針對本發明之一實施形態進行詳細說明。本實施形態之研磨用組成物係含有研磨粒與鹼性化合物。而且此研磨粒係滿足以下之條件者。亦即，以17質量%的濃度含有此研磨粒，同時含有四甲基氫氧化銨，且調製pH為11.3之剪斷黏度測定用液，測定此剪斷黏度測定用液在剪斷速度1000/s之剪斷黏度時，剪斷黏度成為如1.3mPa．s以上的研磨粒。
An embodiment of the present invention will be described in detail. The polishing composition of this embodiment contains abrasive grains and a basic compound. And the abrasive grains meet the following conditions. That is, the abrasive grains are contained at a concentration of 17% by mass, and tetramethylammonium hydroxide is also contained, and a shear viscosity measurement fluid with a pH of 11.3 is prepared, and the shear viscosity measurement fluid is measured at a shear rate of 1000/ When the shear viscosity of s, the shear viscosity becomes such as 1.3mPa. Abrasive grains above s.
如此之本實施形態之研磨用組成物可適合對單晶矽、多晶矽、矽化合物、金屬、陶瓷等之各種研磨對象物的研磨使用，可實現高平坦性。尤其是若將本實施形態之研磨用組成物使用在矽晶圓之研磨，可製得具有高平坦性之矽單結晶晶圓等之矽晶圓。 [0009] 例如，於矽晶圓之製造時對形成硬質雷射標示(Hard laser mark)之矽晶圓實施預備研磨時，有於硬質雷射標示之周緣部生成突起的情況。藉此，降低矽晶圓之平坦性。該硬質雷射標示之周緣部所生成之突起由於無法以拋光研磨去除，故有經完成之矽晶圓的平坦性變不夠充分之虞。 使用本實施形態之研磨用組成物，進行硬質雷射標示所形成之矽晶圓的預備研磨時，可減低於硬質雷射標示之周緣部所生成之突起。因此，若於使用本實施形態之研磨用組成物之預備研磨後，進行拋光研磨，可製得具有高平坦性之矽晶圓。 [0010] 本實施形態之研磨用組成物如上述，雖適合在硬質雷射標示所形成之矽晶圓的預備研磨，但本實施形態之研磨用組成物的用途或研磨之研磨對象物的種類並非被特別限定者。 例如，本實施形態之研磨用組成物亦可使用在未形成硬質雷射標示之研磨對象物。又，不限於預備研磨，亦可在鏡面拋光預備研磨後之研磨對象物的表面上之拋光研磨使用。進而，在硬質雷射標示所形成之矽晶圓的預備研磨，通常雖進行兩面研磨，但本實施形態之研磨用組成物亦可使用在單面研磨。 [0011] 於以下，針對本實施形態之研磨用組成物進行詳細說明。尚，於以下說明之各種操作或物性之測定除非另有說明，係以20℃以上25℃以下之室溫、相對濕度40%以上50%以下的條件下進行者。 1. 針對研磨粒 本實施形態之研磨用組成物中，有必要使用剪斷黏度測定用液之剪斷黏度成為1.3mPa･s以上之研磨粒，優選使用剪斷黏度測定用液之剪斷黏度成為1.5mPa･s以上之研磨粒。剪斷黏度測定用液之剪斷黏度高時，由於研磨粒與研磨面的摩擦增大，提高物理加工力，故提高研磨速度。因此，例如進行硬質雷射標示所形成之矽晶圓的研磨時，可減低硬質雷射標示之周緣部所生成之突起，可實現高平坦性。 [0012] 剪斷黏度測定用液之剪斷黏度係如以下般進行來測定。亦即，於研磨粒添加水，調製剪斷黏度測定用液。而且，將經調製之剪斷黏度測定用液裝填在黏彈性測定裝置，測定在剪斷速度1000/s之剪斷黏度。作為黏彈性測定裝置，例如可使用Anton Paar公司製之黏彈性測定裝置MCR302。測定溫度為25℃。 此時，剪斷黏度測定用液中之研磨粒的濃度成為17質量%。又，剪斷黏度測定用液之pH成為11.3。剪斷黏度測定用液之pH藉由四甲基氫氧化銨的添加來調整。 [0013] 研磨粒的種類並非被特別限定者，可將無機粒子、有機粒子、有機無機複合粒子等作為研磨粒使用。作為無機粒子之具體例，可列舉由二氧化矽、氧化鋁、氧化鈰、氧化鈦等之氧化物所構成之粒子或由氮化矽、碳化矽、氮化硼等之陶瓷所構成之粒子。又，作為有機粒子之具體例，可列舉聚甲基丙烯酸甲酯(PMMA)粒子。作為有機無機複合粒子之具體例，可列舉於二氧化矽鍵結聚甲基丙烯酸甲酯(PMMA)之粒子。此等之粒子當中，較佳為二氧化矽，更佳為膠態二氧化矽。尚，研磨粒可1種單獨使用，亦可混合2種以上使用。 [0014] 本實施形態之研磨用組成物所含有之研磨粒的平均粒徑雖並非被特別限定者，但平均粒徑較大者，有提高研磨速度的傾向。以藉由使用掃描型電子顯微鏡(SEM)之圖像觀察所測定之平均一次粒徑而言，研磨粒之平均一次粒徑較佳為20nm以上，更佳為30nm以上，再更佳為40nm以上，又再更佳為45nm以上。又，以藉由動態光散射法所測定之平均二次粒徑而言，研磨粒之平均二次粒徑較佳為30nm以上，更佳為50nm以上，再更佳為70nm以上，又再更佳為90nm以上。 [0015] 又，從研磨用組成物之分散安定性的觀點來看，研磨粒之平均一次粒徑較佳為500nm以下，更佳為200nm以下，再更佳為100nm以下。研磨粒之平均二次粒徑亦相同，較佳為500nm以下，更佳為250nm以下，再更佳為200nm以下。 [0016] 本實施形態之研磨用組成物中之研磨粒的含量可成為0.01質量%以上，較佳為0.1質量%以上，更佳為0.3質量%以上。若研磨粒的含量為上述的範圍內，容易得到具有高平坦性的表面。另外，研磨用組成物中之研磨粒的含量可成為5質量%以下，較佳為2質量%以下，更佳為1質量%以下。若研磨粒的含量為上述的範圍內，可兼具表面之高平坦性與研磨用組成物之製造成本的減低。 [0017] 2. 針對鹼性化合物 本實施形態之研磨用組成物係含有鹼性化合物。此鹼性化合物對矽晶圓等之研磨對象物的表面給予化學性作用。而且，研磨對象物的表面進行化學性研磨。藉由此化學蝕刻，使得提昇研磨研磨對象物時之研磨速度變容易。 [0018] 鹼性化合物的種類並非被特別限定者，可為有機鹼性化合物，亦可為鹼金屬氫氧化物、鹼金屬碳酸氫鹽、鹼金屬碳酸鹽、氨等之無機鹼性化合物。此等之鹼性化合物可1種單獨使用，亦可組合2種以上使用。 [0019] 鹼金屬氫氧化物的種類雖並非被特別限定者，但例如可列舉氫氧化鈉、氫氧化鉀。又，鹼金屬碳酸氫鹽的種類雖並非被特別限定者，但例如可列舉碳酸氫鈉、碳酸氫鉀。進而，鹼金屬碳酸鹽的種類雖並非被特別限定者，但例如可列舉碳酸鈉、碳酸鉀。 [0020] 作為有機鹼性化合物之例，可列舉四烷基銨鹽等之第四級銨鹽。作為在上述銨鹽之陰離子，可列舉OH-
。併用鹼金屬氫氧化物等之其他鹼性化合物時，作為陰離子亦可使用F-
、Cl-
、Br-
、I-
、ClO4 -
、BH4 -
等。例如可優選使用膽鹼、四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨等之第四級銨鹽。此等當中，更佳為四甲基氫氧化銨。 [0021] 作為有機鹼性化合物之其他例，可列舉四烷基鏻鹽等之第四級鏻鹽。作為在上述鏻鹽之陰離子，可列舉OH-
。併用鹼金屬氫氧化物等之其他鹼性化合物時，作為陰離子，亦可使用F-
、Cl-
、Br-
、I-
、ClO4 -
、BH4 -
等。例如可優選使用四甲基鏻、四乙基鏻、四丙基鏻、四丁基鏻等之鹵素化物、氫氧化物。 [0022] 作為有機鹼性化合物之其他例，可列舉胺類、哌嗪類、唑類、二氮雜雙環烷烴類、其他環狀胺類、胍等。作為胺類，例如可列舉甲基胺、二甲基胺、三甲基胺、乙基胺、二乙基胺、三乙基胺、乙烯二胺、單乙醇胺、N-(β-胺基乙基)乙醇胺、六亞甲基二胺、二乙烯三胺、三乙烯四胺。作為哌嗪類，例如可列舉哌嗪、1-(2-胺基乙基)哌嗪、N-甲基哌嗪。作為唑類，例如可列舉咪唑、三唑。作為二氮雜雙環烷烴類，例如可列舉1,4-二氮雜雙環[2.2.2]辛烷、1,8-二氮雜雙環[5.4.0]十一碳-7-烯、1,5-二氮雜雙環[4.3.0]-5-壬烯。作為其他環狀胺類，例如可列舉哌啶、胺基吡啶。 [0023] 本實施形態之研磨用組成物中之鹼性化合物的含量可成為0.001質量%以上，較佳為0.01質量%以上，更佳為0.05質量%以上。若鹼性化合物的含量為上述的範圍內，則提昇藉由研磨用組成物之研磨對象物的研磨速度。另外，研磨用組成物中之鹼性化合物的含量可成為5質量%以下，較佳為3質量%以下，更佳為1.5質量%以下。若鹼性化合物的含量為上述的範圍內，則增加研磨用組成物之安定性，減低製造成本。 [0024] 3. 針對研磨用組成物之pH 本實施形態之研磨用組成物之pH雖並非被特別限定者，但可成為9.0以上，更佳為10.0以上，再更佳為10.2以上。又，pH可成為12.0以下，更佳為11.4以下，再更佳為11.0以下。若pH為上述範圍內，更加提高研磨速度。研磨用組成物之pH例如可藉由添加後述之pH調整劑來調整。 [0025] 4. 針對添加劑 本實施形態之研磨用組成物中，為了提昇其性能，如有必要可添加pH調整劑、水溶性高分子、界面活性劑、螯合劑、防黴劑等之各種添加劑。於此，水溶性高分子可為水溶性共聚物，可為水溶性高分子或水溶性共聚物之鹽或衍生物。惟，較佳為實質上未含有氧化劑。 [0026] 4-1 針對pH調整劑 本實施形態之研磨用組成物之pH之值可藉由pH調整劑的添加調整。藉由研磨用組成物之pH的調整，可調控研磨對象物之研磨速度或研磨粒之分散性等。pH調整劑的添加量並非被特別限定者，研磨用組成物成為所期望之pH方式適當調整即可。 [0027] 作為pH調整劑之具體例，可列舉無機酸或羧酸、有機硫酸等之有機酸。作為無機酸之具體例，可列舉鹽酸、硫酸、硝酸、氫氟酸、硼酸、碳酸、次磷酸、亞磷酸、磷酸等。又，作為羧酸之具體例，可列舉甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、n-己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、n-庚酸、2-甲基己酸、n-辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸、乳酸、二乙醇酸、2-呋喃羧酸、2,5-呋喃二羧酸、3-呋喃羧酸、2-四氫呋喃羧酸、甲氧基乙酸、甲氧基苯基乙酸、苯氧基乙酸等。進而，作為有機硫酸之具體例，可列舉甲烷磺酸、乙烷磺酸、依沙酸等。此等之酸可1種單獨使用，亦可組合2種以上使用。 [0028] 4-2 針對水溶性高分子 本實施形態之研磨用組成物中，可添加對研磨對象物的表面或研磨粒的表面進行作用之水溶性高分子。於此，水溶性高分子可為水溶性共聚物，亦可為水溶性高分子或水溶性共聚物之鹽或衍生物。作為水溶性高分子、水溶性共聚物、此等之鹽或衍生物之具體例，可列舉聚丙烯酸鹽等之聚羧酸或聚膦酸、聚苯乙烯磺酸等之聚磺酸。又，作為其他具體例，可列舉黃原膠、
海藻酸鈉等之多糖類或羥基乙基纖維素、羧基甲基纖維素等之纖維素衍生物。 [0029] 進而，作為其他具體例，可列舉具有吡咯烷酮單位之水溶性高分子或聚乙二醇、聚乙烯醇、脫水山梨醇單油酸酯、具有單一種或複數種之氧伸烷單位的氧伸烷系聚合物等。作為具有吡咯烷酮單位之水溶性高分子，例如可列舉聚乙烯吡咯烷酮、聚乙烯吡咯烷酮聚丙烯酸共聚物、聚乙烯吡咯烷酮乙酸乙烯酯共聚物。此等之水溶性高分子當中，較佳為具有吡咯烷酮單位之水溶性高分子，更佳為聚乙烯吡咯烷酮。此等之水溶性高分子可1種單獨使用，亦可組合2種以上使用。 [0030] 4-3 針對界面活性劑 本實施形態之研磨用組成物中可添加界面活性劑。作為界面活性劑，可列舉陰離子性界面活性劑、非離子性界面活性劑。此等之界面活性劑當中，適合使用非離子性界面活性劑。 作為非離子性界面活性劑之具體例，可列舉氧伸烷之均聚物、複數種類之氧伸烷的共聚物、聚氧伸烷加成物。此等之非離子性界面活性劑當中，優選使用複數種類之氧伸烷的共聚物或聚氧伸烷加成物。 [0031] 4-4 針對螯合劑 本實施形態之研磨用組成物中可添加螯合劑。螯合劑藉由捕捉研磨系中之金屬雜質成分，形成錯合物，抑制矽晶圓之金屬污染，尤其是抑制因鎳或銅導致之污染。 作為螯合劑之具體例，可列舉葡萄糖酸等之羧酸系螯合劑、乙烯二胺、二乙烯三胺、三甲基四胺等之胺系螯合劑、乙烯二胺四乙酸、氮基(Nitrilo)三乙酸、羥基乙基乙烯二胺三乙酸、三乙烯四胺六乙酸、二乙烯三胺五乙酸等之聚胺基聚羧酸系螯合劑、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)、乙烯二胺肆(亞甲基膦酸)、二乙烯三胺五(亞甲基膦酸)、乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、甲烷羥基膦酸、1-膦醯基丁烷-2,3,4-三羧酸等之有機膦酸系螯合劑、酚衍生物、1,3-二酮等。此等之螯合劑當中，優選使用有機膦酸系螯合劑，尤其是乙烯二胺肆(亞甲基膦酸)。此等之螯合劑可1種單獨使用，亦可組合2種以上使用。 [0032] 4-5 針對防黴劑 本實施形態之研磨用組成物中可添加防黴劑。作為防黴劑之具體例，可列舉唑啶(Oxazolidine)-2,5-二酮等之噁唑啉等。 4-6 針對氧化劑 本實施形態之研磨用組成物，較佳為實質上未包含氧化劑。係因為研磨用組成物中包含氧化劑時，藉由研磨用組成物供給給研磨對象物，研磨對象物的表面氧化而產生氧化膜，藉此增長所需要研磨時間。作為氧化劑之具體例，可列舉過氧化氫(H2
