[0009] 以下，說明本發明之較佳實施形態。又，本說明書中特別提及之事項以外之情況之實施本發明必要之情況係熟悉該技藝者基於該領域中之以往技術能以設計事項而掌握者。本發明可基於本說明書中揭示之內容與該領域中之技術知識而實施。 [0010] 依據本說明書，提供研磨用組成物之製造方法、用以製造該研磨用組成物之研磨用組成物套組及使用該研磨用組成物之矽晶圓之研磨方法。以下，首先針對藉由本文揭示之方法製造之研磨用組成物加以說明，其次依序說明其製造方法、研磨用組成物套組、使用研磨用組成物之研磨方法。 [0011] ＜研磨用組成物＞ (研磨粒) 本文揭示之研磨用組成物含有研磨粒。研磨粒之材質或性狀並未特別限制，可根據使用目的或使用樣態適當選擇。作為研磨粒之例舉例為無機粒子、有機粒子及有機無機複合粒子。無機粒子之具體例列舉為氧化矽粒子、氧化鋁粒子、氧化鈰粒子、氧化鉻粒子、二氧化鈦粒子、氧化鋯粒子、氧化鎂粒子、二氧化錳粒子、氧化鋅粒子、氧化鐵(Bengala)粒子等之氧化物粒子；氮化矽粒子、氮化硼粒子等之氮化物粒子；碳化矽粒子、碳化硼粒子等之碳化物粒子；金剛石粒子；碳酸鈣或碳酸鋇等之碳酸鹽等。有機粒子之具體例列舉為聚甲基丙烯酸甲酯(PMMA)粒子或聚(甲基)丙烯酸粒子、聚丙烯腈粒子等。該等研磨粒可單獨使用1種，亦可組合2種以上使用。又，所謂(甲基)丙烯酸意指包括丙烯酸及甲基丙烯酸。 [0012] 作為上述研磨粒較好為無機粒子，其中較好為由金屬或半金屬之氧化物所成之粒子。本文揭示之技術中作為特佳研磨粒舉例為氧化矽粒子。本文揭示之技術可較好地以研磨粒實質上由氧化矽粒子所成之樣態而實施。本文所謂「實質上」意指構成研磨粒之粒子之95重量%以上，較好98重量%以上，更好99重量%以上為氧化矽粒子，亦可為構成研磨粒之粒子的100重量%為氧化矽粒子。 [0013] 作為氧化矽粒子之具體例，列舉為膠體二氧化矽、發煙二氧化矽、沉降二氧化矽等。氧化矽粒子可單獨使用1種或組合2種以上使用。基於於研磨對象物表面不易產生刮痕，且可更發揮良好研磨性能之觀點，特佳為膠體氧化矽。上述研磨性能係使表面粗糙度降低之性能等。作為膠體氧化矽，可較好地採用將例如以水玻璃(矽酸鈉)為原料藉由離子交換法製作之膠體氧化矽或烷氧化物法膠體氧化矽。所謂烷氧化物法膠體氧化矽係藉由烷氧基矽烷之水解縮合反應而製造之膠體氧化矽。膠體氧化矽可單獨使用1種或組合2種以上使用。 [0014] 構成氧化矽粒子之氧化矽的真比重較好為1.5以上，更好為1.6以上，又更好為1.7以上。藉由增大氧化矽之真比重，有提高研磨速率之傾向。基於該觀點，特佳為真比重2.0以上，例如2.1以上之氧化矽粒子。氧化矽之真比重上限並未特別限制，典型上為2.3以下，例如2.2以下。作為氧化矽之真比重可採用使用乙醇作為置換液之液體置換法所得之測定值。 [0015] 本文揭示之研磨粒之平均一次粒徑並未特別限定。基於研磨速率等之觀點，上述平均一次粒徑為5nm以上為適當，較好為10nm以上，更好為30nm以上，又更好為40nm以上，特佳為45nm以上。於特佳一樣態中，上述平均一次粒徑為例如50nm以上。上述研磨粒典型上為氧化矽粒子。且，基於防止刮傷等之觀點，研磨粒之平均一次粒徑設為200nm以下為適當，較好為100nm以下，更好為80nm以下，又更好為70nm以下，特佳為60nm以下。 又，本說明書中所謂平均一次粒徑意指自利用BET法測定之比表面積(BET值)藉由BET徑(nm)=6000/(真密度(g/cm3
)×BET值(m2
/g))之式算出之粒徑。例如氧化矽粒子時，可藉由BET徑[nm]=2727/BET值[m2
/g]算出BET徑。比表面積之測定例如可使用MICRO MATERIALS公司製之表面積測定裝置，商品名「Flow Sorb II 2300」進行。 [0016] 研磨粒之形狀(外形)可為球形，亦可為非球形。成為非球形之粒子之具體例列舉為花生形狀、繭型形狀、金平糖形狀、橄欖球形狀等。花生形狀即為落花生之殼形狀。例如，可較好地採用粒子大多為花生形狀之研磨粒。 [0017] 雖無特別限制，但研磨粒之長徑/短徑比之平均值(平均長寬比)原理上為1.0以上，較好為1.05以上，更好為1.1以上。藉由增大平均長寬比，可實現更高之研磨速率。且，研磨粒之平均長寬比，基於減少刮痕等之觀點，較好為3.0以下，更好為2.0以下，又更好為1.5以下。 [0018] 研磨粒之形狀(外形)或平均長寬比可利用例如電子顯微鏡觀察而掌握。掌握平均長寬比之具體順序為例如使用掃描型電子顯微鏡(SEM)，針對可辨識獨立粒子形狀之既定個數之氧化矽粒子，描繪出外切於各粒子圖像之最小長方形。所謂既定個數例如為200個。接著，針對對各粒子圖像描繪出之長方形，將其長邊之長度(長徑之值)除以短邊之長度(短徑之值)之值作為長徑/短徑比(長寬比)而算出。藉由算術平均上述既定個數之粒子長寬比，可求出平均長寬比。 [0019] 本文揭示之研磨用組成物中之研磨粒含量並未特別限制，較好為0.05重量%以上，更好為0.1重量%以上，又更好為0.3重量%以上。於進而較佳一樣態中，上述研磨粒含量為0.5重量%以上。藉由增大研磨粒含量，可實現更高之研磨速率。且基於自研磨對象物之去除性等之觀點，上述含量宜為10重量%以下，較好為7重量%以下，更好為5重量%以下，進而更好3重量%以下。進而較佳一樣態中，上述研磨粒含量為例如2重量%以下。 [0020] (水溶性高分子P1) 本文揭示之研磨用組成物包含慣性半徑為100nm以上之水溶性高分子P1。藉由使用具有上述慣性半徑之水溶性高分子P1，而改善邊緣滑離。其理由並未特別限定解釋，但推測研磨用組成物(研磨漿料)中所含之具有特定慣性半徑之水溶性高分子P1可避免過強吸附於研磨對象基板之端部而過度研磨，而抑制了邊緣滑離(端部塌邊)之增大。又，水溶性高分子P1之慣性半徑係水溶液中之水溶性高分子P1一分子之尺寸，主要可由該高分子P1之親水性、分子量等決定。基於邊緣滑離改善之觀點，水溶性高分子P1之慣性半徑較好為105nm以上，更好為120nm以上，特佳為140nm以上。水溶性高分子P1之慣性半徑上限並未特別限定，基於研磨用組成物製造中作為水溶性高分子P1含有液使用之B液之安定性或濃縮效率等之觀點，約為250nm以下為適當，較好為300nm以下，更好為250nm以下，又更好為220nm以下。水溶性高分子P1之慣性半徑亦可為例如150nm以下，120nm以下。又本說明書中之水溶性高分子之慣性半徑可藉後述實施例中記載之方法測定。 [0021] 本文揭示之研磨用組成物所含之水溶性高分子P1之種類並未特別限定，可自研磨用組成物之領域中習知水溶性高分子種類之中適當選擇。水溶性高分子P1可單獨使用1種或組合2種以上使用。作為水溶性高分子P1之例，舉例為纖維素衍生物、澱粉衍生物、含氧基伸烷基單位之聚合物、含有氮原子之聚合物、聚乙烯醇等。其中，基於平坦度提高之觀點，較好為纖維素衍生物、澱粉衍生物，更好為纖維素衍生物。 [0022] 纖維素衍生物係含有β-葡萄糖單位作為主要重複單位之聚合物。作為纖維素衍生物之具體例舉例為羥基乙基纖維素(HEC)、羥基丙基纖維素、羥基乙基甲基纖維素、羥基丙基甲基纖維素、甲基纖維素、乙基纖維素、乙基羥基乙基纖維素、羧基甲基纖維素等。其中以HEC較佳。 [0023] 澱粉衍生物係含有α-葡萄糖單位作為主要重複單位之聚合物。作為澱粉衍生物之具體例舉例為α化澱粉、普魯蘭多糖(pullulan)、羧甲基澱粉、環糊精等。其中較好為普魯蘭多糖。 [0024] 含氧基伸烷基單位之聚合物例示為聚環氧乙烷(PEO)、或環氧乙烷(EO)與環氧丙烷(PO)或與環氧丁烷(BO)之嵌段共聚物、EO與PO或與BO之無規共聚物等。其中，較好為EO與PO之嵌段共聚物或EO與PO之無規共聚物。EO與PO之嵌段共聚物可為含有PEO嵌段與聚環氧丙烷(PPO)嵌段之二嵌段體、三嵌段體等。上述三嵌段體之例包含PEO-PPO-PEO型三嵌段體及PPO-PEO-PPO型三嵌段體。其中更好為PEO-PPO-PEO型三嵌段體。 EO與PO之嵌段共聚物或無規共聚物中，構成該共聚物之EO與PO之莫耳比[EO/PO]，基於於水中之溶解性或洗淨性等之觀點，較好大於1，更好為2以上，又更好為3以上。進而較佳一樣態中，上述莫耳比[EO/PO]為例如5以上。 [0025] 作為含有氮原子之聚合物，主鏈中含有氮原子之聚合物及於側鏈官能基(側鏈基)中具有氮原子之聚合物之任一者均可使用。藉由使用含有氮原子之聚合物，可改善基板表面粗糙度。作為主鏈中含有氮原子之聚合物之例，舉例為N-醯基伸烷基亞胺型單體之均聚物及共聚物。N-醯基伸烷基亞胺型單體之具體例舉例為N-乙醯基伸乙基亞胺、N-丙醯基伸乙基亞胺等。作為於側鏈基中具有氮原子之聚合物舉例為例如含有N-乙烯基型之單體單位之聚合物等。例如可採用N-乙烯基吡咯啶酮之均聚物及共聚物等。本文揭示之技術中，可較好地採用N-乙烯基吡咯啶酮以50莫耳%以上比例聚合之N-乙烯基吡咯啶酮之均聚物及共聚物之至少一種(以下亦稱為「PVP」)。 [0026] 使用聚乙烯醇作為水溶性高分子P1時，該聚乙烯醇之皂化度並未特別限定。 [0027] 本文揭示之技術中水溶性高分子P1之分子量並未特別限定。基於濃縮效率等之觀點，水溶性高分子P1之重量平均分子量(Mw)通常可為約300×104
以下，150×104
以下為適當。上述Mw亦可為例如130×104
以下，亦可為110×104
以下。且，基於基板表面之保護性或研磨性能提高之觀點，Mw為1×104
以上為適當，較好為10×104
以上，更好為20×104
以上。更佳一樣態中，上述Mw為例如50×104
以上，更佳為80×104
以上。上述Mw為例如110×104
以上，可為130×104
以上。上述Mw對於纖維素衍生物可特別佳地採用。作為上述纖維素衍生物舉例為例如HEC。 [0028] 水溶性高分子P1之重量平均分子量(Mw)與數平均分子量(Mn)之關係並未特別限定。基於防止凝集物發生等之觀點，例如較好係分子量分佈[Mw/Mn]為10.0以下者，更好為7.0以下者。 [0029] 又，作為水溶性高分子P1之Mw及Mn，可採用基於水系之凝膠滲透層析法(GPC)之值(水系，聚環氧乙烷換算)。針對後述之水溶性高分子P2亦同樣。 [0030] 上述研磨用組成物中之水溶性高分子P1之含量，基於研磨性能或表面品質提高等之觀點，適當為1×10-5
重量%以上，例如為5×10-5
重量%以上，較好為1×10-4
重量%以上。較佳一樣態中，上述水溶性高分子P1之含量為例如2×10-4
重量%以上。上述研磨用組成物中之水溶性高分子P1之含量上限可為例如1重量%以下。基於濃縮液階段之安定性或研磨速率、洗淨性等之觀點，水溶性高分子P1之含量較好為0.1重量%以下，更好為0.05重量%以下，又更好為0.02重量%以下，特佳為0.01重量%以下。於特佳一樣態中，上述水溶性高分子P1之含量為例如0.005重量%以下，典型上為0.001重量%以下。上述濃縮液典型上為B液。 [0031] 又，本文揭示之研磨用組成物中之水溶性高分子P1之含量，可由與研磨用組成物中所含之研磨粒之相對關係而特定。具體而言，研磨用組成物中之水溶性高分子P1之含量，相對於研磨粒100重量份，設為0.001重量份以上為適當，基於邊緣滑離改善等之觀點，較好為0.005重量份以上，更好為0.01重量份以上，又更好為0.015重量份以上。且，基於安定性或研磨速率等之觀點，水溶性高分子P1之含量，相對於研磨粒100重量份，設為10重量份以下為適當，較好為1重量份以下，更好為0.5重量份以下，又更好為0.3重量份以下。 [0032] (水溶性高分子P2) 本文揭示之技術之較佳一樣態中，研磨用組成物除了慣性半徑為100nm以上之水溶性高分子P1以外，進而包含慣性半徑未達100nm之水溶性高分子P2。該水溶性高分子P2與水溶性高分子P1不同，係負責蝕刻抑制等之基板表面保護之角色且對表面粗糙度減低作出貢獻之成分，故亦稱為基板表面保護劑。水溶性高分子P2之慣性半徑，基於安定性或濃縮效率等之觀點，較好未達90nm，更好未達70nm，又更好未達50nm。進而較佳一樣態中，上述水溶性高分子P2之慣性半徑為例如未達30nm，典型上未達5nm。水溶性高分子P2之慣性半徑之下限並未特別限定，可為0.1nm以上，例如1nm以上。 [0033] 水溶性高分子P2之種類並未特別限定，可自研磨用組成物之領域中習知水溶性高分子種之中適當選擇。水溶性高分子P2之例舉例為作為水溶性高分子P1例示之纖維素衍生物、澱粉衍生物、含氧基伸烷基單位之聚合物、含有氮原子之聚合物、聚乙烯醇等。基於減低表面粗糙度之觀點，水溶性高分子P2較好為纖維素衍生物及/或澱粉衍生物以外之高分子，更好為含有氮原子之聚合物。上述纖維素衍生物及/或澱粉衍生物以外之高分子典型上為纖維素衍生物以外之高分子。作為纖維素衍生物、澱粉衍生物、含氧基伸烷基單位之聚合物、含有氮原子之聚合物、聚乙烯醇之具體例，可使用作為水溶性高分子P1例示者之1種或2種以上。其中，較好為主鏈中含有氮原子之聚合物、於側鏈官能基(側鏈基)中具有氮原子之聚合物，更好為含有N-乙烯基型之單體單位之聚合物。其中，特佳為N-乙烯基吡咯啶酮之均聚物及共聚物(典型上為PVP)等。 [0034] 水溶性高分子P2之分子量並未特別限定。水溶性高分子P2之重量平均分子量(Mw)可為約300×104
以下，150×104
以下，例如50×104
以下為適當。基於安定性等之觀點，上述Mw亦可為30×104
以下，例如可為5×104
以下。且，基於基板表面之保護性提高之觀點，Mw為1×104
以上為適當，較好為2×104
以上，更好為3×104
以上。上述Mw對於N-乙烯基吡咯啶酮之均聚物及共聚物(典型上為PVP)可特別佳地採用。 [0035] 水溶性高分子P2之重量平均分子量(Mw)與數平均分子量(Mn)之關係並未特別限定。基於防止凝集物發生等之觀點，例如較好係分子量分佈[Mw/Mn]為10.0以下者，更好為7.0以下者，又更好為5.0以下者，特佳為4.0以下者，最好為3.0以下者。 [0036] 本文揭示之技術中，作為水溶性高分子組合使用水溶性高分子P1與水溶性高分子P2時，水溶性高分子P1與水溶性高分子P2之調配比例並未特別限定，例如水溶性高分子P1：水溶性高分子P2為1：9~9：1為適當，較好為3：7~8：2，更好為5：5~7：3。又，上述水溶性高分子P1為例如HEC等之纖維素衍生物，上述水溶性高分子P2為例如PVP等之包含N-乙烯基型之單體單位的聚合物。 [0037] 一樣態之研磨用組成物之水溶性高分子P2之含量，於將水溶性高分子P1之含量設為100重量%時，為未達100重量%，基於安定性之觀點，較好未達80重量%，更好未達70重量%。於更佳一樣態中，上述水溶性高分子P2之含量為例如未達60重量%。且基於減低表面粗糙度等之觀點，水溶性高分子P2之含量，於將水溶性高分子P1之含量設為100重量%時，可為約10重量%以上，為30重量%以上為適當，較好為50重量%以上。本文揭示之技術中，研磨用組成物包含水溶性高分子P2之情況或不含之情況，水溶性高分子P1以外之水溶性高分子含量，於將水溶性高分子P1之含量設為100重量%時，均可為未達200重量%左右，例如未達150重量%，進而未達100重量%為適當。基於安定性之觀點，水溶性高分子P1以外之水溶性高分子含量，於將水溶性高分子P1之含量設為100重量%時，較好為未達80重量%，更好未達70重量%，進而未達50重量%，例如可為未達30重量%，亦可為未達10重量%，例如1重量%以下，具體為0~1重量%。更佳一樣態中，水溶性高分子P1以外之水溶性高分子含量，例如為未達60重量%。 [0038] (鹼性化合物) 本文揭示之研磨用組成物含有鹼性化合物。本說明書中所謂鹼性化合物係指具有藉由溶解於水中而提高水溶液之pH之功能的化合物。作為鹼性化合物可使用含氮之有機或無機之鹼性化合物、鹼金屬之氫氧化物、鹼土類金屬之氫氧化物、各種碳酸鹽或碳酸氫鹽等。作為含氮之鹼性化合物之例舉例為四級銨化合物、四級鏻化合物、氨、胺等。上述胺較好為水溶性胺。此等鹼性化合物可單獨使用1種或組合2種以上使用。 [0039] 作為鹼金屬之氫氧化物之具體例舉例為氫氧化鉀、氫氧化鈉等。作為碳酸鹽或碳酸氫鹽之具體例舉例為碳酸氫銨、碳酸銨、碳酸氫鉀、碳酸鉀、碳酸氫鈉、碳酸鈉等。作為胺之具體例舉例為甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙二胺、單乙醇胺、N-(β-胺基乙基)乙醇胺、六亞甲基二胺、二伸乙基三胺、三伸乙基四胺、無水哌嗪、哌嗪六水合物、1-(2-胺基乙基)哌嗪、N-甲基哌嗪、胍、咪唑或三唑等唑(azole)類等。作為四級鏻化合物之具體例舉例為氫氧化四甲基鏻、氫氧化四乙基鏻等之氫氧化四級鏻。 [0040] 作為四級銨化合物可較好地使用四烷基銨鹽、氫氧化烷基三烷基銨鹽等之四級銨鹽。上述四級銨鹽典型為強鹼。該四級銨鹽中之陰離子成分可為例如OH-
、F-
、Cl-
、Br-
、I-
、ClO4 -
、BH4 -
等。其中作為較佳例舉例為陰離子係OH-
之四級銨鹽，亦即氫氧化四級銨。作為氫氧化四級銨之具體例舉例為氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四戊基銨及氫氧化四己基銨等之氫氧化四烷基銨；氫氧化2-羥基乙基三甲基銨(亦稱為膽鹼)等之氫氧化羥基烷基三烷基銨等。該等中較好為氫氧化四烷基銨，其中較好為氫氧化四甲基銨(TMAH)。 [0041] 本文揭示之研磨用組成物可組合含有如上述之四級銨化合物與弱酸鹽。上述四級銨化合物可例如TMAH等之氫氧化四烷基銨。作為弱酸鹽可使用於使用氧化矽粒子之研磨，可適當選擇可藉由與四級銨化合物之組合而發揮期望緩衝作用者。弱酸鹽可單獨使用1種或組合2種以上使用。作為弱酸鹽之具體例舉例為碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、原矽酸鈉、原矽酸鉀、碳酸鈉、乙酸鉀、丙酸鈉、丙酸鉀、碳酸鈣、碳酸氫鈣、乙酸鈣、丙酸鈣、乙酸鎂、丙酸鎂、丙酸鋅、乙酸錳、乙酸鈷等。較好為陰離子成分係碳酸離子或碳酸氫離子之弱酸鹽，特佳為陰離子成分係碳酸離子之弱酸鹽。又，作為陽離子成分，宜為鉀、鈉等之鹼金屬離子。作為特佳之弱酸鹽，舉例為碳酸鈉、碳酸鉀、碳酸氫鈉及碳酸氫鉀。其中，較佳為碳酸鉀(K2
CO3
)。 [0042] 作為鹼性化合物，於組合使用四級銨化合物與弱酸鹽時，四級銨化合物與弱酸鹽之調配比率並未特別限定，例如四級銨化合物：弱酸鹽設為1：9~9：1為適當，較好為3：7~8：2，更好為5：5~7：3。上述四級銨化合物為例如TMAH等之氫氧化四烷基銨。弱酸鹽為例如K2
CO3
等之陰離子成分為碳酸離子之弱酸鹽。 [0043] 本文揭示之技術中，研磨用組成物中之鹼性化合物之含量例如為0.001重量%以上，典型上為0.01重量%以上為適當，基於研磨速率提高之觀點，較好為0.05重量%以上，更好為0.08重量%以上。藉由增加鹼性化合物含量，可提高A液之安定性。上述鹼性化合物含量之上限為5重量%以下為適當，基於表面品質等之觀點，較好為1重量%以下。於較佳一樣態中，上述鹼性化合物之含量為例如0.5重量%以下，典型上為0.2重量%以下。 [0044] (水) 本文揭示之研磨用組成物典型上包含水。水較好使用離子交換水(去離子水)、純水、超純水、蒸餾水等。為了極力避免阻礙研磨用組成物中所含之其他成分之作用，使用之水較好為例如過渡金屬離子之合計含量為100ppb以下。例如，可藉離子交換樹脂去除雜質離子，藉過濾去除異物，藉蒸餾等操作提高水之純度。又，本文揭示之研磨用組成物亦可視需要進一步含有可與水均勻混合之有機溶劑。上述有機溶劑為低級醇、低級酮等。研磨用組成物中所含之溶劑較好其90體積%以上為水，更好95體積%以上為水。更佳一樣態中，典型上濃縮液中所含之溶劑之99~100體積%為水。又本說明書中，有時使用水系溶劑之用語作為包含上述溶劑及水之總稱。 [0045] (螯合劑) 本文揭示之研磨用組成物可含有螯合劑作為任意成分。螯合劑藉由與研磨用組成物中可含之金屬雜質形成錯離子並捕捉其，而抑制因金屬雜質所致之研磨對象物之汙染發揮作用。螯合劑之例列舉為胺基羧酸系螯合劑及有機膦酸系螯合劑。胺基羧酸系螯合劑之例包含乙二胺四乙酸、乙二胺四乙酸鈉、氮基三乙酸、氮基三乙酸鈉、氮基三乙酸銨、羥基乙基乙二胺三乙酸、羥基乙基乙二胺三乙酸鈉、二伸乙基三胺五乙酸、二伸乙基三胺五乙酸鈉、三伸乙基四胺六乙酸及三伸乙基四胺六乙酸鈉。有機膦酸系螯合劑之例包含2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、胺基三(亞甲基膦酸)、乙二胺肆(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)、乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、乙烷-1-羥基-1,1-二膦酸、乙烷-1-羥基-1,1,2-三膦酸、乙烷-1,2-二羧基-1,2-二膦酸、甲烷羥基膦酸、2-膦醯基丁烷-1,2-二羧酸、1-膦醯基丁烷-2,3,4-三羧酸及α-甲基膦醯基琥珀酸。該等中以有機膦酸系螯合劑較佳。其中較佳者列舉為乙二胺肆(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)及二伸乙基三胺五乙酸。特佳之螯合劑列舉為乙二胺肆(亞甲基膦酸)及二伸乙基三胺五(亞甲基膦酸)。螯合劑可單獨使用1種或組合2種以上使用。 [0046] (其他成分) 本文揭示之研磨用組成物在不顯著妨礙本發明效果之範圍內，亦可視需要進一步含有界面活性劑、有機酸、有機酸鹽、無機酸、無機酸鹽、防腐劑、防黴劑等之可使用於研磨漿料之習知添加劑。上述研磨漿料典型為矽基板之拋光步驟所用之研磨漿料。 [0047] 本文揭示之研磨用組成物較好實質上不含氧化劑。其理由為於研磨用組成物中含氧化劑時，藉由將該研磨漿料供給至研磨對象物(此處為矽基板)而使該研磨對象物表面氧化，生成氧化膜，藉此有使研磨速率降低之情況。本文所稱之氧化劑之具體例舉例為過氧化氫(H2
O2
)、過硫酸鈉、過硫酸銨、二氯異氰脲酸鈉等。又，所謂研磨用組成物實質上不含氧化劑意指至少不刻意含有氧化劑。 [0048] 本文揭示之技術之研磨用組成物之pH為8.0以上，較好例如為8.5以上，更好為9.0以上，又更好為9.5以上。進而較佳一樣態中之研磨用組成物之pH例如為10.0以上。研磨用組成物之pH若提高，則有提高研磨速率之傾向。研磨液之pH上限值並未特別限定，但基於更良好研磨研磨對象物之觀點，為12.0以下，較好例如11.5以下，更好11.0以下。基於提高表面品質之觀點，上述pH進而較好為10.8以下。進而較佳一樣態中之研磨用組成物之pH例如為10.6以下，典型上為10.5以下。所謂上述表面品質提高典型上意指表面粗糙度減低。上述pH可較好地採用於例如矽晶圓之研磨所用之研磨液中。上述研磨液為例如粗研磨用之研磨液。 [0049] 又，本文揭示之技術中，液狀組成物之pH係藉由使用pH計，使用標準緩衝液，經3點校正後，將玻璃電極放入測定對象的組成物中，測定經過2分鐘以上安定後之值而掌握。上述液狀組成物可為研磨漿料、A液、B液等、其濃縮液等。又，作為pH計係使用例如堀場製作所製造之玻璃電極式氫離子濃度指示計(型號F-23)。再者，標準緩衝液為鄰苯二甲酸鹽pH緩衝液 pH：4.01(25℃)，中性磷酸鹽pH緩衝液 pH：6.86 (25℃)，碳酸鹽pH緩衝液 pH：10.01(25℃)。 [0050] ＜研磨用組成物之製造方法＞ 本文揭示之研磨用組成物可藉由下述方法製造。具體而言，上述製造方法包含：調製包含研磨粒及鹼性化合物之A液之步驟(A液調製步驟)；調製包含慣性半徑為100nm以上之水溶性高分子P1之B液之步驟(B液調製步驟)；及使上述A液與上述B液混合之步驟(混合步驟)。又，A液調製步驟與B液調製步驟之順序並未特別限定。 [0051] (A液調製步驟) 製造本文揭示之研磨用組成物時，調製包含研磨粒及鹼性化合物之A液。A液中所含之研磨粒種類可使用作為研磨用組成物可含之研磨粒所例示之各種研磨粒之1種或2種以上。作為各種研磨粒舉例為例如氧化矽粒子，較佳為膠體氧化矽。同樣，研磨粒之平均一次粒徑、形狀、平均長寬比，亦可設為研磨用組成物所含之研磨粒可具有之平均一次粒徑、形狀、平均長寬比。 [0052] 基於製造、流通、保存等之便利性等之觀點，A液典型上係以比研磨用組成物更高濃度包含含有成分之形態予以調製。因此，關於A液中之研磨粒含量亦較好高於研磨用組成物之研磨粒含量。具體而言，A液中之研磨粒含量約為1重量%以上，例如10重量%以上為適當，較好為15重量%以上，更好為20重量%以上，又更好為25重量%以上。基於安定性或過濾性等之觀點，A液中之研磨粒含量例如為50重量%以下為適當，較好為45重量%以下。較佳一樣態中，A液中之研磨粒含量例如為40重量%以下，典型上為35重量%以下。 [0053] 較佳一樣態中，基於安定性之觀點，研磨用組成物所含之研磨粒全量均含於A液中，但本文揭示之技術不限定於此。在不顯著損及本發明效果之範圍內，亦可研磨用組成物所含之研磨粒之一部分含於A液中。具體而言，研磨用組成物所含之研磨粒總量設為100重量%時，其中之超過50重量%之量含於A液中為適當，較好研磨用組成物所含之研磨粒總量之80重量%以上，例如90重量%以上，進而95重量%以上，典型上為99重量%~100重量%含於A液中。 [0054] 關於A液中所含之鹼性化合物亦與研磨粒之情況同樣，可使用作為研磨用組成物所含之鹼性化合物所例示之各種鹼性化合物之1種或2種以上。較好為四級銨化合物、弱鹼鹽、或兩者併用。B液中組合包含四級銨化合物及弱鹼鹽作為鹼性化合物時，B液中之四級銨化合物及弱鹼鹽之調配比率並未特別限定，例如四級銨化合物：弱鹼鹽為1：9~9：1為適當，較好為3：7~8：2，更好為5：5~7：3。又上述四級銨化合物為例如TMAH等之氫氧化四烷基銨。上述弱鹼鹽為例如K2
CO3
等之陰離子成分為碳酸離子的弱酸鹽。 [0055] A液之鹼性化合物含量(濃度)，基於研磨速率提高等之觀點，例如為0.1重量%以上，典型上為0.5重量%以上為適當，較好為1重量%以上，更好為1.5重量%以上，又更好為2.0重量%以上。進而較佳一樣態中，A液之鹼性化合物含量，為例如2.5重量%以上。例如A液以高倍率稀釋使用時，稀釋後之研磨粒濃度相對變低，有研磨粒之加工力亦變降低傾向之情況。此等情況中，藉由增量A液階段之鹼性化合物，可強化稀釋後之化學研磨。上述A液之鹼性化合物含量上限，基於保存安定性或表面品質等之觀點，10重量%以下為適當，較好為5重量%以下。較佳一樣態中，A液之鹼性化合物含量為例如3重量%以下。 [0056] 又，A液之鹼性化合物含量亦可根據與A液中所含之研磨粒之相對關係而特定出。具體而言，A液之鹼性化合物含量，相對於研磨粒100重量份，為0.1重量份以上為適當，基於研磨速率提高等之觀點，較好為1重量份以上，更好為3重量份以上，又更好為6重量份以上。且，基於安定性或表面品質等之觀點，鹼性化合物含量，相對於研磨粒100重量份，為50重量份以下為適當，較好為30重量份以下，更好為15重量份以下，又更好為12重量份以下。 [0057] 本文揭示之技術中，研磨用組成物所含之鹼性化合物全量可含於A液中，亦可其一部分含於A液中。具體而言，研磨用組成物所含之鹼性化合物總量設為100重量%時，其中之超過50重量%之量含於A液中為適當，較好研磨用組成物所含之鹼性化合物總量之80重量%以上，例如90重量%以上，進而95重量%以上，典型上為99重量%~100重量%含於A液中。基於與後述之B液混合時減低與B液之pH差之觀點，較好採用研磨用組成物所含之鹼性化合物之一部分含於A液，其餘部分含於後述B液之樣態。依據該樣態，A液中所含之鹼性化合物量，於將研磨用組成物所含之鹼性化合物總量設為100重量%時，可為99.999重量%以下，例如99.99重量%以下，典型上為99.9重量%左右。 [0058] 本文揭示之研磨用組成物包含上述水溶性高分子P2時，該研磨用組成物之製造中，水溶性高分子P2較好含於A液中。藉此，有改善研磨粒之分散安定性之傾向。作為A液中可含之水溶性高分子P2，可使用作為研磨用組成物中可含之水溶性高分子P2而例示之各種水溶性高分子P2之1種或2種以上。A液含水溶性高分子P2時，A液中之水溶性高分子P2含量(濃度)，基於可充分獲得水溶性高分子P2之添加效果之觀點，設為1×10-4
重量%以上為適當，較好為1×10-3
重量%以上。較佳一樣態中，A液中之水溶性高分子P2含量為例如3×10-3
重量%以上。A液中之水溶性高分子P2含量上限並未特別限定，可設為例如1×10-1
重量%以下，典型上設為1×10-2
