830 TT1911 | RB830 I PAA ω Oh RB830 1 TT1911 RB830 共聚物(A-1) 量(質量份） 〇 § 〇 § 〇 〇\ JO rs o 〇\ § o o \r\ ON o 種類 A210K 1 A210K N0200H A210K AN4225C N2030 A210K N1560 N1560 A210K N1560 N1560 A210K N1560 1 1 N1560 A210K 1 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例ίο 實施例11 實施例12 實施例13 實施例14 比較例1 比較例2 比較例3 比較例4 比較例5 -26- 200930498 上述表1中，各成分之簡稱分別爲如下意義。 <共聚物（A-l)> A210K :丙烯酸一乙烯共聚物（商品名「RecsParl A210K」，日本聚乙烯（股）製造，爲7質量％丙烯酸與93 質量％乙烯之無規共聚物）。 N0200H ：甲基丙烯酸一乙烯共聚物（商品名「Unierel N0200H」，三井杜邦聚化學（股）製造，爲2質量％甲基丙 Q 烯酸及98質量％乙烯之無規共聚物）。 AN4225C:甲基丙烯酸一乙烯共聚物（商品名 「AN4225C」，三井杜邦聚化學（股）製造，爲5質量％甲 基丙烯酸及95質量％乙烯之無規共聚物）。 N2030H :甲基丙烯酸一乙烯共聚物（商品名「Unicrel N2030H」，三井杜邦聚化學（股）製造，爲20質量％甲基 丙烯酸及80質量％乙烯之無規共聚物）。 N1560:甲基丙烯酸一乙烯共聚物（商品名「Unicrel 〇 N1560」，三井杜邦聚化學（股）製造，爲15質量％甲基丙 烯酸及85質量％乙烯之無規共聚物）。 <其他聚合物（A-2)> RB830: 1，2-聚丁二烯（熱可塑性樹脂，商品名 「RB83 0」，JSR(股）製造）。 TR2827 :苯乙烯一丁二烯無規共聚物（商品名 「TR2827」，JSR(股）製造）。 TT1191:馬來酸酐改質之苯乙烯—丁二烯-苯乙烯 嵌段共聚物之氫化物（接枝共聚物’商品名「Toughtek -27- 200930498 1911」’旭化成（股）製造，酸價；2mg，cH3ONa/g，相當 於 2.07mg KOH/g)。 PAA :聚丙烯酸（商品名r Aqualic Η」，日本觸媒（股） 製造）。 ΡΕ :聚乙烯（商品名「yF3〇」，日本聚乙烯（股）製 造）。 比較例1、2及5係分別合倂使用兩種類之聚合物作 0 爲其他聚合物（Α-2)。 <多官能性化合物（Α-3)> TAIC :三烯丙基異氰酸酯（商品名「TAIC」，日本化 成（股）製造）。 TMP :三羥甲基丙烷三甲基丙烯酸酯（商品名 「AcryesterTMP」，三菱縲縈（股）製造）。 <(B)水溶性物質> 沒-CD :召-環糊精（商品名「Dexsparl沒-100」，鹽 〇 水港精糖（股）製造，平均粒徑15μιη) ΡΕΟ:聚環氧乙烷（商品名「Alcoks Ε30」，明成化學 工業（股）製造） K2S04:硫酸鉀（大塚化學（股）製造，平均粒徑50μπι) <交聯劑> PQD40: Percumyl D40(商品名，日油（股）製造，含有 40質量％之過氧化二異丙苯，表1中顯示換算成純的過氧 化二異丙苯之値）。 -28- 200930498 表21« Crosslinking structure formation method Electron beam electron beam electron beam electron beam X (X electron beam electron beam o electron beam electron beam electron beam electron beam O Ph O CL, O Oh electron beam o a. o P-. o cu Coupling dose (mass) 〇〇〇〇〇〇ο 对 o Ο Ο ο ο 寸 O Ν o inch o inch · pair d & 1 1 1 1 PQD40 1 1 PQD40 1 1 1 1 PQD40 PQD40 PQD40 1 PQD40 PQD40 PQD40 (B ice soluble mass (parts by mass) 00 m 00 〇〇00 00 Ο 卜 225 m 286 00 m 00 b o 00 m species stone-CD call-CD /3-CD cold-CD /3-CD β- CO β-CO β-CO ΡΕΟ K2S04 β-CO K2S04 K2S04 β-CO β-CD β-CO β-CO 1 /3-CD (A) Water-insoluble matrix precursor component polyfunctional compound (A-3) Quantity (mass parts) 〇〇〇〇〇in ο ^Τ) o O cn oo Type 1 1 1 TAIC TAIC TAIC TMP TAIC 1 TAIC TAIC TAIC TAIC 1 1 TAIC 1 TAIC 1 Other polymer (A-2) Quantity (Quality )ο om W-ί (N oo CN 00 >〇oo Category 1 RB830 1 1 TR2827 1 1 RB830 RB830 TR2827 RB830 RB830 1 RB830 TT1911 | RB830 I PAA ω Oh RB830 1 TT19 11 RB830 Copolymer (A-1) Amount (parts by mass) 〇§ 〇§ 〇〇\ JO rs o 〇\ § oo \r\ ON o Type A210K 1 A210K N0200H A210K AN4225C N2030 A210K N1560 N1560 