O2
)、過硫酸鈉、過硫酸銨、過錳酸鉀、二氯異氰脲酸鈉等。 [0033] 尚，所謂「研磨用組成物實質上未包含氧化劑」，係意指至少意圖上未含有氧化劑。據此，源自原料或製法等不可避免包含微量之氧化劑的不可避的研磨用組成物，可包含在於此所謂「實質上未包含氧化劑之研磨用組成物」的概念。在研磨用組成物中之氧化劑的莫耳濃度，例如為0.0005莫耳/L以下，較佳為0.0001莫耳以下，更佳為0.00001莫耳/L以下，特佳為0.000001莫耳/L以下。 [0034] 5. 針對水 本實施形態之研磨用組成物可含有水。水係作為用以分散或溶解研磨用組成物之各成分，亦即研磨粒、鹼性化合物、添加劑等之分散媒或溶劑進行機能。為了極力回避阻礙研磨用組成物所含有之其他成分的作用，例如優選使用過渡金屬離子之合計的含量為100ppb以下之水。例如，可藉由使用離子交換樹脂之雜質離子的去除、藉由過濾器之粒子的去除、藉由蒸餾等之操作提高水之純度。具體而言，優選使用離子交換水、純水、超純水、蒸餾水等。 [0035] 6. 針對研磨用組成物之製造方法 本實施形態之研磨用組成物的製造方法並非被特別限定者，可藉由將研磨粒、與鹼性化合物、與視期望之pH調整劑、水溶性高分子等之各種添加劑於水中進行攪拌、混合而製得。混合時之溫度雖並非被特別限定者，但較佳為10℃以上40℃以下，為了提昇溶解速度可進行加熱。又，混合時間亦並未特別限定。 [0036] 7. 針對矽晶圓等之研磨對象物之研磨方法 使用本實施形態之研磨用組成物之研磨對象物的研磨，可藉由使用在通常之研磨的研磨裝置或研磨條件進行。例如可使用單面研磨裝置或兩面研磨裝置。 例如，將研磨對象物定為矽晶圓等之晶圓，使用單面研磨裝置進行研磨時，藉由使用被稱為載體之保持具來保持晶圓，於貼附研磨布之定盤擠壓晶圓之單面，邊供給研磨用組成物邊使定盤回轉，來研磨晶圓的單面。 [0037] 又，使用兩面研磨裝置研磨晶圓時，藉由使用被稱為載體之保持具，來保持晶圓，將貼附研磨布之定盤從晶圓的兩側分別擠壓在晶圓的兩面，邊供給研磨用組成物，邊使兩側的定盤回轉，來研磨晶圓的兩面。 即使使用任一種研磨裝置的情況下，皆為藉由研磨布及研磨用組成物與晶圓的摩擦之物理性作用、與研磨用組成物帶給晶圓之化學性作用，來研磨晶圓。 [0038] 作為研磨布，可使用聚胺基甲酸酯、不織布、絨面等之各種素材者。又，除了使用素材不同之外，亦可使用硬度或厚度等之物性各種不同者。進而，雖包含研磨粒者、未包含研磨粒者皆可使用，但較佳為使用未包含研磨粒者。進而，可使用實施如滯留液狀之研磨用組成物般之溝加工者。 [0039] 進而，研磨條件當中，針對對研磨對象物負荷之壓力即研磨荷重，雖並未特別限定，但可成為5kPa以上50kPa以下，較佳為8kPa以上40kPa以下，更佳為10kPa以上30kPa以下。若研磨荷重為此範圍內，發揮充分之研磨速度，可抑制藉由荷重破損研磨對象物，或於研磨對象物的表面產生傷等之缺陷。 [0040] 又，研磨條件當中，研磨所使用之研磨布與矽晶圓等之研磨對象物的相對速度(線速度)雖並未特別限定，但可成為10m/分鐘以上300m/分鐘以下，較佳為30m/分鐘以上200m/分鐘以下。若研磨布與研磨對象物的相對速度為此範圍內，得到充分之研磨速度。又，可抑制因研磨對象物的摩擦導致之研磨布的破損，進而對研磨對象物充分傳達摩擦，亦即可抑制研磨對象物滑動的狀態，可充分進行研磨。 [0041] 進而，研磨條件當中，針對研磨用組成物的供給量，雖因研磨對象物的種類、研磨裝置的種類、研磨條件而有所不同，但於研磨對象物與研磨布之間，為了無不均全面供給研磨用組成物，有足夠的量即可。研磨用組成物的供給量較少時，有研磨用組成物無法供給於研磨對象物全體，或乾燥凝固研磨用組成物而於研磨對象物的表面產生缺陷的情況。反之，研磨用組成物的供給量較多時，除了不經濟之外，恐有因過剩之研磨用組成物導致妨礙摩擦，而阻礙研磨之虞。尤其是有因水導致妨礙摩擦，而阻礙研磨之虞。 [0042] 進而，本實施形態之研磨用組成物可於使用在研磨對象物之研磨後進行回收，再使用在研磨對象物之研磨。作為再使用研磨用組成物之方法之一例，可列舉將從研磨裝置排出之研磨用組成物回收至桶，對再度研磨裝置內使其循環而使用在研磨之方法。若循環使用研磨用組成物，由於減低被作為廢液排出之研磨用組成物的量，故可減低環境負荷。又，由於可減低所使用之研磨用組成物的量，故可抑制研磨對象物之研磨所需要之製造成本。 [0043] 再使用本實施形態之研磨用組成物時，可將藉由使用在研磨所導致經消費、損失之研磨粒、鹼性化合物、添加劑等之一部分或全部，作為組成調整劑添加並且進行再使用。作為組成調整劑，可使用以任意之混合比率混合研磨粒、鹼性化合物、添加劑等者。可藉由以追加添加組成調整劑，為了再使用研磨用組成物調整成適當之組成，進行適當之研磨。組成調整劑所含有之研磨粒、鹼性化合物及其他添加劑的濃度為任意，並未特別限定，因應桶的大小或研磨條件適當調整即可。 [0044] 尚，本實施形態係表示本發明之一例者，本發明並非被限定於本實施形態者。又，本實施形態可加上各種變更或改良，加上如此之變更或改良的形態亦可包含在本發明。例如，本實施形態之研磨用組成物可為一液型，亦可為以任意之比率混合研磨用組成物之成分的一部分或全部的二液型等之多液型。又，在研磨對象物之研磨，雖可直接使用本實施形態之研磨用組成物的原液進行研磨，但亦可使用將原液以水等之稀釋液，例如稀釋成10倍以上之研磨用組成物的稀釋物進行研磨。 [0045] [實施例] 於以下表示實施例，邊參照表1邊進一步具體說明本發明。 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與2種之添加劑、與超純水，製造實施例1之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，2種之添加劑為螯合劑、水溶性高分子。 [0046] 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與2種之添加劑、與超純水，製造實施例2之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，2種之添加劑為螯合劑、水溶性高分子。 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與2種之添加劑、與超純水，製造實施例3之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，2種之添加劑為螯合劑、水溶性高分子。 [0047] 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與添加劑、與超純水，製造實施例4之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，添加劑為螯合劑。 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與2種之添加劑、與超純水，製造實施例5之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，2種之添加劑為螯合劑、水溶性高分子。 [0048] 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與2種之添加劑、與超純水，製造比較例1之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，2種之添加劑為螯合劑、水溶性高分子。 混合膠態二氧化矽所構成之研磨粒、與3種之鹼性化合物、與2種之添加劑、與超純水，製造比較例2之研磨用組成物。3種之鹼性化合物為氫氧化鉀、碳酸鉀、四甲基氫氧化銨，2種之添加劑為螯合劑、水溶性高分子。 [0049] 任何研磨用組成物的情況皆藉由將原液以超純水稀釋成30倍，來製造研磨用組成物。在原液之膠態二氧化矽的濃度為11.7質量%，氫氧化鉀的濃度為0.13質量%，碳酸鉀的濃度為1.12質量%，四甲基氫氧化銨的濃度為1.72質量%，螯合劑之乙烯二胺肆(亞甲基膦酸)的濃度為0.08質量%，水溶性高分子之聚乙烯吡咯烷酮K-30的濃度為0.0073質量%。 [0050] 在實施例1、2、3、4、5及比較例1、2之研磨用組成物的差異主要為膠態二氧化矽的種類。在實施例1、2、3、4、5及比較例1、2之研磨用組成物，含有經使用之各膠態二氧化矽之剪斷黏度測定用液的剪斷黏度、藉由使用掃描型電子顯微鏡(SEM)之圖像觀察所測定之各膠態二氧化矽的平均一次粒徑及藉由動態光散射法所測定之各膠態二氧化矽的平均二次粒徑係如表1所示。 [0051] 含有各膠態二氧化矽之剪斷黏度測定用液的剪斷黏度係如以下般進行而測定者。將膠態二氧化矽添加於水使其分散，調製以17質量%的濃度含有膠態二氧化矽的分散液。於此分散液添加四甲基氫氧化銨，將pH調整至11.3，而得到剪斷黏度測定用液。而且，將剪斷黏度測定用液裝填在Anton Paar公司製之黏彈性測定裝置MCR302，以測定溫度25℃、剪斷速度1000/s的條件測定剪斷黏度。在黏彈性測定裝置所使用之錐板的種類為CP50。 [0052][0053] 使用實施例1、2、3、4、5及比較例1、2之研磨用組成物，以下述之研磨條件進行直徑4英寸之裸矽晶圓的研磨。於此矽晶圓的表面，形成硬質雷射標示。又，此矽晶圓的傳導型為P型，結晶方位為＜100＞，電阻率為0.1Ω･cm以上未滿100Ω･cm。 [0054] (研磨條件) 研磨裝置：日本恩吉斯股份有限公司製之單面研磨裝置、型式「EJ-380IN」 研磨墊(研磨布)：Nitta Haas股份有限公司製「MH-S15A」 研磨荷重：16.7kPa 定盤之回轉速度：50min-1
頭(載體)之回轉速度：40min-1