重量%以下為適當。又，研磨用組成物包含上述水溶性高分子P2時，研磨用組成物所含之水溶性高分子P2全量可含於A液中，亦可其一部分含於A液中，其餘部分含於B液中，亦可其全量含於B液中。 [0059] 本文揭示之技術，可較好地以A液實質上不含水溶性高分子P1之樣態實施，但在不顯著損及本發明效果之範圍內，研磨用組成物所含之水溶性高分子P1之一部分亦可含於A液中。又，上述A液中，典型上可含有以水為代表之水系溶劑。A液可根據需要進而含有於本文揭示之研磨用組成物中可作為任意成分含有之螯合劑、界面活性劑、有機酸、有機酸鹽、無機酸、無機酸鹽、防腐劑、防黴劑等之添加劑。 [0060] 本文揭示之A液之pH典型上為8.0以上，較好為8.5以上，更好為9.0以上，又更好為9.5以上，例如10.0以上，特佳為10.5以上。A液之pH若高，則有提高研磨性能之傾向。另一方面，基於不妨礙研磨粒之溶解、抑制該研磨粒之機械研磨作用降低之觀點，A液之pH為12.0以下為適當，較好為11.8以下，更好為11.5以下。上述研磨粒為例如氧化矽粒子。 [0061] A液之調製方法並未特別限制。例如可使用翼式攪拌機、超音波分散機、均質混合機等之習知混合裝置，混合A液中所含之各成分。混合該等成分之樣態並未特別限制，例如可一次混合全部成分，亦可依適當設定之順序混合。關於後述之B液亦可適當採用同樣混合方法。 [0062] (B液調製步驟) 本文揭示之研磨用組成物之製造所使用之B液包含慣性半徑為100nm以上之水溶性高分子P1。作為B液所含之水溶性高分子P1，可使用作為研磨用組成物中可含之水溶性高分子P1而例示之各種水溶性高分子之1種或2種以上。 [0063] B液亦與A液同樣，基於製造、流通、保存等之便利性等之觀點，典型上係以比研磨用組成物更高濃度包含含有成分之形態予以調製。因此，關於B液中之水溶性高分子P1含量亦較好高於研磨用組成物之水溶性高分子P1含量。具體而言，B液中之水溶性高分子P1含量約為0.01重量%以上，例如0.02重量%以上為適當，較好為0.05重量%以上。較佳一樣態中，B液中之水溶性高分子P1含量例如為0.1重量%以上。基於安定性或過濾性等之觀點，B液中之水溶性高分子P1含量例如為10重量%以下為適當，較好為3重量%以下。較佳一樣態中，B液中之水溶性高分子P1含量例如為1重量%以下，典型上為0.55重量%以下。 [0064] 較佳一樣態中，基於安定性之觀點，研磨用組成物所含之水溶性高分子P1全量可含於B液中，但本文揭示之技術不限定於此。在不顯著損及本發明效果之範圍內，可為研磨用組成物所含之水溶性高分子P1之一部分含於A液中。具體而言，將研磨用組成物所含之水溶性高分子P1總量設為100重量%時，其中之超過50重量%之量含於B液中為適當，較好研磨用組成物所含之水溶性高分子P1總量之80重量%以上，例如90重量%以上，進而95重量%以上，典型上為99重量%以上含於B液中。 [0065] 較佳一樣態之B液中，含有研磨用組成物所含之鹼性化合物之一部分。藉此，可減低與含鹼性化合物之A液之pH差，可順利混合A液與B液。B液包含鹼性化合物時，作為該鹼性化合物並未特別限定，但較好使用與所混合之A液中所含之鹼性化合物或循環使用時之添加劑中使用之鹼性化合物之至少1種同種者。例如可使用氫氧化鉀或四級銨化合物。上述四級銨化合物為例如TMAH等之氫氧化四烷基銨。 [0066] 又，本文揭示之研磨用組成物包含水溶性高分子P2時，該水溶性高分子P2之全量或一部分可含於B液中。該情況下，B液所含之全部水溶性高分子之慣性半徑可設為未達100nm，但B液包含水溶性高分子P2時，且當然亦於不含時，B液所含之全部水溶性高分子之慣性半徑均較好為100nm以上。更佳一樣態中，B液所含之全部水溶性高分子之慣性半徑為105nm以上，進而較好為120nm以上，特佳為140 nm以上。B液所含之全部水溶性高分子之慣性半徑上限並未特別限定，基於B液之安定性或濃縮效率等之觀點，約為500nm以下為適當，較好為300nm以下，更好為250nm以下，又更好為220nm以下，或約為150nm以下，例如可為120nm以下。 [0067] 本文揭示之技術，可較好地以B液實質上不含研磨粒之樣態實施，但在不顯著損及本發明效果之範圍內，研磨用組成物所含之研磨粒之一部分亦可含於B液中。又，上述B液中，典型上可含有以水為代表之水系溶劑。B液可根據需要進而含有於本文揭示之研磨用組成物中可作為任意成分含有之螯合劑、界面活性劑、有機酸、有機酸鹽、無機酸、無機酸鹽、防腐劑、防黴劑等之添加劑。 [0068] 本文揭示之B液之pH並未特別限定。基於抑制與A液混合時之pH變化之觀點，B液之pH於A液之pH±3以內為適當，較好為±2以內，更好為±1以內。更佳一樣態中，B液之pH為例如±0.5以內。 [0069] (混合步驟) 其次，混合如上述調製之A液與B液。混合方法並未特別限定，可根據需要使用習知、慣用之混合裝置進行即可。上述混合時點並未特別限定，只要在使用研磨用組成物之前，亦即於使用該研磨用組成物進行研磨前之適當時點使A液與B液混合即可。例如較好在上述混合與使用所得研磨用組成物亦即研磨之間不包含保存等之步驟。自上述混合直至使用研磨用組成物之期間可設為例如2週以內，3日以內為適當。考慮混合後之研磨用組成物中之分散狀態等，較好設為開始使用上述研磨用組成物之研磨的24小時以內，典型上為12小時以內，更好於正要開始研磨之前例如6小時以內，典型上為3小時以內實施上述混合步驟。或者，連續進行A液與B液之混合，同時將所製造之研磨用組成物供給於研磨對象物。 [0070] A液與B液之混合比，係適當設定為使研磨用組成物之組成成為期望範圍。較佳一樣態中，上述混合步驟中，A液：B液以體積基準計為1：1~100：1，例如5：1~70：1，典型上為15：1~50：1之比例混合。 [0071] 較佳一樣態中，上述A液與B液之混合前後，或與該混合之同時使用水等之水系溶劑進行稀釋。藉由以該時點進行稀釋，於研磨用組成物之使用前後，可以A液、B液之狀態，兼具濃縮液之優點與安定性。濃縮液之優點為便利性、成本減低等。又，藉由進行稀釋所得之研磨用組成物可發揮優異之邊緣滑離減低效果。特佳一樣態係A液、B液及稀釋用水系溶劑幾乎同時混合，或連續投入混合。連續混合A液、B液及稀釋用水系溶劑時，添加順序並未特別限定。為了減低混合所致之pH變化之影響，較好採用以稀釋用水系溶劑稀釋A液後，於稀釋之A液中添加B液之樣態。作為稀釋所用之液體，基於處理性、作業性等之觀點，較好使用實質上由水所成之水系溶劑。水典型上為離子交換水。上述水系溶劑係例如99.5~100體積%為水的水系溶劑。又，上述水系溶劑為混合溶劑時，可僅添加該水系溶劑之構成成分中之一部分成分進行稀釋，亦可添加以與上述水系溶劑不同之量比含有該等之構成成分之混合溶劑予以稀釋。 [0072] 上述稀釋用水系溶劑之稀釋倍率，相對於A液及B液之總量，以體積基準計，大於2倍之倍率為適當。藉由以上述倍率稀釋，可自濃縮形態之A液、B液，獲得具有適於研磨之組成的研磨用組成物。依據本文揭示之技術，以A液及B液之總量為基準，較好以體積基準大於10倍之倍率，典型上為15倍以上，例如25倍以上之倍率進行稀釋。上述稀釋倍率之上限並未特別限定，但以體積基準為約100倍以下，例如50倍以下，典型上可為40倍以下。因此，A液與B液之單純混合物本身之組成可與以上述倍率濃縮本文揭示之研磨用組成物之組成對應。具體而言，A液與B液之混合液可為將具有上述說明組成之研磨用組成物以體積基準濃縮為超過2倍之倍率(濃縮倍率)的濃縮液。上述濃縮倍率較好以體積基準計為大於10倍之倍率，典型上為15倍以上，例如可為25倍以上。 [0073] A液、B液、根據需要使用之稀釋用水系溶劑之混合方法並未特別限定。可根據需要使用例如翼式攪拌機、超音波分散機、均質混合機等之習知混合裝置，混合上述液即可。混合上述液之樣態並未特別限制，例如可一次混合A液、B液、稀釋用水系溶劑，亦可依適當設定之順序混合。又，本文揭示之研磨用組成物之製造中，除了A液及B液以外，液可混合含有研磨用組成物所含之成分之一部分的1或2種以上之追加劑(可稱為C液、D液)作為任意構成要素。 [0074] ＜研磨用組成物套組＞ 本文揭示之研磨用組成物套組係用以製造上述研磨用組成物之多劑型研磨用組成物套組，且至少具備上述之A液及B液。A液至少含有研磨粒及鹼性化合物，B液至少含有水溶性高分子P1。較佳一樣態之研磨用組成物套組係由A液與B液所成之2劑型套組。又，A液及B液之細節如上述，故此處不再反覆重複說明。且，本文揭示之研磨用組成物套組除了A液及B液以外，液可混合含有研磨用組成物所含之成分之一部分的1或2種以上之追加劑(可稱為C液、D液)作為任意構成要素之3劑型以上之套組。上述A液、B液及作為任意構成要素之追加劑典型上於研磨用組成物製造之混合步驟之前，係分別保存於不同容器中。 [0075] (用途) 本文揭示之技術，可較好地適用於以矽基板(尤其是矽晶圓)為研磨對象物之研磨中。本文所稱之矽晶圓之典型例為矽單晶晶圓，例如切割矽單晶錠塊所得之矽單晶晶圓。本文揭示之技術中之研磨對象面典型上為由矽所成之表面。 [0076] 上述矽基板，於使用本文揭示之研磨液之研磨步驟之前，亦可施以磨削或蝕刻等之比粗研磨步驟更上游之步驟中之可對矽基板實施之一般處理。又，本文揭示之技術中，使用上述研磨液之研磨步驟(粗研磨步驟)之後，可對矽基板實施精研磨步驟。上述精研磨包含1或2次以上之拋光步驟，經過最終拋光，將矽晶圓精加工為高品質鏡面。又，最終拋光係指目的物製造製程中之最終拋光步驟。亦即，最終拋光係指該步驟後不再進行拋光之步驟。因此，本文揭示之研磨液、或A液、B液可用於經過磨削之矽晶圓之拋光。且，上述研磨液等可用於矽晶圓之最終拋光前進行之粗研磨中。粗研磨亦稱為預拋光。 [0077] ＜研磨＞ 研磨對象物之研磨可例如以下般進行。亦即，採用本文揭示之製造方法，具體而言，實施A液調製步驟、A液調製步驟及該A液與B液之混合步驟，根據需要進行稀釋，而準備研磨用組成物(研磨漿料)。其次，將該研磨漿料(作用漿料)供給於研磨對象物，藉由常用方法予以研磨。矽晶圓之粗研磨中，典型上將經過研削步驟之研磨對象物(矽晶圓)裝設於研磨裝置，通過固定於該研磨裝置之壓盤(研磨壓盤)之研磨墊，於上述研磨對象物表面(研磨對象面)供給研磨漿料。典型上，邊連續供給上述研磨漿料，邊對研磨對象物表面抵壓研磨墊使兩者相對移動。經過該研磨步驟而完成研磨對象物之研磨。上述移動可為例如旋轉移動。 [0078] 上述研磨步驟使用之研磨墊並無特別限制。例如可使用發泡聚胺基甲酸酯類型、不織布類型、麂皮類型等之研磨墊。各研磨墊可含研磨粒，亦可不含研磨粒。 [0079] 作為研磨裝置可使用同時對磨研磨對象物兩面進行研磨之兩面研磨裝置，亦可使用僅對研磨對象物單面進行研磨之單面研磨裝置。雖未特別限定，但例如粗研磨步驟中，可較好地採用兩面研磨裝置。兩面研磨裝置為例如批式之兩面研磨裝置。研磨裝置可為構成為每次研磨一片研磨對象物之單片式研磨裝置，亦可為於同一壓盤上可同時研磨複數研磨對象物之批式研磨裝置。 [0080] 雖未特別限定，但使用本文揭示之套組製造之研磨用組成物，於其製造後，較好以比較短的時間內使用於研磨。藉此，可更充分地活用將用以製造該研磨用組成物之套組構成為多劑型亦即具備複數劑之構成之優點。研磨用組成物之製造後至使用前之期間可為例如2週以內，設為3日以內為適當，較好設為24小時以內，更好設為12小時以內。上述期間亦可為6小時以內，進而亦可為3小時以內。或者，連續進行使用上述套組之上述研磨用組成物之製造，並且將製造之研磨用組成物供給於研磨對象物。 [0081] 上述研磨用組成物可以一旦研磨使用後即拋棄之樣態之所謂「源源流出」而使用，亦可循環重複使用。作為循環使用研磨用組成物之方法之一例，舉例為將自研磨裝置排出之使用過研磨用組成物回收於槽內，將回收之研磨用組成物再度供給於研磨裝置之方法。循環使用研磨用組成物之情況，相較於源源流出使用之情況，藉由減少作為廢液被處理之使用過之研磨用組成物之量而可減低環境負荷。且，藉由減少研磨用組成物之使用量而可抑制成本。本文揭示之研磨用組成物由於pH維持性優異，故對於此種循環使用之使用樣態係較佳。若為該使用樣態，可特別良好地發揮採用本發明構成之意義。循環使用本文揭示之研磨用組成物時，其使用中之研磨用組成物中，亦可於任意時點添加新的成分、因使用而減少之成分或期望增加之成分。 [0082] ＜洗淨＞ 結束粗研磨步驟之研磨對象物於開始精研磨步驟之前，典型上經洗淨。該洗淨可使用適當洗淨液進行。所使用之洗淨液並未特別限制，可使用例如半導體等領域中之一般SC-1洗淨液、SC-2洗淨液等。SC-1洗淨液係氫氧化銨(NH4
OH)與過氧化氫(H2
O2
)與水(H2
O)之混合液)。SC-2洗淨液係HCl、H2
O2
與H2
O之混合液。洗淨液之溫度可為例如室溫以上、至多約90℃左右之範圍。此處所謂室溫典型上指約15℃ ~25℃。基於提高洗淨效果之觀點，可較好使用50℃~85℃左右之洗淨液。 [0083] 經過如上述之粗研磨步驟、或洗淨步驟、精研磨步驟，而完成研磨對象物之研磨。上述研磨對象物於本文為矽基板，典型上為矽單晶晶圓。因此，依據本說明書，提供包含上述研磨步驟之研磨物之製造方法。上述製造方法具體而言為矽晶圓之製造方法。 [0084] 以上，依據本實施形態，提供製造包含研磨粒、鹼性化合物及水溶性高分子之矽晶圓粗研磨用組成物之方法。該製造方法包含：調製包含前述研磨粒及前述鹼性化合物之A液之步驟；及調製包含慣性半徑為100nm以上之水溶性高分子P1作為前述水溶性高分子之B液之步驟；及使前述A液與前述B液混合之步驟。藉由該方法所得之研磨用組成物藉由含有具有特定以上之慣性半徑之水溶性高分子P1，而可改善矽基板研磨中之邊緣滑離。且，完成前，換言之，使用前之研磨用組成物為具有A液及B液之多劑型，藉由使各液高濃度化(濃縮液化)，而可享受便利性、成本減低等之濃縮液之優點。且由於研磨粒、水溶性高分子P1分別收容於A液、B液中，故可避免因研磨粒之存在而阻礙水溶性高分子P1分散之情況。其結果，完成前之研磨用組成物以A液、B液之狀態顯示優異安定性。因此，依據本發明，可享受濃縮液之優點，同時可製造安定性優異且得以改善邊緣滑離之矽晶圓粗研磨用組成物。 [0085] 本文揭示之技術之較佳一樣態包含使前述A液、前述B液、及該A液與該B液之混合液之至少一種稀釋之步驟。又，前述稀釋步驟之稀釋倍率，以相對於前述A液及前述B液之總量之體積基準，係大於10倍之倍率。藉由採用此等方法，完成前之研磨用組成物可兼具濃縮液之優點與安定性，使用時作成將A液與B液混合而得之研磨用組成物，可發揮邊緣滑離減低效果。濃縮液之優點為便利性、成本減低等。上述稀釋步驟可在A液與B液混合之步驟前、與該混合步驟同時、或於該混合步驟之後實施。又，本文揭示之技術，於本說明書中，包含矽晶圓粗研磨用組成物之製造方法、矽晶圓粗研磨用組成物套組、矽晶圓之研磨方法等。 [0086] 本文揭示之技術之較佳一樣態係前述B液所含之水溶性高分子之慣性半徑為100nm以上。調製該B液後，根據需要予以保存，接著於研磨用組成物之使用時藉由與A液混合，可較好地發揮本發明揭示技術之效果。 [0087] 本文揭示之技術之較佳一樣態係前述A液中之前述研磨粒含量為10重量%以上。使用以特定以上濃度含有研磨粒之A液之樣態中，可較好地發揮本發明揭示技術之效果。 [0088] 本文揭示之技術之較佳一樣態係前述B液中之前述水溶性高分子P1含量為0.01重量%以上。使用以特定以上濃度含有水溶性高分子P1之B液之樣態中，可較好地發揮本發明揭示技術之效果。 [0089] 又，依據本實施形態，提供用以製造包含研磨粒、鹼性化合物及水溶性高分子之矽晶圓粗研磨用組成物之研磨用組成物套組。該研磨用組成物套組具備：包含前述研磨粒及前述鹼性化合物之A液，及包含慣性半徑為100nm以上之水溶性高分子P1作為前述水溶性高分子之B液。藉由該構成，使用前例如保存時A液及B液分別設為濃縮液時，可享受濃縮液之優點，同時個別之安定性優異。因此，於適當時點混合A液及B液，作成研磨用組成物(研磨漿料)，藉由使用其，可改善係基板之邊緣滑離。濃縮液之優點為便利性、成本減低等。 [0090] 又，依據本實施形態，提供包含粗研磨步驟及精研磨步驟的矽晶圓之研磨方法。該研磨方法於前述粗研磨步驟之前，包含調製該粗研磨步驟中使用之粗研磨用組成物之步驟。又，調製前述粗研磨用組成物之步驟包含：調製包含研磨粒及鹼性化合物之A液之步驟；及調製包含慣性半徑為100nm以上之水溶性高分子P1之B液之步驟；及使前述A液與前述B液混合之步驟。依據該方法，使用前之研磨用組成物以分離為A液與B液之狀態，可成為安定性優異之濃縮液。且，藉由使用該研磨用組成物實施粗研磨，可改善係基板之邊緣滑離。 [0091] 本文揭示之技術之典型一樣態中，前述粗研磨用組成物使用於經過研削之矽晶圓之拋光。更具體而言，上述粗研磨用組成物使用於矽晶圓之最終拋光前所進行之粗研磨(預拋光)中。 [實施例] [0092] 以下，說明本發明有關之數個實施例，但並非意圖將本發明限制於該實施例所示者。又，以下說明中之「%」只要未特別說明，則為重量基準。 [0093] ＜實施例1＞ 將作為研磨粒之膠體氧化矽(平均一次粒徑55nm)、TMAH、K2
CO3
、水溶性高分子P2(PVP，Mw 4.5×104
)與離子交換水混合，而調製含有研磨粒、TMAH、K2
CO3
及水溶性高分子P2分別為32.97%、1.62%、1.05%及0.0069%之濃度之A液。A液之pH為11.2。 且，藉由使水溶性高分子P1(HEC)、TMAH及離子交換水混合，而調製含有水溶性高分子P1及TMAH分別為0.25%及0.018%之濃度之B液。B液之pH為11.0。 所得之A液及B液以離子交換水稀釋混合，獲得本例之研磨液(作用漿料)。上述混合係以A液；B液：離子交換水以體積基準成為3.3：0.1：96.6之比率進行。 [0094] ＜實施例2~3、比較例1＞ 除了使用慣性半徑不同之HEC作為水溶性高分子P1以外，與實施例1同樣調製A液及B液，獲得本例之研磨液(作用漿料)。 [0095] ＜實施例4＞ 除了不使用水溶性高分子P2以外，與實施例3同樣調製A液及B液，獲得本例之研磨液(作用漿料)。 [0096] ＜實施例5＞ 將作為研磨粒之膠體氧化矽(平均一次粒徑55nm)、TMAH、K2
CO3
與離子交換水混合，而調製含有研磨粒、TMAH及K2
CO3
分別為32.97%、1.62%及1.05%之濃度之A液。A液之pH為11.2。 且，藉由使水溶性高分子P1(HEC)、水溶性高分子P2(PVP，Mw 4.5×104
)、TMAH及離子交換水混合，而調製含有水溶性高分子P1、水溶性高分子P2及TMAH分別為0.25%、0.28%及0.018%之濃度之B液。B液之pH為11.0。 除了使用所得之A液及B液以外，與實施例1同樣獲得本例之研磨液(作用漿料)。 [0097] ＜實施例6＞ 實施例3中，除了B液所含之TMAH 0.018%變更為氫氧化鉀(KOH) 0.011%以外，與實施例3同樣，獲得本例之研磨液(作用漿料)。 [0098] ＜比較例2~5＞ 將作為研磨粒之膠體氧化矽(平均一次粒徑55nm)、水溶性高分子P1(HEC)、TMAH、K2
CO3
、水溶性高分子P2(PVP，Mw 4.5×104
)與離子交換水混合，分別調製比較例2~5之研磨用組成物之濃縮液(1劑型)。各例之濃縮液中之研磨粒、水溶性高分子P1、TMAH、K2
CO3
及水溶性高分子P2之濃度分別為32.97%、0.0061%、1.62%、1.05%及0.0069%。 所得濃縮液以離子交換水稀釋混合，獲得本例之研磨液(作用漿料)。上述稀釋係以濃縮液；離子交換水以體積基準成為3.3：96.7之比率進行。 [0099] ＜比較例6＞ 除了不使用水溶性高分子P2以外，與比較例5同樣獲得本例之研磨液(作用漿料)。 [0100] [慣性半徑之測定方法] 水溶性高分子之慣性半徑之測定係首先以使水溶性高分子濃度成為0.1~1mg/mL之範圍之方式調製水溶液，針對所調製之各樣品使用光散射光度計「DLS-8000」(大塚電子公司製)，以測定角度20~150度之範圍每10度進行測定，藉由1濃法作圖解析進行慣性半徑[nm]之計算。測定係針對水溶性高分子P1與B液中所含之水溶性高分子實施。B液中含複數種水溶性高分子時，以成為其濃度比之方式調節水溶性高分子進行測定。測定結果示於表1。 [0101] [安定性] 將實施例1~6、比較例1調製之A液及B液分別為100g放入直徑2.5cm、高25cm之玻璃管中，分別於25℃靜置保存。且，比較例2~6之濃縮液以與上述同樣條件保存。藉由目視以下述2基準評價自保存開始後經過24小時後之A液、B液、濃縮液之狀態。亦即，未見到液中成分之分離或凝集時評價為「A」，見到分離或凝集時評價為「B」。結果示於表1。 [0102] [矽晶圓之研磨] 使用各例之研磨液(作用漿料)以下述條件實施粗研磨。 (研磨條件) 研磨裝置：日本THINKY公司製的單面研磨機，型號「EJ-380IN」 研磨墊：NITTA HAAS公司製，商品名「MH S-15A」 研磨壓力：26.6kPa 漿料流量：100mL/分鐘 壓盤旋轉數：50rpm 壓頭旋轉數：50rpm 研磨量：8μm 工件種類：裸矽P-
＜100＞ 工件尺寸：□60mm×60mm [0103] [邊緣滑離] 使用非接觸表面形狀測定機(商品名「NewView 5032」，Zygo公司製，可由CANON公司獲得)，求出距離上述研磨後之研磨物表面中心部(自中心起20mm見方)之基準高度，測定距離該研磨物之外周端約2.5mm位置之高度變化，將其設為邊緣滑離量。所測定之邊緣滑離量以下述4基準進行評價。 A：邊緣滑離量未達250nm B：邊緣滑離量為250nm以上且未達280nm C：邊緣滑離量為280nm以上且未達300nm D：邊緣滑離量為300nm以上 A~C為實用上合格程度，D視為不合格。結果示於表1。 [0104] [表面粗糙度Ra] 針對各例之粗研磨後之矽晶圓(完成粗研磨及隨後之洗淨之試驗片)，使用非接觸表面形狀測定機(商品名「NewView 5032」，Zygo公司製，可由CANON公司獲得)，測定表面粗糙度Ra(算術平均表面粗糙度)。所得測量值換算為以實施例4之表面粗糙度Ra設為100%之相對值，藉以下2階段評價。結果示於表1。 A：未達100% B：100%以上 [0105][0106] 如表1所示，分別調製含研磨粒及鹼性化合物之A液與含水溶性高分子P1之B液的實施例1~6，A液、B液均安定性優異。另一方面，使用1劑型之濃縮液之比較例3~6，無法獲得良好安定性。且，使用慣性半徑為100nm以上之水溶性高分子P1的實施例1~6，與使用慣性半徑未達100nm之水溶性高分子的比較例1、2相比，邊緣滑離性獲得改善。再者，併用水溶性高分子P2之實施例1~3、5及6，與未使用水溶性高分子P2之實施例4相比，見到表面粗糙度Ra亦獲得改善之傾向。 [0107] 以上，雖已詳細說明本發明之具體例，但該等不過為例示，並非限定專利申請範圍者。專利申請範圍所記載之技術中包含以上例示之具體例的各種變形、變更者。[0009] Hereinafter, preferred embodiments of the present invention will be described. It is to be noted that the implementation of the present invention other than the matters specifically mentioned in this specification is a person skilled in the art can grasp design matters based on conventional technology in the field. The present invention can be implemented based on the contents disclosed in this specification and technical knowledge in the field. [0010] According to this specification, a method for manufacturing a polishing composition, a polishing composition set for manufacturing the polishing composition, and a method for polishing a silicon wafer using the polishing composition are provided. Hereinafter, the polishing composition manufactured by the method disclosed herein will be described first, and then the manufacturing method, the polishing composition set, and the polishing method using the polishing composition will be described in order. [0011] <Polishing Composition> (Abrasive Particles) 之 The polishing composition disclosed herein contains abrasive particles. The material or properties of the abrasive grains are not particularly limited, and can be appropriately selected according to the purpose or state of use. Examples of the abrasive particles include inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include silicon oxide particles, aluminum oxide particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconia particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and iron oxide (Bengala) particles. Oxide particles; nitride particles such as silicon nitride particles and boron nitride particles; carbide particles such as silicon carbide particles and boron carbide particles; diamond particles; carbonates such as calcium carbonate or barium carbonate. Specific examples of the organic particles include polymethylmethacrylate (PMMA) particles, poly (meth) acrylic particles, and polyacrylonitrile particles. These abrasive grains may be used individually by 1 type, and may be used in combination of 2 or more type. The term (meth) acrylic acid includes acrylic acid and methacrylic acid. [0012] The abrasive particles are preferably inorganic particles, and among them, particles made of a metal or semi-metal oxide are preferred. An example of particularly good abrasive particles in the technology disclosed herein is silicon oxide particles. The technique disclosed herein can be better implemented in a state where the abrasive particles are substantially made of silica particles. The term "substantially" herein means that 95% by weight or more of the particles constituting the abrasive particles, preferably 98% by weight or more, more preferably 99% by weight or more are silica particles, and 100% by weight of the particles constituting the abrasive particles are Silicon oxide particles. [0013] Specific examples of the silica particles include colloidal silica, fumed silica, and precipitated silica. The silica particles can be used singly or in combination of two or more kinds. Based on the viewpoint