A210K N1560 N1560 A210K N1560 1 1 N1560 A210K 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment ίο Example 11 Example 12 Example 13 Example 14 Comparison Example 1 Comparison Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 -26- 200930498 In Table 1, the abbreviations of the respective components are as follows. <Copolymer (A-1)> A210K: Acrylic-ethylene copolymer (trade name "RecsParl A210K", manufactured by Nippon Polyethylene Co., Ltd., is a random copolymer of 7 mass% of acrylic acid and 93 mass% of ethylene). N0200H: a monovinyl methacrylate copolymer (trade name "Unierel N0200H", manufactured by Mitsui DuPont Poly Chemical Co., Ltd., which is a random copolymer of 2% by mass of methacrylic acid and 98% by mass of ethylene). AN4225C: a monovinyl methacrylate copolymer (trade name "AN4225C", manufactured by Mitsui DuPont Poly Chemical Co., Ltd., which is a random copolymer of 5% by mass of methacrylic acid and 95% by mass of ethylene). N2030H: a methacrylic acid-ethylene copolymer (trade name "Unicrel N2030H", manufactured by Mitsui DuPont Poly Chemical Co., Ltd., which is a random copolymer of 20% by mass of methacrylic acid and 80% by mass of ethylene). N1560: a monovinyl methacrylate copolymer (trade name "Unicrel 〇 N1560", manufactured by Mitsui DuPont Poly Chemical Co., Ltd., which is a random copolymer of 15% by mass of methacrylic acid and 85% by mass of ethylene). <Other polymer (A-2)> RB830: 1,2-polybutadiene (thermoplastic resin, trade name "RB83 0", manufactured by JSR Co., Ltd.). TR2827: Styrene-butadiene random copolymer (trade name "TR2827", manufactured by JSR). TT1191: a hydride of a maleic anhydride modified styrene-butadiene-styrene block copolymer (graft copolymer 'trade name "Toughtek -27- 200930498 1911", manufactured by Asahi Kasei Co., Ltd., acid value; 2 mg, cH3ONa/g, equivalent to 2.07 mg KOH/g). PAA: Polyacrylic acid (trade name r Aqualic Η), manufactured by Nippon Shokubai Co., Ltd.). ΡΕ : Polyethylene (trade name "yF3〇", made of Japanese polyethylene (share)). Comparative Examples 1, 2, and 5 were used in combination with two types of polymers as 0 for other polymers (Α-2). <Polyfunctional compound (Α-3)> TAIC: triallyl isocyanate (trade name "TAIC", manufactured by Nippon Kasei Co., Ltd.). TMP: Trimethylolpropane trimethacrylate (trade name "AcryesterTMP", manufactured by Mitsubishi Rayon Co., Ltd.). <(B) Water-soluble substance> No-CD: Call-cyclodextrin (trade name "Dexsparl not-100", manufactured by Yanshuigang Jingjing (stock), average particle