研磨時間：藉由研磨之去除餘量成為5μm為止的時間(惟，去除餘量未到達5μm的情況下以60min結束研磨) 研磨用組成物之供給速度：100mL/min(流出使用) 研磨用組成物之溫度：23～26℃ [0055] 而且，測定研磨前之矽晶圓的質量、與研磨後之矽晶圓的質量，由其質量差、研磨時間、研磨面的面積、矽之密度等算出研磨速度。將結果示於表1。 又，分析研磨結束後之矽晶圓的表面，測定硬質雷射標示之周緣部所生成之突起的高度。將結果示於表1。突起的高度係使用東京精密股份有限公司製之形狀測定裝置SURFCOM DX-12測定。 [0056] 由表1可清楚明白，實施例1、2、3、4、5之研磨用組成物，由於含有膠態二氧化矽之剪斷黏度測定用液的剪斷黏度高，且膠態二氧化矽的平均粒徑有適當之大小，故研磨速度高且硬質雷射標示之周緣部所生成之突起的高度較低。由此結果，瞭解到若將硬質雷射標示所形成之矽晶圓的表面使用實施例1、2、3、4、5之研磨用組成物進行研磨，可減低硬質雷射標示之周緣部所生成之突起。 [0057] 對此，比較例2之研磨用組成物由於含有膠態二氧化矽之剪斷黏度測定用液的剪斷黏度較低，故硬質雷射標示之周緣部所生成之突起的高度較高。由此結果，瞭解到即使將硬質雷射標示所形成之矽晶圓的表面使用比較例2之研磨用組成物進行研磨，亦無法充分減低硬質雷射標示之周緣部所生成之突起。 又，比較例1之研磨用組成物由於含有膠態二氧化矽之剪斷黏度測定用液的剪斷黏度低，且膠態二氧化矽之平均二次粒徑較小，故無法研磨矽晶圓的表面。In this way, the polishing composition of the present embodiment can be suitably used for polishing various polishing objects such as monocrystalline silicon, polycrystalline silicon, silicon compounds, metals, ceramics, etc., and can achieve high flatness. In particular, if the polishing composition of the present embodiment is used for polishing of silicon wafers, silicon wafers such as silicon single crystal wafers with high flatness can be produced. [0009] For example, when a silicon wafer forming a hard laser mark is preliminarily polished during the manufacture of a silicon wafer, protrusions may be formed on the periphery of the hard laser mark. In this way, the flatness of the silicon wafer is reduced. Since the protrusions generated on the periphery of the hard laser mark cannot be removed by polishing, the flatness of the completed silicon wafer may become insufficient. Using the polishing composition of this embodiment to perform preliminary polishing of a silicon wafer formed by a hard laser mark can reduce the protrusions generated on the periphery of the hard laser mark. Therefore, if polishing and polishing are performed after the preliminary polishing using the polishing composition of this embodiment, a silicon wafer with high flatness can be obtained. [0010] As described above, the polishing composition of this embodiment is suitable for pre-polishing silicon wafers formed by hard laser markers, but the use of the polishing composition of this embodiment or the type of polishing object to be polished It is not specifically limited. For example, the polishing composition of the present embodiment can also be used for polishing objects that are not formed with a hard laser mark. In addition, it is not limited to preliminary polishing, and it can also be used for polishing and polishing the surface of the object to be polished after mirror polishing and preliminary polishing. Furthermore, in the pre-polishing of the silicon wafer formed by the hard laser marker, double-side polishing is usually performed, but the polishing composition of this embodiment can also be used for single-side polishing. [0011] In the following, the polishing composition of this embodiment will be described in detail. In addition, unless otherwise specified, the various operations or physical properties described below are carried out under the conditions of room temperature above 20°C and below 25°C and relative humidity above 40% and below 50%. 1. For the abrasive grains of the polishing composition of this embodiment, it is necessary to use the abrasive grains with the shear viscosity of the liquid for measuring the shear viscosity of 1.3 mPa･s or more. It is preferable to use the shear viscosity of the liquid for measuring the shear viscosity. Become abrasive grains above 1.5mPa･s. When the shear viscosity of the shear viscosity measurement fluid is high, the friction between the abrasive grains and the polishing surface increases, and the physical processing force is increased, so the polishing speed is increased. Therefore, for example, when polishing a silicon wafer formed by a hard laser mark, the protrusions generated on the periphery of the hard laser mark can be reduced, and high flatness can be achieved. [0012] The shear viscosity of the liquid for measuring the shear viscosity is measured as follows. That is, water is added to the abrasive grains to prepare a liquid for measuring the shear viscosity. Furthermore, the prepared liquid for measuring the shearing viscosity was filled in a viscoelasticity measuring device, and the shearing viscosity at a shearing speed of 1000/s was measured. As the viscoelasticity measuring device, for example, a viscoelasticity measuring device MCR302 manufactured by Anton Paar Corporation can be used. The measurement temperature is 25°C. At this time, the concentration of abrasive grains in the fluid for measuring the shear viscosity was 17% by mass. In addition, the pH of the shear viscosity measurement liquid was 11.3. The pH of the shear viscosity measurement liquid is adjusted by adding tetramethylammonium hydroxide. [0013] The type of abrasive particles is not particularly limited, and inorganic particles, organic particles, organic-inorganic composite particles, etc. can be used as abrasive particles. Specific examples of inorganic particles include particles composed of oxides such as silicon dioxide, aluminum oxide, cerium oxide, and titanium oxide, or particles composed of ceramics such as silicon nitride, silicon carbide, and boron nitride. In addition, as a specific example of the organic particles, polymethyl methacrylate (PMMA) particles can be cited. As a specific example of organic-inorganic composite particles, silicon dioxide bonded polymethyl methacrylate (PMMA) particles can be cited. Among these particles, silica is preferred, and colloidal silica is more preferred. However, the abrasive grains may be used alone or in combination of two or more kinds. [0014] Although the average particle size of the abrasive grains contained in the polishing composition of the present embodiment is not particularly limited, a larger average particle size tends to increase the polishing rate. In terms of the average primary particle size measured by image observation using a scanning electron microscope (SEM), the average primary particle size of the abrasive particles is preferably 20nm or more, more preferably 30nm or more, and still more preferably 40nm or more , And more preferably 45nm or more. Furthermore, in terms of the average secondary particle size