that the surface of the object to be polished is less prone to scratches, and that it can further exert good polishing performance, colloidal silica is particularly preferred. The above-mentioned polishing performance is a performance for reducing the surface roughness and the like. As the colloidal silica, colloidal silica or an alkoxide-based colloidal silica produced by, for example, water glass (sodium silicate) by an ion exchange method can be preferably used. The so-called alkoxide colloidal silica is colloidal silica produced by the hydrolysis and condensation reaction of an alkoxysilane. Colloidal silica can be used alone or in combination of two or more. [0014] The true specific gravity of the silicon oxide constituting the silicon oxide particles is preferably 1.5 or more, more preferably 1.6 or more, and even more preferably 1.7 or more. By increasing the true specific gravity of silicon oxide, there is a tendency to increase the polishing rate. Based on this viewpoint, particularly preferred are silica particles having a true specific gravity of 2.0 or more, such as 2.1 or more. The upper limit of the true specific gravity of silicon oxide is not particularly limited, and is typically 2.3 or less, for example, 2.2 or less. The true specific gravity of silica can be measured by a liquid replacement method using ethanol as a replacement liquid. [0015] The average primary particle diameter of the abrasive particles disclosed herein is not particularly limited. From the viewpoint of polishing rate and the like, the average primary particle diameter is preferably 5 nm or more, preferably 10 nm or more, more preferably 30 nm or more, still more preferably 40 nm or more, and particularly preferably 45 nm or more. In a particularly preferred embodiment, the average primary particle diameter is, for example, 50 nm or more. The abrasive particles are typically silicon oxide particles. From the viewpoint of preventing scratches, etc., the average primary particle diameter of the abrasive particles is preferably 200 nm or less, preferably 100 nm or less, more preferably 80 nm or less, still more preferably 70 nm or less, and particularly preferably 60 nm or less. In addition, the average primary particle diameter in this specification means the specific surface area (BET value) measured by the BET method, and the BET diameter (nm) = 6000 / (true density (g / cm)3
) × BET value (m2
/ g)). For example, for silica particles, the BET diameter [nm] = 2727 / BET value [m2
/ g] Calculate the BET diameter. The measurement of the specific surface area can be performed using, for example, a surface area measuring device manufactured by MICRO MATERIALS, under the trade name "Flow Sorb II 2300". [0016] The shape (outer shape) of the abrasive particles may be spherical or non-spherical. Specific examples of the non-spherical particles include a peanut shape, a cocoon shape, a gold candy shape, a football shape, and the like. The peanut shape is the shape of the groundnut shell. For example, abrasive grains whose particles are mostly peanut-shaped can be preferably used. [0017] Although not particularly limited, the average value of the major diameter / minor diameter ratio (average aspect ratio) of the abrasive grains is in principle 1.0 or more, preferably 1.05 or more, and more preferably 1.1 or more. By increasing the average aspect ratio, higher grinding rates can be achieved. The average aspect ratio of the abrasive particles is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less from the viewpoint of reducing scratches and the like. [0018] The shape (outer shape) or average aspect ratio of the abrasive grains can be grasped by, for example, observation with an electron microscope. The specific order of grasping the average aspect ratio is, for example, using a scanning electron microscope (SEM), to draw a smallest rectangle circumscribed on each particle image for a predetermined number of silicon oxide particles that can identify the shape of independent particles. The predetermined number is, for example, 200. Next, for the rectangle drawn on each particle image, the value of the length of the long side (the value of the long diameter) divided by the length of the short side (the value of the short diameter) is used as the length / length ratio (aspect ratio). ). By arithmetically averaging the predetermined aspect ratio of the particles, the average aspect ratio can be obtained. [0019] The content of the abrasive particles in the polishing composition disclosed herein is not particularly limited, but is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and even more preferably 0.3% by weight or more. In a further preferred aspect, the content of the abrasive particles is 0.5% by weight or more. By increasing the content of abrasive particles, higher grinding rates can be achieved. From the viewpoint of removability from the object to be polished, the content is preferably 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less. In a further preferred aspect, the content of the abrasive particles is, for example, 2% by weight or less. [0020] (Water-soluble polymer P1) 研磨 The polishing composition disclosed herein includes a water-soluble polymer P1 having an inertia radius of 100 nm or more. By using the water-soluble polymer P1 having the above-mentioned inertial radius, the edge slippage is improved. The reason for this is not particularly limited, but it is speculated that the water-soluble polymer P1 having a specific radius of inertia contained in the polishing composition (polishing slurry) can prevent excessive polishing by excessively adsorbing on the ends of the substrate to be polished, and The increase in edge slipping off (slump at the end) is suppressed. The inertia radius of the water-soluble polymer P1 is the size of one molecule of the water-soluble polymer P1 in the aqueous solution, which is mainly determined by the hydrophilicity and molecular weight of the polymer P1. From the viewpoint of improving the edge slippage, the inertial radius of the water-soluble polymer P1 is preferably 105 nm or more, more preferably 120 nm or more, and particularly preferably 140 nm or more. The upper limit of the radius of inertia of the water-soluble polymer P1 is not particularly limited. From the viewpoint of the stability or concentration efficiency of the B liquid used as the water-soluble polymer P1-containing liquid in the manufacture of a polishing composition, it is appropriate to be about 250 nm or less. It is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 220 nm or less. The inertial radius of the water-soluble polymer P1 may be, for example, 150 nm or less and 120 nm or less. The radius of inertia of the water-soluble polymer in this specification can be measured by a method described in Examples described later. [0021] The type of the water-soluble polymer P1 contained in the polishing composition disclosed herein is not particularly limited, and can be appropriately selected from among the types of water-soluble polymers known in the field of polishing compositions. The water-soluble polymer P1 can be used singly or in combination of two or more kinds. Examples of the water-soluble polymer P1 include cellulose derivatives, starch derivatives, polymers containing oxyalkylene units, polymers containing nitrogen atoms, polyvinyl alcohol, and the like. Among these, from the viewpoint of improving flatness, cellulose derivatives and starch derivatives are preferred, and cellulose derivatives are more preferred. [0022] Cellulose derivatives are polymers containing β-glucose units as the main repeating unit. Specific examples of the cellulose derivative include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, and ethyl cellulose , Ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and the like. Among them, HEC is preferred. [0023] Starch derivatives are polymers containing α-glucose units as the main repeating unit. Specific examples of the starch derivative include alpha starch, pullulan, carboxymethyl starch, cyclodextrin, and the like. Among them, pullulan polysaccharide is preferred. [0024] Polymers containing oxyalkylene units are exemplified by polyethylene oxide (PEO), or blocks of ethylene oxide (EO) and propylene oxide (PO) or with butylene oxide (BO) Copolymers, random copolymers of EO and PO or BO. Among them, a block copolymer of EO and PO or a random copolymer of EO and PO is preferred. The block copolymer of EO and PO may be a diblock body, a triblock body, etc. containing a PEO block and a polypropylene oxide (PPO) block. Examples of the triblock include a PEO-PPO-PEO type triblock and a PPO-PEO-PPO type triblock. Among these, a PEO-PPO-PEO type triblock is more preferable. Among block copolymers or random copolymers of EO and PO, the molar ratio [EO / PO] of EO and PO constituting the copolymer is preferably greater than the viewpoint of solubility in water or detergency. 1, more preferably 2 or more, and even more preferably 3 or more. In a further preferred aspect, the above-mentioned molar ratio [EO / PO] is, for example, 5 or more. [0025] As the nitrogen atom-containing polymer, any one of a polymer containing a nitrogen atom in the main chain and a polymer having a nitrogen atom in a side chain functional group (side chain group) can be used. By using a polymer containing a nitrogen atom, the substrate surface roughness can be improved. Examples of polymers containing a nitrogen atom in the main chain include homopolymers and copolymers of N-fluorenylalkyleneimine-type monomers. Specific examples of the N-fluorenylalkyleneimine-type monomer include N-ethylfluorenylethylimine, N-propylfluorenylethylimine, and the like. Examples of the polymer having a nitrogen atom in the side chain group include, for example, a polymer containing an N-vinyl monomer unit. For example, homopolymers and copolymers of N-vinylpyrrolidone can be used. Among the techniques disclosed herein, at least one of the homopolymers and copolymers of N-vinylpyrrolidone (hereinafter also referred to as " PVP "). [0026] When polyvinyl alcohol is used as the water-soluble polymer P1, the saponification degree of the polyvinyl alcohol is not particularly limited. [0027] The molecular weight of the water-soluble polymer P1 in the technology disclosed herein is not particularly limited. From the viewpoint of concentration efficiency, etc., the weight-average molecular weight (Mw) of the water-soluble polymer P1 can usually be about 300 × 104
Below, 150 × 104
The following is appropriate. The above Mw may also be, for example, 130 × 104
The following may also be 110 × 104
the following. In addition, from the viewpoint of improving the protection or polishing performance of the substrate surface, Mw is 1 × 10.4
The above is appropriate, preferably 10 × 104
Above, more preferably 20 × 104
the above. In a more preferable state, the Mw is, for example, 50 × 10.4
Above, more preferably 80 × 104
the above. The Mw is, for example, 110 × 104
Above, can be 130 × 104
the above. The above-mentioned Mw is particularly preferably used for cellulose derivatives. Examples of the cellulose derivative include HEC. [0028] The relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble polymer P1 is not particularly limited. From the viewpoint of preventing the occurrence of agglomerates, for example, it is preferable that the molecular weight distribution [Mw / Mn] is 10.0 or less, and more preferably 7.0 or less. [0029] In addition, as Mw and Mn of the water-soluble polymer P1, values based on water-based gel permeation chromatography (GPC) (water-based, polyethylene oxide conversion) can be used. The same applies to the water-soluble polymer P2 described later. 00 [0030] The content of the water-soluble polymer P1 in the polishing composition is appropriately 1 × 10 from the viewpoint of polishing performance, surface quality improvement, and the like.-5
Above weight%, for example, 5 × 10-5
Above 1% by weight, preferably 1 × 10-4
More than% by weight. In a preferred embodiment, the content of the water-soluble polymer P1 is, for example, 2 × 10.-4