size 15μιη) ΡΕΟ: Polyepoxy Alkane (trade name "Alcoks Ε30", manufactured by Mingcheng Chemical Industry Co., Ltd.) K2S04: Potassium sulphate (manufactured by Otsuka Chemical Co., Ltd., average particle size 50 μm) <crosslinking agent> PQD40: Percumyl D40 (trade name, day) The oil (stock) was produced and contained 40% by mass of dicumyl peroxide, and the amount shown in Table 1 was converted to pure dicumyl peroxide. -28- 200930498 Table 2
評價結果 硏磨速度(mn/分） 硏磨量之面內均勻性(％) 刮痕(個/晶圓） 實施例1 730 2.8 32 實施例2 830 3.2 45 實施例3 650 5.8 57 實施例4 780 2.9 43 實施例5 770 3.5 28 實施例6 810 3.3 44 實施例7 780 2.9 26 實施例8 840 2.6 18 實施例9 820 2.8 35 實施例10 760 3.5 28 實施例11 770 2.9 38 實施例12 790 4.4 24 實施例13 630 5.5 45 實施例14 750 3.8 28 比較例1 580 6.8 130 比較例2 420 8.3 65 比較例3 620 4.5 82 比較例4 570 4.8 58 比較例5 380 9.8 75 -29- 200930498Evaluation results Honing speed (mn/min) In-plane uniformity of honing amount (%) Scratches (pieces/wafer) Example 1 730 2.8 32 Example 2 830 3.2 45 Example 3 650 5.8 57 Example 4 780 2.9 43 Example 5 770 3.5 28 Example 6 810 3.3 44 Example 7 780 2.9 26 Example 8 840 2.6 18 Example 9 820 2.8 35 Example 10 760 3.5 28 Example 11 770 2.9 38 Example 12 790 4.4 24 Example 13 630 5.5 45 Example 14 750 3.8 28 Comparative Example 1 580 6.8 130 Comparative Example 2 420 8.3 65 Comparative Example 3 620 4.5 82 Comparative Example 4 570 4.8 58 Comparative Example 5 380 9.8 75 -29- 200930498
Cu之化學機械硏磨步驟中’若硏磨速度在600nm/ min以上，硏磨量之面內均勻性6%以下且刮痕60個以下 則被認爲具有良好之硏磨特性。依據表2，可明瞭實施例 1〜14中之本發明之化學機械硏磨墊具有良好之硏磨特 性。相對於該等，非本發明之比較例之化學機械硏磨 墊於硏磨速度、硏磨量之面內均勻性及刮痕性能均顯示非 爲良好結果者。 0 由以上說明，依據本發明，提供一種硏磨速度優異， 硏磨量之面內均勻性優異且獲得刮痕少之被硏磨面之化學 機械硏磨墊及化學機械硏磨方法。 ❿ -30-In the chemical mechanical honing step of Cu, if the honing speed is 600 nm/min or more, the in-plane uniformity of the honing amount is 6% or less and the scratches are 60 or less, it is considered to have good honing characteristics. According to Table 2, it is understood that the chemical mechanical honing pads of the present invention in Examples 1 to 14 have good honing characteristics. With respect to these, the chemical mechanical honing pad of the comparative example of the present invention showed no good results in terms of honing speed, in-plane uniformity of honing amount, and scratch performance. As described above, according to the present invention, there is provided a chemical mechanical honing pad and a chemical mechanical honing method which are excellent in honing speed, excellent in-plane uniformity of honing amount, and which have a small scratching surface. ❿ -30-