measured by the dynamic light scattering method, the average secondary particle size of the abrasive grains is preferably 30nm or more, more preferably 50nm or more, still more preferably 70nm or more, and still more Preferably, it is 90 nm or more. [0015] Also, from the viewpoint of the dispersion stability of the polishing composition, the average primary particle size of the abrasive grains is preferably 500 nm or less, more preferably 200 nm or less, and still more preferably 100 nm or less. The average secondary particle size of the abrasive grains is also the same, preferably 500 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. [0016] The content of abrasive grains in the polishing composition of the present embodiment can be 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.3% by mass or more. If the content of abrasive grains is within the above range, it is easy to obtain a surface with high flatness. In addition, the content of abrasive grains in the polishing composition can be 5 mass% or less, preferably 2 mass% or less, and more preferably 1 mass% or less. If the content of the abrasive grains is within the above-mentioned range, both the high flatness of the surface and the reduction of the manufacturing cost of the polishing composition can be achieved. [0017] 2. Basic compound The polishing composition system of this embodiment contains a basic compound. This alkaline compound gives a chemical action to the surface of a polishing object such as a silicon wafer. Furthermore, the surface of the polishing object is chemically polished. With this chemical etching, it is easy to increase the polishing speed when polishing the object to be polished. [0018] The type of the basic compound is not particularly limited, and may be an organic basic compound, or an inorganic basic compound such as an alkali metal hydroxide, an alkali metal bicarbonate, an alkali metal carbonate, and ammonia. These basic compounds may be used singly or in combination of two or more kinds. [0019] Although the type of alkali metal hydroxide is not particularly limited, examples include sodium hydroxide and potassium hydroxide. Moreover, although the kind of alkali metal bicarbonate is not specifically limited, for example, sodium bicarbonate and potassium bicarbonate can be mentioned. Furthermore, although the kind of alkali metal carbonate is not specifically limited, for example, sodium carbonate and potassium carbonate are mentioned. [0020] Examples of organic basic compounds include quaternary ammonium salts such as tetraalkylammonium salts. As salts of the above-described anion include OH -. When using a basic compound and other alkali metal hydroxides, etc., can also be used as the anion F -, Cl -, Br - , I -, ClO 4 -, BH 4 - and the like. For example, quaternary ammonium salts such as choline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide can be preferably used. Among these, tetramethylammonium hydroxide is more preferable. [0021] As other examples of organic basic compounds, fourth-level phosphonium salts such as tetraalkylphosphonium salts can be cited. Examples of the anion of the phosphonium salt in the above, include OH -. When using a basic compound and other alkali metal hydroxides, etc., as the anion, can also use F -, Cl -, Br - , I -, ClO 4 -, BH 4 - and the like. For example, halides and hydroxides such as tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, and tetrabutylphosphonium can be preferably used. [0022] As other examples of organic basic compounds, amines, piperazines, azoles, diazabicycloalkanes, other cyclic amines, guanidines, etc. can be cited. Examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl Base) ethanolamine, hexamethylene diamine, diethylene triamine, triethylene tetramine. Examples of piperazines include piperazine, 1-(2-aminoethyl)piperazine, and N-methylpiperazine. Examples of azoles include imidazole and triazole. Examples of diazabicycloalkanes include 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1, 5-Diazabicyclo[4.3.0]-5-nonene. Examples of other cyclic amines include piperidine and aminopyridine. [0023] The content of the basic compound in the polishing composition of the present embodiment can be 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. When the content of the basic compound is within the above-mentioned range, the polishing rate of the object to be polished by the polishing composition is increased. In addition, the content of the basic compound in the polishing composition can be 5% by mass or less, preferably 3% by mass or less, and more preferably 1.5% by mass or less. If the content of the basic compound is within the above-mentioned range, the stability of the polishing composition is increased, and the manufacturing cost is reduced. 