More than% by weight. The upper limit of the content of the water-soluble polymer P1 in the polishing composition may be, for example, 1% by weight or less. From the viewpoint of stability, grinding rate, detergency, etc. of the concentrated liquid phase, the content of the water-soluble polymer P1 is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and still more preferably 0.02% by weight or less. Particularly preferred is 0.01% by weight or less. In a particularly preferred embodiment, the content of the water-soluble polymer P1 is, for example, 0.005% by weight or less, and typically 0.001% by weight or less. The above-mentioned concentrated liquid is typically B liquid. [0031] The content of the water-soluble polymer P1 in the polishing composition disclosed herein can be specified by the relative relationship with the abrasive particles contained in the polishing composition. Specifically, the content of the water-soluble polymer P1 in the polishing composition is preferably 0.001 part by weight or more relative to 100 parts by weight of the abrasive grains, and is preferably 0.005 part by weight from the viewpoint of improvement in edge slippage and the like. The above is more preferably 0.01 parts by weight or more, and still more preferably 0.015 parts by weight or more. In addition, from the viewpoints of stability, polishing rate, etc., the content of the water-soluble polymer P1 is preferably 10 parts by weight or less with respect to 100 parts by weight of the abrasive particles, preferably 1 part by weight or less, and more preferably 0.5 weight by weight Parts or less, more preferably 0.3 parts by weight or less. [0032] (water-soluble polymer P2) 中 In a preferred embodiment of the technology disclosed herein, the polishing composition includes water-soluble polymers P1 with an inertia radius of 100 nm or more, and further includes water-soluble polymers having an inertia radius of less than 100 nm. Molecule P2. This water-soluble polymer P2 is different from the water-soluble polymer P1 and is a component that is responsible for the surface protection of the substrate such as etching suppression and contributes to the reduction of the surface roughness. Therefore, it is also called a substrate surface protective agent. The radius of inertia of the water-soluble polymer P2 is preferably less than 90 nm, more preferably less than 70 nm, and more preferably less than 50 nm from the viewpoint of stability or concentration efficiency. In a further preferred state, the inertia radius of the water-soluble polymer P2 is, for example, less than 30 nm, and typically less than 5 nm. The lower limit of the radius of inertia of the water-soluble polymer P2 is not particularly limited, and may be 0.1 nm or more, for example, 1 nm or more. [0033] The type of the water-soluble polymer P2 is not particularly limited, and can be appropriately selected from among water-soluble polymer species known in the field of polishing compositions. Examples of the water-soluble polymer P2 include cellulose derivatives, starch derivatives, polymers containing an oxyalkylene unit, polymers containing a nitrogen atom, polyvinyl alcohol, and the like exemplified as the water-soluble polymer P1. From the viewpoint of reducing surface roughness, the water-soluble polymer P2 is preferably a polymer other than a cellulose derivative and / or a starch derivative, and more preferably a polymer containing a nitrogen atom. The polymers other than the cellulose derivative and / or starch derivative are typically polymers other than the cellulose derivative. As specific examples of the cellulose derivative, the starch derivative, the polymer containing an oxyalkylene unit, the polymer containing a nitrogen atom, and polyvinyl alcohol, one or two of the examples of the water-soluble polymer P1 can be used. the above. Among them, a polymer containing a nitrogen atom in the main chain, a polymer having a nitrogen atom in a side chain functional group (side chain group) is preferable, and a polymer containing an N-vinyl monomer unit is more preferable. Among them, particularly preferred are homopolymers and copolymers of N-vinylpyrrolidone (typically PVP) and the like. [0034] The molecular weight of the water-soluble polymer P2 is not particularly limited. The weight average molecular weight (Mw) of the water-soluble polymer P2 can be about 300 × 104
Below, 150 × 104
Below, for example, 50 × 104
The following is appropriate. From the viewpoint of stability, etc., the above Mw can also be 30 × 104
Below, for example, 5 × 104
the following. From the viewpoint of improving the protection of the substrate surface, Mw is 1 × 10.4
The above is appropriate, preferably 2 × 104
Above, preferably 3 × 104
the above. The aforementioned Mw can be particularly preferably used for homopolymers and copolymers of N-vinylpyrrolidone (typically PVP). [0035] The relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble polymer P2 is not particularly limited. From the viewpoint of preventing the occurrence of agglomerates, for example, those having a molecular weight distribution [Mw / Mn] of 10.0 or less, more preferably 7.0 or less, more preferably 5.0 or less, particularly preferably 4.0 or less, and most preferably Below 3.0. [0036] In the technology disclosed herein, when a water-soluble polymer P1 and a water-soluble polymer P2 are used in combination as a water-soluble polymer, the mixing ratio of the water-soluble polymer P1 and the water-soluble polymer P2 is not particularly limited, such as water-soluble The polymer P1: the water-soluble polymer P2 is suitably 1: 9 to 9: 1, preferably 3: 7 to 8: 2, more preferably 5: 5 to 7: 3. The water-soluble polymer P1 is, for example, a cellulose derivative such as HEC, and the water-soluble polymer P2 is, for example, a polymer including an N-vinyl monomer unit such as PVP. [0037] The content of the water-soluble polymer P2 in the same polishing composition is less than 100% by weight when the content of the water-soluble polymer P1 is 100% by weight. From the viewpoint of stability, it is better. It is less than 80% by weight, and more preferably 70% by weight. In a more preferred embodiment, the content of the water-soluble polymer P2 is, for example, less than 60% by weight. From the viewpoint of reducing surface roughness, etc., when the content of the water-soluble polymer P2 is 100% by weight, the content of the water-soluble polymer P1 may be about 10% by weight or more, and 30% by weight or more is appropriate. It is preferably at least 50% by weight. In the technology disclosed herein, when the polishing composition contains or does not contain water-soluble polymer P2, the content of water-soluble polymers other than water-soluble polymer P1, and the content of water-soluble polymer P1 is set to 100 weight. In the case of%, it may be less than about 200% by weight, for example, less than 150% by weight, and further preferably less than 100% by weight. From the viewpoint of stability, when the content of the water-soluble polymer P1 other than the water-soluble polymer P1 is 100% by weight, it is preferably less than 80% by weight, and more preferably 70% by weight. %, Further less than 50% by weight, for example, less than 30% by weight, or less than 10% by weight, such as 1% by weight or less, and specifically 0 to 1% by weight. In a more preferred embodiment, the water-soluble polymer content other than the water-soluble polymer P1 is, for example, less than 60% by weight. [0038]] (Basic Compound) 研磨 The polishing composition disclosed herein contains a basic compound. The term “basic compound” used herein refers to a compound having a function of increasing the pH of an aqueous solution by dissolving it in water. As the basic compound, a nitrogen-containing organic or inorganic basic compound, a hydroxide of an alkali metal, a hydroxide of an alkaline earth metal, various carbonates or bicarbonates, and the like can be used. Examples of the nitrogen-containing basic compound include quaternary ammonium compounds, quaternary amidine compounds, ammonia, amines, and the like. The amine is preferably a water-soluble amine. These basic compounds may be used alone or in combination of two or more. [0039] Specific examples of the hydroxide of the alkali metal include potassium hydroxide, sodium hydroxide, and the like. Specific examples of the carbonate or bicarbonate include ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, and the like. Specific examples of the amine include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, and hexamethylene Diamine, diethylene triamine, triethylene tetramine, anhydrous piperazine, piperazine hexahydrate, 1- (2-aminoethyl) piperazine, N-methylpiperazine, guanidine, Imidazole or azoles such as triazole. Specific examples of the quaternary phosphonium compound include quaternary phosphonium hydroxide such as tetramethylphosphonium hydroxide and tetraethylphosphonium hydroxide. [0040] As the quaternary ammonium compound, a quaternary ammonium salt such as a tetraalkylammonium salt, an alkyl trialkylammonium salt, or the like can be preferably used. The above-mentioned quaternary ammonium salt is typically a strong base. The anionic component in the quaternary ammonium salt may be, for example, OH-
, F-
, Cl-
Br-
, I-
ClO4 -
, BH4 -
Wait. Among them, a preferable example is anionic OH-
The quaternary ammonium salt, that is, quaternary ammonium hydroxide. Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, and tetrahexyl hydroxide Tetraalkylammonium hydroxide such as ammonium; 2-hydroxyethyltrimethylammonium hydroxide (also known as choline); hydroxyalkyltrialkylammonium hydroxide and the like. Among these, tetraalkylammonium hydroxide is preferred, and among these, tetramethylammonium hydroxide (TMAH) is preferred. [0041] The polishing composition disclosed herein may contain a quaternary ammonium compound as described above and a weak acid salt in combination. Examples of the quaternary ammonium compound include tetraalkylammonium hydroxide such as TMAH. As a weak acid salt, it can be used for grinding using silicon oxide particles, and a suitable buffering effect can be appropriately selected by combining with a quaternary ammonium compound. The weak acid salts can be used alone or in combination of two or more. Specific examples of weak acid salts include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium orthosilicate, potassium orthosilicate, sodium carbonate, potassium acetate, sodium propionate, potassium propionate, calcium carbonate, Calcium bicarbonate, calcium acetate, calcium propionate, magnesium acetate, magnesium propionate, zinc propionate, manganese acetate, cobalt acetate, and the like. It is preferably a weak acid salt of an anion component type carbonate ion or bicarbonate ion, and particularly preferably a weak acid salt of an anion component type carbonate ion. The cationic component is preferably an alkali metal ion such as potassium or sodium. Particularly preferred weak acid salts include sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Among them, potassium carbonate (K2
CO3
). [0042] As a basic compound, when a quaternary ammonium compound and a weak acid salt are used in combination, the mixing ratio of the quaternary ammonium compound and the weak acid salt is not particularly limited. For example, the quaternary ammonium compound: the weak acid salt is set to 1: 9 ~ 9: 1 is appropriate, preferably 3: 7 ~ 8: 2, more preferably 5: 5 ~ 7: 3. The quaternary ammonium compound is, for example, tetraalkylammonium hydroxide such as TMAH. Weak acid salts are for example K2
CO3