3. Regarding the pH of the polishing composition Although the pH of the polishing composition of this embodiment is not particularly limited, it can be 9.0 or more, more preferably 10.0 or more, and still more preferably 10.2 or more. In addition, the pH may be 12.0 or less, more preferably 11.4 or less, and still more preferably 11.0 or less. If the pH is within the above range, the grinding speed will be further increased. The pH of the polishing composition can be adjusted, for example, by adding a pH adjuster described later. [0025] 4. Additives In the polishing composition of this embodiment, in order to improve its performance, various additives such as pH adjusters, water-soluble polymers, surfactants, chelating agents, and antifungal agents can be added if necessary . Here, the water-soluble polymer may be a water-soluble copolymer, and may be a water-soluble polymer or a salt or derivative of the water-soluble copolymer. However, it is preferable that the oxidizing agent is not contained substantially. [0026] 4-1 Regarding the pH adjuster The pH value of the polishing composition of this embodiment can be adjusted by adding a pH adjuster. By adjusting the pH of the polishing composition, the polishing speed of the polishing object or the dispersibility of the abrasive particles can be controlled. The addition amount of the pH adjuster is not particularly limited, and the polishing composition may be appropriately adjusted to the desired pH method. [0027] As specific examples of the pH adjuster, organic acids such as inorganic acids, carboxylic acids, and organic sulfuric acids can be cited. Specific examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, phosphoric acid, and the like. In addition, specific examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, and 2-ethyl Butyric acid, 4-methylvaleric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, diglycolic acid, 2-furan carboxylic acid, 2,5- Furandicarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid, etc. Furthermore, as specific examples of organic sulfuric acid, methanesulfonic acid, ethanesulfonic acid, and ethanoic acid can be cited. These acids may be used singly or in combination of two or more kinds. [0028] 4-2 Regarding the water-soluble polymer In the polishing composition of this embodiment, a water-soluble polymer that acts on the surface of the object to be polished or the surface of the abrasive grain can be added. Here, the water-soluble polymer may be a water-soluble copolymer, or a salt or derivative of a water-soluble polymer or a water-soluble copolymer. Specific examples of water-soluble polymers, water-soluble copolymers, and salts or derivatives thereof include polycarboxylic acids such as polyacrylates or polysulfonic acids such as polyphosphonic acid and polystyrene sulfonic acid. Moreover, as other specific examples, polysaccharides such as xanthan gum and sodium alginate, or cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be cited. [0029] Further, as other specific examples, water-soluble polymers having pyrrolidone units or polyethylene glycol, polyvinyl alcohol, sorbitan monooleate, and oxyethylene units having a single or plural kinds of Oxyethylene series polymers, etc. Examples of the water-soluble polymer having a pyrrolidone unit include polyvinylpyrrolidone, polyvinylpyrrolidone polyacrylic acid copolymer, and polyvinylpyrrolidone vinyl acetate copolymer. Among these water-soluble polymers, a water-soluble polymer having a pyrrolidone unit is preferred, and polyvinylpyrrolidone is more preferred. These water-soluble polymers can be used singly or in combination of two or more. [0030] 4-3 Regarding Surfactant Surfactants can be added to the polishing composition of this embodiment. Examples of the surfactant include anionic surfactants and nonionic surfactants. Among these surfactants, nonionic surfactants are suitable. Specific examples of nonionic surfactants include homopolymers of oxyethylene, copolymers of plural kinds of oxyethylene, and polyoxyethylene adducts. Among these nonionic surfactants, it is preferable to use plural kinds of copolymers of oxyethylene or polyoxyethylene adducts. [0031] 4-4 Regarding Chelating Agent A chelating agent can be added to the polishing composition of this embodiment. The chelating agent captures the metal impurities in the polishing system to form complexes and inhibits the metal contamination of silicon wafers, especially the contamination caused by nickel or copper. Specific examples of chelating agents include carboxylic acid chelating agents such as gluconic acid, amine chelating agents such as ethylene diamine, diethylene triamine, and trimethyl tetraamine, ethylene diamine tetraacetic acid, and nitrogen (Nitrilo )Polyaminopolycarboxylic acid chelating agents such as triacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid, 2-aminoethylphosphonic acid, 1-hydroxyl Ethylene-1,1-diphosphonic acid, amino tris (methylene phosphonic acid), ethylene diamine four (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), ethane -1,1-Diphosphonic acid, ethane-1,1,2-triphosphonic acid, methane hydroxyphosphonic acid, 1-phosphoranylbutane-2,3,4-tricarboxylic acid and other organic phosphonic acids Chelating agents, phenol derivatives, 1,3-diketones, etc. Among these chelating agents, organic phosphonic acid chelating agents are preferably used, especially ethylene diamine (methylene phosphonic acid). These chelating agents may be used singly or in combination of two or more kinds. [0032] 4-5 Antifungal agent An antifungal agent can be added to the polishing composition of this embodiment. As a specific example of the antifungal agent, oxazolidine such as oxazolidine-2,5-dione and the like can be cited. 4-6 Regarding the oxidizing agent, the polishing composition of this embodiment preferably does not substantially contain an oxidizing agent. This is because when the polishing composition contains an oxidizing agent, the polishing composition is supplied to the polishing object, and the surface of the polishing object is oxidized to generate an oxide film, thereby increasing the required polishing time. Specific examples of the oxidizing agent include hydrogen peroxide (H 2 O 2 ), sodium persulfate, ammonium persulfate, potassium permanganate, sodium dichloroisocyanurate, and the like. [0033] In addition, the phrase "the polishing composition does not substantially contain an oxidizing agent" means that it does not contain an oxidizing agent at least intentionally. Accordingly, the unavoidable polishing composition derived from the raw material or the production method that inevitably contains a trace amount of an oxidizing agent may include the concept of "a polishing composition that does not substantially contain an oxidizing agent". The molar concentration of the oxidizing agent in the polishing composition is, for example, 0.0005 mol/L or less, preferably 0.0001 mol/L or less, more preferably 0.00001 mol/L or less, particularly preferably 0.000001 mol/L or less. [0034] 5. Regarding water The polishing composition of this embodiment may contain water. The water system functions as a dispersion medium or solvent for dispersing or dissolving the components of the polishing composition, that is, abrasive grains, alkaline compounds, additives, and the like. In order to avoid hindering the effect of other components contained in the polishing composition as much as possible, for example, it is preferable to use water whose total content of transition metal ions is 100 ppb or less. For example, the purity of water can be improved by operations such as the removal of impurity ions using ion exchange resins, the removal of particles by filters, and distillation. Specifically, ion exchange water, pure water, ultrapure water, distilled water, etc. are preferably used. [0035] 6. The manufacturing method of the polishing composition The manufacturing method of the polishing composition of this embodiment is not particularly limited. It can be achieved by combining abrasive grains, a basic compound, and an optional pH adjuster, Various additives such as water-soluble polymers are prepared by stirring and mixing in water. Although the temperature during mixing is not particularly limited, it is preferably 10°C or more and 40°C or less, and heating may be performed in order to increase the dissolution rate. In addition, the mixing time is not particularly limited. [0036] 7. Polishing method for polishing objects such as silicon wafers The polishing of the polishing objects using the polishing composition of this embodiment can be performed by using a polishing device or polishing conditions that are used in ordinary polishing. For example, a single-side polishing device or a double-side polishing device can be used. For example, when the object to be polished is a wafer such as a silicon wafer, when a single-sided polishing device is used for polishing, a holder called a carrier is used to hold the wafer, and the polishing cloth is applied to the table to squeeze it. The single side of the wafer is polished by rotating the platen while supplying the polishing composition. [0037] In addition, when the wafer is polished using a double-sided polishing device, a holder called a carrier is used to hold the wafer, and the platen to which the polishing cloth is attached is pressed against the wafer from both sides of the wafer. While supplying the polishing composition on both sides of the wafer, the fixed disks on both sides are rotated to grind both sides of the wafer. Even when any type of polishing device is used, the wafer is polished by the physical effect of the friction between the polishing cloth and the polishing composition and the wafer, and the chemical effect of the polishing composition on the wafer. [0038] As the polishing cloth, various materials such as polyurethane, non-woven fabric, and suede can be used. Moreover, in addition to different materials used, various physical properties such as hardness and thickness can also be used. Furthermore, although both those containing abrasive grains and those not containing abrasive grains can be used, it is preferable to use those that do not contain abrasive grains. Furthermore, it is possible to use one that performs groove processing like a polishing composition in the form of a retained liquid. [0039] Furthermore, among the polishing conditions, the pressure applied to the object to be polished, that is, the polishing load, is not particularly limited, but may be 5 kPa or more and 50 kPa or less, preferably 8 kPa or more and 40 kPa or less, and more preferably 10 kPa or more and 30 kPa or less. . If the polishing load is within this range, a sufficient polishing speed can be exerted, and defects such as damage to the polishing object due to the load and scratches on the surface of the polishing object can be suppressed. [0040] In addition, in the polishing conditions, the relative speed (linear speed) between the polishing cloth used for polishing and the polishing object such as the silicon wafer is not particularly limited, but it can be 10 m/min or more and 300 m/min or less. Preferably, it is 30 m/min or more and 200 m/min or less. If the relative speed between the polishing cloth and the polishing object is within this range, a sufficient polishing speed can be obtained. In addition, it is possible to suppress the damage of the polishing cloth due to the friction of the polishing object, and to further