And other anionic components are weak acid salts of carbonate ions. [0043] In the technology disclosed herein, the content of the basic compound in the polishing composition is, for example, 0.001% by weight or more, typically 0.01% by weight or more is appropriate. From the viewpoint of improving the polishing rate, it is preferably 0.05% by weight. The above is more preferably 0.08% by weight or more. By increasing the content of basic compounds, the stability of liquid A can be improved. The upper limit of the content of the basic compound is suitably 5% by weight or less, and from the viewpoint of surface quality and the like, it is preferably 1% by weight or less. In a preferred embodiment, the content of the basic compound is, for example, 0.5% by weight or less, and typically 0.2% by weight or less. [0044] (Water)) The polishing composition disclosed herein typically contains water. Water is preferably ion-exchanged water (deionized water), pure water, ultrapure water, distilled water, or the like. In order to avoid as much as possible hindering the effects of other components contained in the polishing composition, the water used is preferably, for example, a total content of transition metal ions of 100 ppb or less. For example, ion exchange resin can be used to remove impurity ions, filtration can be used to remove foreign matter, and distillation can be used to improve the purity of water. In addition, the polishing composition disclosed herein may further contain an organic solvent that can be uniformly mixed with water, if necessary. The organic solvent is a lower alcohol, a lower ketone, or the like. The solvent contained in the polishing composition is preferably 90% by volume or more of water, and more preferably 95% by volume or more of water. In a better state, 99 to 100% by volume of the solvent contained in the concentrated solution is typically water. In addition, in this specification, the term of an aqueous solvent may be used as a general term including the said solvent and water. 004 [0045] (chelating agent) 研磨 The polishing composition disclosed herein may contain a chelating agent as an optional ingredient. The chelating agent functions to suppress the contamination of the object to be polished due to the metal impurities by forming the wrong ions with the metal impurities that may be contained in the polishing composition and trapping them. Examples of the chelating agent include an aminocarboxylic acid-based chelating agent and an organic phosphonic acid-based chelating agent. Examples of amino carboxylic acid-based chelating agents include ethylenediamine tetraacetic acid, sodium ethylenediamine tetraacetate, nitrogen triacetic acid, sodium nitrogen triacetate, ammonium nitrogen triacetate, hydroxyethyl ethylenediamine triacetic acid, and hydroxyl groups. Ethyl ethylenediamine triacetate, diethylene triamine pentaacetic acid, sodium diethylene triamine pentaacetate, triethylene tetraamine hexaacetic acid, and sodium triethylene tetraamine hexaacetate. Examples of the organic phosphonic acid-based chelating agent include 2-aminoethylphosphonic acid, 1-hydroxyethylene-1,1-diphosphonic acid, aminotris (methylenephosphonic acid), and ethylenediamine Methylphosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1- Hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxyl-1,2-diphosphonic acid, methane hydroxyphosphonic acid, 2-phosphinofluorenylbutane-1,2-dicarboxylic acid, 1-phosphinofluorenylbutane-2,3,4-tricarboxylic acid and α-methylphosphinofluorenylsuccinic acid. Among these, an organic phosphonic acid-based chelating agent is preferred. Among them, preferred are ethylenediamine (methylenephosphonic acid), dimethylethylenetriaminepenta (methylenephosphonic acid), and dimethylethylenetriaminepentaacetic acid. Particularly preferred chelating agents are ethylenediamine (methylenephosphonic acid) and diethylene triaminepenta (methylenephosphonic acid). The chelating agent may be used singly or in combination of two or more kinds. [0046] 其他 (Other ingredients) 研磨 The grinding composition disclosed herein may further contain a surfactant, an organic acid, an organic acid salt, an inorganic acid, an inorganic acid salt, and a preservative within a range that does not significantly impede the effects of the present invention. , Antifungal agents, etc. can be used in conventional additives for grinding slurry. The above-mentioned polishing slurry is typically a polishing slurry used in a polishing step of a silicon substrate. [0047] The polishing composition disclosed herein is preferably substantially free of an oxidizing agent. The reason is that when an oxidant is contained in the polishing composition, the polishing slurry is supplied to the object to be polished (here, a silicon substrate) to oxidize the surface of the object to be polished, thereby forming an oxide film. Case of reduced rate. Specific examples of oxidants referred to herein are hydrogen peroxide (H2
O2
), Sodium persulfate, ammonium persulfate, sodium dichloroisocyanurate, etc. In addition, the fact that the polishing composition does not substantially contain an oxidant means that at least the oxidant is not intentionally contained. [0048] The pH of the polishing composition of the technology disclosed herein is 8.0 or higher, preferably, for example, 8.5 or higher, more preferably 9.0 or higher, and even more preferably 9.5 or higher. Furthermore, the pH of the polishing composition in a preferred state is, for example, 10.0 or more. Increasing the pH of the polishing composition tends to increase the polishing rate. The upper limit of the pH of the polishing liquid is not particularly limited, but it is 12.0 or less, preferably 11.5 or less, and more preferably 11.0 or less, from the viewpoint of better polishing the object to be polished. From the viewpoint of improving the surface quality, the pH is more preferably 10.8 or less. Furthermore, the pH of the polishing composition in a preferred state is, for example, 10.6 or less, and typically 10.5 or less. The above-mentioned improvement in surface quality typically means a reduction in surface roughness. The above-mentioned pH can be preferably used in a polishing liquid for polishing silicon wafers, for example. The polishing liquid is, for example, a polishing liquid for rough polishing. [0049] In the technology disclosed herein, the pH of the liquid composition is adjusted by using a pH meter and a standard buffer solution after 3 points correction, and the glass electrode is placed in the composition of the measurement object. You can grasp the value after settling for more than minutes. The liquid composition may be a polishing slurry, a liquid A, a liquid B, or the like, a concentrated liquid thereof, or the like. As the pH meter, for example, a glass electrode type hydrogen ion concentration indicator (model F-23) manufactured by Horiba, Ltd. is used. Moreover, the standard buffer solution is phthalate pH buffer pH: 4.01 (25 ° C), neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C) ). [0050] <Manufacturing method of polishing composition> The polishing composition disclosed herein can be manufactured by the following method. Specifically, the above-mentioned manufacturing method includes a step of preparing a liquid A containing abrasive particles and a basic compound (a liquid preparing step); a step of preparing a liquid B containing a water-soluble polymer P1 having an inertia radius of 100 nm or more (the liquid B Preparing step); and a step of mixing the A liquid and the B liquid (mixing step). The order of the A liquid preparation step and the B liquid preparation step is not particularly limited. [0051] (A liquid preparation step) When producing the polishing composition disclosed herein, an A liquid containing abrasive particles and a basic compound is prepared. As the kind of abrasive grains contained in the liquid A, one kind or two or more kinds of the abrasive grains exemplified as the abrasive grains which can be contained in the polishing composition can be used. Examples of the various abrasive particles include silica particles, and colloidal silica is preferred. Similarly, the average primary particle diameter, shape, and average aspect ratio of the abrasive particles can also be the average primary particle diameter, shape, and average aspect ratio that the abrasive particles contained in the polishing composition can have. [0052] From the standpoint of convenience in manufacturing, distribution, storage, etc., A liquid is typically prepared in a form that contains a higher concentration than a polishing composition. Therefore, the content of the abrasive particles in the liquid A is also preferably higher than the content of the abrasive particles in the polishing composition. Specifically, the content of abrasive particles in the liquid A is about 1% by weight or more, for example, 10% by weight or more is appropriate, preferably 15% by weight or more, more preferably 20% by weight or more, and even more preferably 25% by weight or more. . From the viewpoints of stability, filterability, etc., the content of the abrasive particles in the liquid A is, for example, 50% by weight or less, and preferably 45% by weight or less. In a preferable aspect, the content of the abrasive particles in the liquid A is, for example, 40% by weight or less, and typically 35% by weight or less. [0053] In a preferred embodiment, from the viewpoint of stability, the entire amount of abrasive particles contained in the polishing composition is contained in the liquid A, but the technology disclosed herein is not limited thereto. As long as the effect of the present invention is not significantly impaired, part of the abrasive grains contained in the polishing composition may be contained in the A liquid. Specifically, when the total amount of the abrasive particles contained in the polishing composition is 100% by weight, it is appropriate that the amount of more than 50% by weight is contained in the liquid A. The total amount of the abrasive particles contained in the polishing composition is preferred. 80% by weight or more, for example, 90% by weight or more, and 95% by weight or more, typically 99% to 100% by weight are contained in the liquid A. [0054] The basic compounds contained in the liquid A can be used in the same manner as in the case of the abrasive grains. One or two or more of the various basic compounds exemplified as the basic compounds contained in the polishing composition can be used. It is preferred to use a quaternary ammonium compound, a weak base salt, or both. When the combination of the quaternary ammonium compound and the weak base salt in the liquid B is used as the basic compound, the mixing ratio of the quaternary ammonium compound and the weak base salt in the liquid B is not particularly limited. : 9 ~ 9: 1 is appropriate, preferably 3: 7 ~ 8: 2, more preferably 5: 5 ~ 7: 3. The quaternary ammonium compound is tetraalkylammonium hydroxide such as TMAH. The weak base salt is, for example, K2
CO3
The anionic component is a weak acid salt of a carbonate ion. [0055] The content (concentration) of the basic compound in the liquid A is, for example, 0.1% by weight or more, typically 0.5% by weight or more, more preferably 1% by weight or more, and more preferably from the viewpoint of improving the polishing rate. 1.5% by weight or more, and more preferably 2.0% by weight or more. In a more preferred embodiment, the content of the basic compound in the liquid A is, for example, 2.5% by weight or more. For example, when liquid A is used at a high dilution rate, the concentration of the abrasive particles after dilution is relatively low, and the processing power of the abrasive particles may also decrease. In these cases, the chemical milling after dilution can be enhanced by increasing the alkaline compound in the A-phase. The upper limit of the content of the basic compound in the liquid A is from the viewpoint of storage stability, surface quality, and the like, and is preferably 10% by weight or less, and preferably 5% by weight or less. In a preferred embodiment, the content of the basic compound in the liquid A is, for example, 3% by weight or less. [0056] In addition, the content of the basic compound in liquid A can also be specified based on the relative relationship with the abrasive particles contained in liquid A. Specifically, the content of the basic compound in the liquid A is preferably 0.1 part by weight or more relative to 100 parts by weight of the abrasive grains. From the viewpoint of improving the polishing rate, it is preferably 1 part by weight or more, and more preferably 3 parts by weight. The above is more preferably 6 parts by weight or more. From the viewpoints of stability and surface quality, the content of the basic compound is preferably 50 parts by weight or less, preferably 30 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the abrasive grains. It is more preferably 12 parts by weight or less. [0057] In the technology disclosed herein, the entire amount of the basic compound contained in the polishing composition may be contained in the A solution, or a part thereof may be contained in the A solution. Specifically, when the total amount of basic compounds contained in the polishing composition is 100% by weight, it is appropriate that the amount of more than 50% by weight is contained in the A liquid. The basicity contained in the polishing composition is preferred. 80% by weight or more of the total amount of the compound, such as 90% by weight or more, and 95% by weight or more, typically 99% to 100% by weight are contained in the liquid A. From the viewpoint of reducing the pH difference with the B solution when mixed with the B solution described later, it is preferred to use a part of the basic compound contained in the polishing composition to be contained in the A solution, and the remaining part to be contained in the B solution described later. According to this aspect, when the total amount of the basic compounds contained in the liquid A is 100% by weight, the amount of the basic compounds contained in the polishing composition may be 99.999% by weight or less, for example, 99.99% by weight or less. It is typically about 99.9% by weight. [0058] When the polishing composition disclosed herein contains the water-soluble polymer P2, the water-soluble polymer P2 is preferably contained in the A liquid in the production of the polishing composition. This tends to improve the dispersion stability of the abrasive particles. As the water-soluble polymer P2 that can be contained in the liquid A, one or two or more kinds of various water-soluble polymers P2 exemplified as the water-soluble polymer P2 that can be contained in the polishing composition can be used. When the liquid A contains the water-soluble polymer P2, the content (concentration) of the water-soluble polymer P2 in the liquid A is set to 1 × 10 based on the viewpoint that the additive effect of the water-soluble polymer P2 can be sufficiently obtained.-4