transmit the friction to the polishing object sufficiently, that is, the sliding state of the polishing object can be suppressed, and the polishing can be performed sufficiently. [0041] Furthermore, among the polishing conditions, the supply amount of the polishing composition differs depending on the type of polishing object, the type of polishing device, and the polishing conditions. However, the difference between the polishing object and the polishing cloth is The polishing composition is supplied completely without unevenness, and the amount is sufficient. When the supply amount of the polishing composition is small, the polishing composition cannot be supplied to the entire polishing object, or the polishing composition is dried and solidified, and defects may occur on the surface of the polishing object. Conversely, when the supply amount of the polishing composition is large, in addition to being uneconomical, the excess polishing composition may hinder friction and hinder polishing. In particular, water may hinder friction and hinder polishing. [0042] Furthermore, the polishing composition of the present embodiment can be used for polishing an object to be polished and then recovered, and then used for polishing the object to be polished. As an example of a method of reusing the polishing composition, a method of recovering the polishing composition discharged from the polishing device into a bucket and recycling it in the repolishing device is used for polishing. If the polishing composition is recycled, the amount of the polishing composition that is discharged as a waste liquid can be reduced, so that the environmental load can be reduced. In addition, since the amount of the polishing composition used can be reduced, the manufacturing cost required for polishing of the polishing object can be suppressed. [0043] When the polishing composition of this embodiment is reused, some or all of the abrasive grains, alkaline compounds, additives, etc. consumed or lost due to the use of polishing can be added as a composition adjuster. reuse. As the composition modifier, one that mixes abrasive grains, basic compounds, additives, etc. at any mixing ratio can be used. The composition adjuster can be additionally added to adjust the composition to an appropriate composition in order to reuse the polishing composition, and perform appropriate polishing. The concentration of abrasive grains, basic compounds, and other additives contained in the composition adjuster is arbitrary and is not particularly limited, and may be adjusted appropriately according to the size of the barrel or the polishing conditions. [0044] This embodiment is an example of the present invention, and the present invention is not limited to this embodiment. In addition, various changes or improvements can be added to the present embodiment, and forms with such changes or improvements can also be included in the present invention. For example, the polishing composition of the present embodiment may be a one-liquid type, or a two-liquid type, such as a two-liquid type, in which a part or all of the components of the polishing composition are mixed at an arbitrary ratio. In addition, in the polishing of the object to be polished, although the original solution of the polishing composition of this embodiment can be used directly for polishing, it is also possible to use a diluted solution of the original solution with water, for example, a polishing composition diluted to 10 times or more. The dilutions are ground. [Examples] Examples are shown below, and the present invention will be described in further detail with reference to Table 1. An abrasive grain composed of colloidal silica, 3 kinds of alkaline compounds, 2 kinds of additives, and ultrapure water were mixed to produce the polishing composition of Example 1. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the two additives are chelating agents and water-soluble polymers. [0046] An abrasive grain composed of colloidal silica, 3 kinds of alkaline compounds, 2 kinds of additives, and ultrapure water were mixed to produce the polishing composition of Example 2. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the two additives are chelating agents and water-soluble polymers. An abrasive grain composed of colloidal silica, 3 kinds of alkaline compounds, 2 kinds of additives, and ultrapure water were mixed to produce the polishing composition of Example 3. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the two additives are chelating agents and water-soluble polymers. [0047] The abrasive grains composed of colloidal silica, 3 kinds of alkaline compounds, additives, and ultrapure water were mixed to produce the polishing composition of Example 4. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the additive is a chelating agent. The abrasive grains composed of colloidal silica, 3 kinds of alkaline compounds, 2 kinds of additives, and ultrapure water were mixed to produce the polishing composition of Example 5. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the two additives are chelating agents and water-soluble polymers. [0048] An abrasive grain composed of colloidal silica, 3 kinds of alkaline compounds, 2 kinds of additives, and ultrapure water were mixed to produce the polishing composition of Comparative Example 1. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the two additives are chelating agents and water-soluble polymers. An abrasive grain composed of colloidal silica, 3 kinds of alkaline compounds, 2 kinds of additives, and ultrapure water were mixed to produce a polishing composition of Comparative Example 2. The three basic compounds are potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide, and the two additives are chelating agents and water-soluble polymers. [0049] In the case of any polishing composition, the polishing composition is manufactured by diluting the stock solution 30 times with ultrapure water. The concentration of colloidal silica in the stock solution is 11.7% by mass, the concentration of potassium hydroxide is 0.13% by mass, the concentration of potassium carbonate is 1.12% by mass, and the concentration of tetramethylammonium hydroxide is 1.72% by mass. The concentration of ethylene diamine 4 (methylene phosphonic acid) is 0.08% by mass, and the concentration of polyvinylpyrrolidone K-30, which is a water-soluble polymer, is 0.0073% by mass. [0050] The difference in the polishing composition of Examples 1, 2, 3, 4, 5 and Comparative Examples 1 and 2 is mainly the type of colloidal silica. In the polishing compositions of Examples 1, 2, 3, 4, 5 and Comparative Examples 1 and 2, the shear viscosity of each colloidal silica used for measuring the shear viscosity of the liquid for measuring the shear viscosity was scanned by using Table 1 Shown. [0051] The shear viscosity of the shear viscosity measurement fluid containing each colloidal silica was measured as follows. The colloidal silica was added to water and dispersed to prepare a dispersion liquid containing colloidal silica at a concentration of 17% by mass. Tetramethylammonium hydroxide was added to this dispersion liquid to adjust the pH to 11.3, and a liquid for measuring shear viscosity was obtained. Furthermore, the shear viscosity measurement liquid was filled in the viscoelasticity measuring device MCR302 manufactured by Anton Paar, and the shear viscosity was measured under the conditions of a measurement temperature of 25°C and a shear speed of 1000/s. The type of cone and plate used in the viscoelasticity measuring device is CP50. [0052] [0053] Using the polishing compositions of Examples 1, 2, 3, 4, 5 and Comparative Examples 1 and 2, the bare silicon wafers with a diameter of 4 inches were polished under the following polishing conditions. On the surface of this silicon wafer, a hard laser mark is formed. In addition, the conductivity type of this silicon wafer is P type, the crystal orientation is <100>, and the resistivity is 0.1Ω･cm or more but less than 100Ω･cm. [0054] (Polishing conditions) Polishing device: Single-side polishing device manufactured by Nippon Engis Co., Ltd., type "EJ-380IN" Polishing pad (grinding cloth): "MH-S15A" manufactured by Nitta Haas Co., Ltd. Polishing load : 16.7kPa Rotation speed of fixed plate: 50min -1 Rotation speed of head (carrier): 40min -1 Grinding time: Time until the removal margin by polishing becomes 5μm (except when the removal margin does not reach 5μm Polishing is finished in 60min) The supply rate of the polishing composition: 100mL/min (for flow-out use) The temperature of the polishing composition: 23～26°C [0055] Furthermore, the quality of the silicon wafer before polishing and the difference after polishing are measured The quality of the silicon wafer is calculated from the difference in quality, the polishing time, the area of the polishing surface, and the density of silicon to calculate the polishing speed. The results are shown in Table 1. In addition, the surface of the silicon wafer after polishing was analyzed, and the height of the protrusions formed on the peripheral edge of the hard laser marker was measured. The results are shown in Table 1. The height of the protrusion was measured using a shape measuring device SURFCOM DX-12 manufactured by Tokyo Seiki Co., Ltd. [0056] It can be clearly understood from Table 1 that the polishing composition of Examples 1, 2, 3, 4, and 5 has a high shear viscosity and a colloidal state due to the shear viscosity measurement fluid containing colloidal silica The average particle size of the silicon dioxide has an appropriate size, so the polishing speed is high and the height of the protrusions formed on the periphery of the hard laser marking is low. From this result, it is understood that if the surface of the silicon wafer formed by the hard laser marker is polished using the polishing composition of Examples 1, 2, 3, 4, and 5, the peripheral edge of the hard laser marker can be reduced. Generated protrusions. [0057] In this regard, the polishing composition of Comparative Example 2 has a lower shear viscosity of the shear viscosity measurement fluid containing colloidal silica, so the height of the protrusions generated at the periphery of the hard laser marker is higher. high. From this result, it is understood that even if the surface of the silicon wafer formed by the hard laser mark is polished with the polishing composition of Comparative Example 2, the protrusions generated on the peripheral edge of the hard laser mark cannot be sufficiently reduced. In addition, the polishing composition of Comparative Example 1 cannot grind silicon crystals because the shear viscosity of the shear viscosity measurement fluid containing colloidal silica is low, and the average secondary particle size of the colloidal silica is small. Round surface.