A weight% or more is appropriate, and preferably 1 × 10-3
More than% by weight. In a preferred state, the content of the water-soluble polymer P2 in the liquid A is, for example, 3 × 10-3
More than% by weight. The upper limit of the content of the water-soluble polymer P2 in the liquid A is not particularly limited, and may be, for example, 1 × 10-1
Weight% or less, typically set to 1 × 10-2
The weight% or less is appropriate. When the polishing composition includes the water-soluble polymer P2, the entire amount of the water-soluble polymer P2 contained in the polishing composition may be contained in the A liquid, or a part of the water-soluble polymer P2 may be contained in the A liquid, and the remaining portion may be contained in the B liquid. In the liquid, the entire amount may be contained in the B liquid. [0059] The technology disclosed herein can be better implemented in a state where the liquid A does not substantially contain the water-soluble polymer P1, but the water-solubility contained in the polishing composition is within a range not significantly impairing the effect of the present invention A part of the polymer P1 may be contained in the A liquid. The A liquid may typically contain an aqueous solvent typified by water. Liquid A may be further contained in the polishing composition disclosed herein as a chelating agent, a surfactant, an organic acid, an organic acid salt, an inorganic acid, an inorganic acid salt, a preservative, a mold inhibitor, etc. Of additives. [0060] The pH of the A liquid disclosed herein is typically 8.0 or higher, preferably 8.5 or higher, more preferably 9.0 or higher, and even more preferably 9.5 or higher, such as 10.0 or higher, particularly preferably 10.5 or higher. If the pH of liquid A is high, the polishing performance tends to be improved. On the other hand, from the viewpoint of not hindering the dissolution of the abrasive grains and suppressing the reduction of the mechanical polishing action of the abrasive grains, the pH of the A liquid is preferably 12.0 or less, preferably 11.8 or less, and more preferably 11.5 or less. The abrasive particles are, for example, silica particles. [0061] The method for preparing A liquid is not particularly limited. For example, a conventional mixing device such as a wing mixer, an ultrasonic disperser, and a homomixer can be used to mix the components contained in the liquid A. The form of mixing these components is not particularly limited, and for example, all the components may be mixed at a time, or they may be mixed in an appropriately set order. The same mixing method can also be suitably used for the liquid B mentioned later. [0062] (B liquid preparation step) 液 The B liquid used in the manufacture of the polishing composition disclosed herein contains a water-soluble polymer P1 having an inertia radius of 100 nm or more. As the water-soluble polymer P1 contained in the liquid B, one or two or more kinds of various water-soluble polymers exemplified as the water-soluble polymer P1 that can be contained in the polishing composition can be used. [0063] Liquid B is similar to liquid A in that it is typically prepared in a form that contains a higher concentration than the polishing composition from the viewpoint of convenience in manufacturing, distribution, and storage. Therefore, the content of the water-soluble polymer P1 in the liquid B is also preferably higher than the content of the water-soluble polymer P1 in the polishing composition. Specifically, the content of the water-soluble polymer P1 in the liquid B is about 0.01% by weight or more, for example, 0.02% by weight or more is appropriate, and preferably 0.05% by weight or more. In a preferred embodiment, the content of the water-soluble polymer P1 in the liquid B is, for example, 0.1% by weight or more. From the viewpoints of stability, filterability, etc., the content of the water-soluble polymer P1 in the liquid B is preferably 10% by weight or less, and preferably 3% by weight or less. In a preferred embodiment, the content of the water-soluble polymer P1 in the liquid B is, for example, 1% by weight or less, and typically 0.55% by weight or less. [0064] In a preferred embodiment, from the viewpoint of stability, the entire amount of the water-soluble polymer P1 contained in the polishing composition may be contained in the liquid B, but the technology disclosed herein is not limited thereto. As long as it does not significantly impair the effect of the present invention, a part of the water-soluble polymer P1 contained in the polishing composition may be contained in the A liquid. Specifically, when the total amount of the water-soluble polymer P1 contained in the polishing composition is 100% by weight, it is appropriate that the amount of more than 50% by weight is contained in the B liquid, and the polishing composition is preferably included. 80% by weight or more of the total amount of the water-soluble polymer P1, for example, 90% by weight or more, and 95% by weight or more, and typically 99% by weight or more are contained in the B liquid. [0065] The liquid B, which is preferably in the same state, contains a part of the basic compound contained in the polishing composition. Thereby, the pH difference between the liquid A and the liquid A containing a basic compound can be reduced, and the liquid A and the liquid B can be smoothly mixed. When the liquid B contains a basic compound, the basic compound is not particularly limited, but it is preferable to use at least one of the basic compound contained in the mixed liquid A or the basic compound used in the additive at the time of recycling. The same species. For example, potassium hydroxide or a quaternary ammonium compound can be used. The quaternary ammonium compound is, for example, tetraalkylammonium hydroxide such as TMAH. [0066] When the polishing composition disclosed herein includes a water-soluble polymer P2, all or part of the water-soluble polymer P2 may be contained in the B liquid. In this case, the inertia radius of all water-soluble polymers contained in liquid B can be set to less than 100 nm. The inertia radius of the polymer is preferably 100 nm or more. In a more preferable state, the inertia radius of all water-soluble polymers contained in the liquid B is 105 nm or more, more preferably 120 nm or more, and particularly preferably 140 nm or more. The upper limit of the radius of inertia of all water-soluble polymers contained in the B liquid is not particularly limited. From the viewpoint of the stability or concentration efficiency of the B liquid, it is appropriate to be about 500 nm or less, preferably 300 nm or less, more preferably 250 nm or less. , And more preferably 220 nm or less, or about 150 nm or less, for example, 120 nm or less. [0067] The technology disclosed herein can be better implemented in a state that the B liquid does not substantially contain abrasive particles, but within a range that does not significantly impair the effect of the present invention, a part of the abrasive particles contained in the polishing composition Can also be contained in the B solution. The B liquid may typically contain an aqueous solvent typified by water. Liquid B may be further contained in the polishing composition disclosed herein as a chelating agent, a surfactant, an organic acid, an organic acid salt, an inorganic acid, an inorganic acid salt, a preservative, a mold inhibitor, etc. Of additives. [0068] The pH of the liquid B disclosed herein is not particularly limited. From the viewpoint of suppressing the change in pH when mixed with the A liquid, the pH of the B liquid is preferably within ± 3 of the pH of the A liquid, preferably within ± 2, and more preferably within ± 1. In a more preferable state, the pH of the liquid B is, for example, within ± 0.5. [0069] (mixing step) (2) Second, A liquid and B liquid prepared as described above are mixed. The mixing method is not particularly limited, and may be performed using a conventional or conventional mixing device as required. The mixing point is not particularly limited, as long as the A liquid and the B liquid are mixed at an appropriate time before the polishing composition is used, that is, before the polishing composition is used for polishing. For example, it is preferable not to include a step such as storage between the above mixing and use of the obtained polishing composition, that is, polishing. The period from the above mixing to the use of the polishing composition can be, for example, within 2 weeks and within 3 days. In consideration of the dispersion state of the polishing composition after mixing, it is preferably within 24 hours, typically within 12 hours, of starting polishing using the above-mentioned polishing composition, and more preferably, for example, 6 hours before the polishing is started. The above mixing step is typically performed within 3 hours. Alternatively, while continuously mixing the A liquid and the B liquid, the manufactured polishing composition is supplied to the object to be polished. [0070] The mixing ratio of the A liquid and the B liquid is appropriately set so that the composition of the polishing composition is within a desired range. In a preferred state, in the above mixing step, the A liquid and the B liquid are 1: 1 to 100: 1 on a volume basis, such as 5: 1 to 70: 1, and typically a ratio of 15: 1 to 50: 1 mixing. [0071] In a preferred embodiment, the liquid A and the liquid B are diluted before and after the mixing of the A liquid and the B liquid, or at the same time as the mixing. By diluting at this point, before and after the polishing composition is used, it can be in the state of liquid A and liquid B, and has the advantages and stability of concentrated liquid. The advantages of the concentrated solution are convenience and cost reduction. Moreover, the polishing composition obtained by diluting can exhibit an excellent edge slip reduction effect. The particularly good homogeneous system A liquid, B liquid and dilution water-based solvent are mixed almost simultaneously, or continuously mixed. When the A liquid, the B liquid, and the dilution water-based solvent are continuously mixed, the order of addition is not particularly limited. In order to reduce the effect of pH change caused by mixing, it is preferable to use the state in which the liquid A is diluted with a water-based solvent for dilution, and the liquid B is added to the diluted liquid A. As the liquid used for the dilution, from the viewpoints of handleability, workability, and the like, it is preferable to use an aqueous solvent substantially composed of water. Water is typically ion-exchanged water. The aqueous solvent is, for example, an aqueous solvent in which 99.5 to 100% by volume is water. When the water-based solvent is a mixed solvent, only a part of the constituents of the water-based solvent may be added for dilution, or a mixed solvent containing such constituents in an amount ratio different from that of the water-based solvent may be added for dilution. [0072] The dilution ratio of the above-mentioned dilution water-based solvent is appropriate on a volume basis with respect to the total amount of the liquids A and B, which is more than 2 times. By diluting at the above-mentioned ratio, it is possible to obtain a polishing composition having a composition suitable for polishing from the concentrated liquids A and B. According to the technology disclosed herein, dilution is performed based on the total amount of liquid A and liquid B, preferably on a volume basis greater than 10 times, typically 15 times or more, such as 25 times or more. The upper limit of the dilution ratio is not particularly limited, but it is about 100 times or less on a volume basis, for example, 50 times or less, and typically 40 times or less. Therefore, the composition of the simple mixture of liquid A and liquid B may correspond to the composition of the polishing composition disclosed herein that is concentrated at the above-mentioned ratio. Specifically, the mixed liquid of liquid A and liquid B may be a concentrated liquid in which the polishing composition having the composition described above is concentrated on a volume basis to a factor (concentration ratio) of more than 2 times. The above-mentioned concentration magnification is preferably a magnification greater than 10 times on a volume basis, typically 15 times or more, and for example, 25 times or more. [0073] A mixing method of the A liquid, the B liquid, and a diluting water-based solvent used as necessary is not particularly limited. If necessary, a conventional mixing device such as a wing mixer, an ultrasonic disperser, a homomixer, and the like can be used to mix the above liquids. The state of mixing the above-mentioned liquids is not particularly limited. For example, the liquids A, B, and a water-based solvent for dilution can be mixed at one time, or they can be mixed in an appropriately set order. In addition, in the production of the polishing composition disclosed herein, in addition to liquids A and B, the liquid may be mixed with one or two or more additives (which may be referred to as liquid C) containing a part of the components contained in the polishing composition. , D liquid) as arbitrary constituent elements. [0074] <Grinding composition kit> 研磨 The polishing composition kit disclosed herein is a multi-dose polishing composition kit for manufacturing the above-mentioned polishing composition, and includes at least the above-mentioned liquids A and B. Liquid A contains at least abrasive particles and basic compounds, and liquid B contains at least water-soluble polymer P1. The preferred uniform composition set for polishing is a two-component set composed of liquid A and liquid B. In addition, the details of the A liquid and the B liquid are as described above, so the repeated description will not be repeated here. In addition, in the polishing composition set disclosed herein, in addition to liquids A and B, the liquid may be mixed with one or two or more additives (which may be referred to as liquids C and D) containing a part of the components contained in the polishing composition. Liquid) as a set of 3 or more dosage forms as arbitrary constituent elements. The above-mentioned liquids A and B and the additives as optional constituents are typically stored in different containers before the mixing step for producing the polishing composition. [0075] (Usage) The technology disclosed herein can be applied to polishing with silicon substrates (especially silicon wafers) as polishing objects. A typical example of a silicon wafer referred to herein is a silicon single crystal wafer, such as a silicon single crystal wafer obtained by cutting a silicon single crystal ingot. The polishing target surface in the technology disclosed herein is typically a surface made of silicon. [0076] Prior to the polishing step using the polishing liquid disclosed herein, the above-mentioned silicon substrate may also be subjected to general processing that can be performed on the silicon substrate in a step upstream of the rough polishing step such as grinding or etching. In addition, in the technology disclosed herein, after the polishing step (rough polishing step) using the above-mentioned polishing liquid, a fine polishing step may be performed on the silicon substrate. The above-mentioned fine grinding includes one or more polishing steps. After the final polishing, the silicon wafer is finished into a high-quality mirror surface. The final polishing refers to the final polishing step in the manufacturing process of the object. That is, the final polishing refers to a step in which polishing is not performed after this step. Therefore, the polishing liquids disclosed in this article, or liquids A and B, can be used for polishing silicon wafers after grinding. In addition, the above-mentioned polishing liquid and the like can be used for rough polishing before final polishing of a silicon wafer. Rough grinding is also called pre-polishing. [0077] <Polishing> 研磨 The polishing of the object to be polished can be performed, for example, as follows. That is, using the manufacturing method disclosed herein, specifically, implementing the A liquid preparation step, the A liquid preparation step, and the A liquid and B liquid mixing steps, and diluting as necessary to prepare a polishing composition (polishing slurry) ). Next, this polishing slurry (action slurry) is supplied to an object to be polished, and is polished by a usual method. In the rough polishing of silicon wafers, the grinding object (silicon wafer) that has undergone the grinding step is typically installed in a polishing device. A polishing slurry is supplied to the surface of the object (surface to be polished). Typically, while the polishing slurry is continuously supplied, the polishing pad is pressed against the surface of the object to be polished to move the two relative to each other. After the polishing step, polishing of the object to be polished is completed. The above-mentioned movement may be, for example, a rotational movement. [0078] The polishing pad used in the above-mentioned polishing step is not particularly limited. For example, a polishing pad of foamed polyurethane type, non-woven type, suede type, or the like can be used. Each polishing pad may or may not contain abrasive particles. [0079] As the polishing device, a two-side polishing device that simultaneously grinds both sides of the object to be polished may be used, or a single-sided polishing device that only polishes one side of the object to be polished may be used. Although not particularly limited, for example, in the rough grinding step, a double-sided grinding device can be preferably used. The double-sided polishing device is, for example, a batch-type double-sided polishing device. The grinding device may be a single-piece grinding device configured to grind one grinding object at a time, or a batch grinding device capable of simultaneously grinding multiple grinding objects on the same platen. [0080] Although not particularly limited, the polishing composition manufactured using the kit disclosed herein is preferably used for polishing in a relatively short time after its manufacture. Thereby, it is possible to make full use of the advantage that the set for manufacturing the polishing composition is configured into a multi-dose form, that is, it has a composition of multiple agents. The period from the manufacture of the polishing composition to the period before use can be, for example, within 2 weeks, and within 3 days is appropriate, preferably within 24 hours, and more preferably within 12 hours. The above period may be within 6 hours, and may be within 3 hours. Alternatively, production of the polishing composition using the kit described above is continuously performed, and the manufactured polishing composition is supplied to an object to be polished. [0081] The above-mentioned polishing composition can be used in a so-called "source outflow" state which is discarded once it is ground and used, and can also be recycled and reused. As an example of a method for recycling the polishing composition, for example, a method of recovering the used polishing composition discharged from the polishing device in a tank, and supplying the recovered polishing composition to the polishing device again. In the case of recycling the polishing composition, the environmental load can be reduced by reducing the amount of the used polishing composition to be treated as a waste liquid, compared to the case of using the source. In addition, cost can be suppressed by reducing the amount of the polishing composition used. Since the polishing composition disclosed herein has excellent pH maintenance, it is preferable to use it in such a cycle. In this use case, the significance of adopting the constitution of the present invention can be exerted particularly well. When the polishing composition disclosed herein is cyclically used, new components, components that are reduced due to use, or components that are expected to increase may be added to the polishing composition in use at any time. [0082] <Washing> 典型 The grinding target which has finished the rough grinding step is typically washed before the fine grinding step is started. This washing | cleaning can be performed using an appropriate washing | cleaning liquid. The cleaning liquid used is not particularly limited, and for example, general SC-1 cleaning liquid, SC-2 cleaning liquid, etc. in the field of semiconductors and the like can be used. SC-1 washing liquid system ammonium hydroxide (NH4
OH) and hydrogen peroxide (H2
O2
) And water (H2
O) of the mixture). SC-2 washing liquid system HCl, H2
O2
With H2
O of mixed solution. The temperature of the cleaning liquid may be, for example, a range of room temperature or higher and at most about 90 ° C. The so-called room temperature here typically refers to about 15 ° C to 25 ° C. From the viewpoint of improving the cleaning effect, a cleaning solution of about 50 ° C to 85 ° C can be preferably used. [0083] After the rough grinding step, the washing step, and the fine grinding step as described above, the grinding of the object to be polished is completed. The above-mentioned object to be polished is a silicon substrate, and is typically a silicon single crystal wafer. Therefore, according to this specification, a method for manufacturing an abrasive including the above-mentioned polishing step is provided. The above-mentioned manufacturing method is specifically a manufacturing method of a silicon wafer. [0084] Above, according to this embodiment, a method for manufacturing a composition for rough polishing of a silicon wafer including abrasive particles, an alkaline compound, and a water-soluble polymer is provided. The manufacturing method includes the steps of preparing a liquid A containing the abrasive particles and the basic compound; and preparing a liquid B containing a water-soluble polymer P1 having an inertial radius of 100 nm or more as the water-soluble polymer; and The step of mixing liquid A and liquid B described above. The polishing composition obtained by this method can improve edge slippage during polishing of a silicon substrate by containing a water-soluble polymer P1 having a specific inertia radius or more. In addition, before completion, in other words, the polishing composition before use is a multi-dose form with liquids A and B. By increasing the concentration of each liquid (concentrated liquefaction), it is possible to enjoy convenience, cost reduction and other concentrated liquids Advantages. In addition, since the abrasive particles and the water-soluble polymer P1 are respectively contained in the liquid A and the liquid B, the situation that the water-soluble polymer P1 is prevented from being dispersed due to the presence of the abrasive particles can be avoided. As a result, the polishing composition before completion showed excellent stability in the state of liquid A or liquid B. Therefore, according to the present invention, the advantages of the concentrated liquid can be enjoyed, and at the same time, a silicon wafer rough polishing composition having excellent stability and improved edge slippage can be manufactured. [0085] A preferred aspect of the technology disclosed herein includes the step of diluting at least one of the aforementioned A liquid, the aforementioned B liquid, and a mixed liquid of the A liquid and the B liquid. In addition, the dilution ratio in the aforementioned dilution step is greater than 10 times based on the volume basis of the total amount of the A liquid and the B liquid. By adopting these methods, the polishing composition before completion can have both the advantages and stability of a concentrated liquid. When used, a polishing composition obtained by mixing liquid A and liquid B can be used to achieve the effect of reducing edge slippage. . The advantages of the concentrated solution are convenience and cost reduction. The above-mentioned dilution step may be performed before the step of mixing the A liquid and the B liquid, simultaneously with the mixing step, or after the mixing step. In addition, the technology disclosed in this document includes a method for manufacturing a composition for rough polishing of a silicon wafer, a set of a composition for rough polishing of a silicon wafer, a method for polishing a silicon wafer, and the like. [0086] A preferred aspect of the technology disclosed herein is that the radius of inertia of the water-soluble polymer contained in the aforementioned B liquid is 100 nm or more. After the B liquid is prepared, it is stored as needed, and then it is mixed with the A liquid when the polishing composition is used, so that the effects of the disclosed technology of the present invention can be better exerted. [0087] A preferred aspect of the technology disclosed herein is that the content of the abrasive particles in the A solution is 10% by weight or more. When the liquid A containing abrasive grains at a specific concentration or more is used, the effect of the disclosed technology of the present invention can be better exerted. [0088] A preferred aspect of the technology disclosed herein is that the aforementioned water-soluble polymer P1 content in the aforementioned B solution is 0.01% by weight or more. When the liquid B containing the water-soluble polymer P1 at a specific concentration or more is used, the effects of the disclosed technology of the present invention can be better exerted. [0089] In addition, according to this embodiment, a polishing composition set for manufacturing a silicon wafer rough polishing composition including abrasive particles, an alkaline compound, and a water-soluble polymer is provided. The polishing composition set includes a liquid A containing the abrasive particles and the basic compound, and a liquid B containing a water-soluble polymer P1 having an inertia radius of 100 nm or more as the water-soluble polymer. With this configuration, when liquids A and B are respectively used as concentrated liquids before storage, the advantages of the concentrated liquids can be enjoyed, and individual stability is excellent. Therefore, the A liquid and the B liquid are mixed at an appropriate point to prepare a polishing composition (polishing slurry). By using this, the edge slip of the substrate can be improved. The advantages of the concentrated solution are convenience and cost reduction. [0090] According to this embodiment, a method for polishing a silicon wafer including a rough polishing step and a fine polishing step is provided. The polishing method includes a step of preparing a composition for rough polishing used in the rough polishing step before the rough polishing step. In addition, the step of preparing the composition for rough grinding includes: a step of preparing a liquid A containing abrasive particles and a basic compound; and a step of preparing a liquid B containing a water-soluble polymer P1 having an inertia radius of 100 nm or more; and The step of mixing liquid A and liquid B described above. According to this method, the polishing composition before use can be separated into A liquid and B liquid, and it can be a concentrated liquid with excellent stability. In addition, by performing rough polishing using the polishing composition, it is possible to improve edge slippage of the substrate. [0091] In a typical aspect of the technology disclosed herein, the aforementioned rough polishing composition is used for polishing a silicon wafer after grinding. More specifically, the above-mentioned composition for rough polishing is used for rough polishing (pre-polishing) performed before final polishing of a silicon wafer. [Embodiments] [0092] Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in the embodiments. In addition, "%" in the following description is a weight basis unless there is particular notice. [0093] <Example 1> Colloidal silica (average primary particle size 55nm), TMAH, K2
CO3
、 Water-soluble polymer P2 (PVP, Mw 4.5 × 104
) Mixed with ion-exchanged water to prepare abrasive particles, TMAH, K2
CO3
And water-soluble polymer P2 are A liquids with concentrations of 32.97%, 1.62%, 1.05%, and 0.0069%, respectively. The pH of solution A was 11.2. Furthermore, by mixing the water-soluble polymer P1 (HEC), TMAH, and ion-exchanged water, the B liquid containing the water-soluble polymer P1 and TMAH at a concentration of 0.25% and 0.018%, respectively, was prepared. The pH of solution B was 11.0. The obtained liquid A and liquid B were diluted and mixed with ion-exchanged water to obtain a polishing liquid (acting slurry) of this example. The above-mentioned mixing was performed with a liquid A; a liquid B: ion-exchanged water at a ratio of 3.3: 0.1: 96.6 on a volume basis. [0092] <Examples 2 to 3 and Comparative Example 1> A liquid A and liquid B were prepared in the same manner as in Example 1 except that HEC having a different inertia radius was used as the water-soluble polymer P1 to obtain a polishing liquid (acting slurry) of this example. material). [0095] 实施 <Example 4> A liquid and A liquid were prepared in the same manner as in Example 3 except that the water-soluble polymer P2 was not used to obtain a polishing liquid (acting slurry) of this example. [0096] <Example 5> Colloidal silica (average primary particle size 55 nm), TMAH, K2
CO3
Mix with ion-exchanged water to prepare abrasive particles, TMAH and K2
CO3
Solution A was at a concentration of 32.97%, 1.62%, and 1.05%. The pH of solution A was 11.2. In addition, the water-soluble polymer P1 (HEC) and the water-soluble polymer P2 (PVP, Mw 4.5 × 10)4
), TMAH and ion-exchanged water are mixed to prepare a liquid B containing water-soluble polymer P1, water-soluble polymer P2 and TMAH at concentrations of 0.25%, 0.28% and 0.018%, respectively. The pH of solution B was 11.0. A polishing liquid (acting slurry) of this example was obtained in the same manner as in Example 1 except that the obtained liquids A and B were used. 〈〈 Example 6 〉〉 In Example 3, except that TMAH contained in the B liquid was changed from 0.018% to potassium hydroxide (KOH) 0.011%, the polishing liquid (working slurry) of this example was obtained in the same manner as in Example 3. ). [0098] <Comparative Examples 2 to 5> Colloidal silica (average primary particle size 55 nm), water-soluble polymer P1 (HEC), TMAH, K as abrasive particles2
CO3
、 Water-soluble polymer P2 (PVP, Mw 4.5 × 104
) Was mixed with ion-exchanged water to prepare a concentrated solution (1 dosage form) of the polishing composition of Comparative Examples 2 to 5, respectively. Abrasive particles, water-soluble polymers P1, TMAH, K in the concentrate of each example2
CO3
And the concentration of water-soluble polymer P2 were 32.97%, 0.0061%, 1.62%, 1.05%, and 0.0069%, respectively. The obtained concentrated liquid was diluted and mixed with ion-exchanged water to obtain a polishing liquid (acting slurry) of this example. The above dilution was performed with a concentrated solution; ion-exchanged water was performed at a ratio of 3.3: 96.7 on a volume basis. [0099] <Comparative Example 6> A polishing liquid (acting slurry) of this example was obtained in the same manner as in Comparative Example 5 except that the water-soluble polymer P2 was not used. [0100] [Measurement method of the radius of inertia] 测定 The measurement of the radius of inertia of the water-soluble polymer is to first prepare an aqueous solution so that the concentration of the water-soluble polymer is in the range of 0.1 to 1 mg / mL, and use light scattering for each sample prepared. The photometer "DLS-8000" (manufactured by Otsuka Electronics Co., Ltd.) measures every 10 degrees in a range of 20 to 150 degrees from the measurement angle, and calculates the radius of inertia [nm] by 1-concentration mapping analysis. The measurement is performed on water-soluble polymers contained in the water-soluble polymers P1 and B. When a plurality of water-soluble polymers are contained in the liquid B, the water-soluble polymers are adjusted so as to have a concentration ratio and measured. The measurement results are shown in Table 1. [0101] [Stability] Liquids A and B prepared in Examples 1 to 6 and Comparative Example 1 were placed in glass tubes having a diameter of 2.5 cm and a height of 25 cm, respectively, and stored at 25 ° C. The concentrated liquids of Comparative Examples 2 to 6 were stored under the same conditions as described above. The states of the A liquid, the B liquid, and the concentrated liquid after the lapse of 24 hours from the start of storage were evaluated visually on the following two criteria. That is, when separation or agglutination of components in the liquid was not seen, it was evaluated as "A", and when separation or agglutination was seen, it was evaluated as "B". The results are shown in Table 1. [0102] [Polishing of silicon wafer] 粗 Rough polishing was performed under the following conditions using the polishing liquid (action slurry) of each example. (Grinding conditions) Grinding device: Single-side grinder manufactured by THINKY, Japan, model "EJ-380IN" Grinding pad: Made by NITTA HAAS, trade name "MH S-15A" Grinding pressure: 26.6kPa Slurry flow rate: 100mL / Number of platen rotations per minute: 50rpm 数 Number of rotations of indenter: 50rpm Grinding amount: 8μm 种类 Work type: bare silicon P-
<100> Workpiece size: □ 60mm × 60mm [0103] [Edge slip off] Use a non-contact surface shape measuring machine (trade name "NewView 5032", manufactured by Zygo, available from CANON), and find the distance from the above grinding The reference height of the central part of the surface of the abrasive (20 mm square from the center) was measured as a change in height from a position about 2.5 mm from the outer peripheral end of the abrasive, and this was set as the amount of edge slip. The measured edge slippage was evaluated on the basis of the following 4 criteria. A: Edge slippage is less than 250nm B: Edge slippage is 250nm or more and less than 280nm C: Edge slippage is 280nm or more and less than 300nm D: Edge slippage is 300nm or more A ~ C is practical Eligibility, D is considered unacceptable. The results are shown in Table 1. [0104] 表面 [Surface Roughness Ra] For each example of the rough-polished silicon wafer (the test piece after the rough polishing and subsequent cleaning), a non-contact surface shape measuring machine (trade name "NewView 5032", Zygo (Manufactured by the company, available from CANON), and the surface roughness Ra (arithmetic average surface roughness) is measured. The obtained measured value was converted into a relative value with the surface roughness Ra of Example 4 set to 100%, and evaluated in the following two stages. The results are shown in Table 1. A: less than 100% B: more than 100% [0105][0106] As shown in Table 1, Examples 1 to 6 in which liquid A containing abrasive particles and a basic compound and liquid B containing water-soluble polymer P1 were separately prepared were excellent in stability both in liquid A and liquid B. On the other hand, in Comparative Examples 3 to 6 using the one-component concentrated solution, good stability could not be obtained. In addition, Examples 1 to 6 using the water-soluble polymer P1 having a radius of inertia of 100 nm or more improved edge slippage properties compared to Comparative Examples 1 and 2 using a water-soluble polymer having an inertia radius of less than 100 nm. In addition, in Examples 1 to 3, 5, and 6 in which the water-soluble polymer P2 was used in combination, compared with Example 4 in which the water-soluble polymer P2 was not used, the surface roughness Ra also tended to be improved. [0107] Although the specific examples of the present invention have been described in detail above, these are merely examples and do not limit the scope of patent applications. The technology described in the scope of the patent application includes various modifications and changes of the specific examples illustrated above.