201213522 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於對研磨對象物之被研磨面進行化 學機械研磨之研磨劑及研磨方法。更詳細而言，關於一種 適於碳化梦基板等之精研磨之化學機械研磨用研磨劑、及 使用其之研磨方法。 【先前技術】 貫現電此之低4貝耗化及而性能化之電子器件（功率器件） 係直接有助於電力消耗之大幅度節省，因此，近年來不斷 利用於較多領域中。而且，作為功率器件用之基材，正在 研究使用碳化矽（SiC)或氮化鎵（GaN)等化合物半導體材料 以取代石夕。 為了於SiC之基板上，藉由磊晶成長而形成GaN等之結 晶薄膜並將其器件化，而關鍵在於獲得結晶學上低缺陷且 高品質之基板表面。而且，為獲得低缺陷、高平滑之表 面’化學機械研磨（Chemical Mechanical Polishing，以 下’有時亦稱為CMP)技術受到關注。201213522 VI. Description of the Invention: [Technical Field] The present invention relates to an abrasive and a polishing method for chemically polishing a surface to be polished of an object to be polished. More specifically, the present invention relates to an abrasive for chemical mechanical polishing suitable for polishing a carbonized dream substrate or the like, and a polishing method using the same. [Prior Art] The electronic device (power device) which consumes and consumes 4 lbs of low power directly contributes to a large saving in power consumption, and thus has been utilized in many fields in recent years. Further, as a substrate for a power device, a compound semiconductor material such as lanthanum carbide (SiC) or gallium nitride (GaN) has been studied to replace Shi Xi. For the SiC substrate, a crystal thin film of GaN or the like is formed by epitaxial growth and deviceized, and the key is to obtain a crystallographically low defect and high quality substrate surface. Further, in order to obtain a low defect, high smooth surface, "Chemical Mechanical Polishing" (hereinafter sometimes referred to as CMP) technology has attracted attention.
SiC基板（SiC晶圓）係由如下方式製造。即，將已成長之 SiC單晶錠切割成晶圓狀，並由研磨機調整厚度後，藉由 含有金剛石研磨粒之研磨劑對表面進行研磨（初研磨），調 整表面之平坦度，進而對表面進行精研磨，從而製造表面 平坦度較高之基板（晶圓）。 精研磨係要求藉由化學機械研磨而將初研磨中產生於基 板表面之加工變質層去除，並且使加工變質層去除後所露 158824.doc 201213522 出之基板表面高度地平坦化、平滑化。如此決定siC基板 之品質之精研磨中，先前以來使用氧化矽微粒子。然而， SiC或GaN均為硬度極高且化學穩定性亦較高，因此·，存 在難以一面確保平坦性、平滑性一面以較高之研磨效率 (研磨速度）進行研磨，導致研磨所需之時間極長之問題。 作為sic基板之精研磨用之研磨劑，例如於專利文獻 揭不有含有膠體二氧化矽之pH4〜9之研磨劑，但並未記載 粒度分佈之寬度，且專利文獻丨所示之研磨劑，因Sic基板 之研磨速度較低’而存在研磨時間變長之問題。 又，於專利文獻2中，揭示有含有包含氧化鉻之研磨粒 及氧化劑之研磨劑，但該研磨劑不僅含有環境有害性較高 之氧化鉻，而且具有存在研磨後之SiC基板之表面被氧化 鉻污染之虞等來自環境污染觀點之問題。 進而’於專利文獻3中，揭示有含有膠體二氧化珍、叙 酸鹽及氧化劑之研磨劑，但於使用該研磨劑之情形時，亦 存在如下問題：SiC基板之研磨速度不充分，且為獲得特 定之研磨量’而使研磨所需之時間變長。 先前技術文獻 專利文獻 專利文獻1:日本專利特開2005-117027號公報 專利文獻2:曰本專利特開2004-327952號公報 專利文獻3 :日本專利特開2008-179655號公報 【發明内容】 發明所欲解決之問題 158824.doc •4- 201213522 本發明係為解決上述問題研製而成者，其目的在於提供 一種更高速地對如SiC基板之硬度極高且化學穩定性較高 之研磨對象物之被研磨面進行研磨，並且研磨後之表面平 坦性及平滑性亦優異之研磨劑及研磨方法。 解決問題之技術手段 本發明係提供一種包含以下構成之研磨劑。 Π] —種研磨劑’其係用於對研磨對象物之被研磨面進 打化學機械研磨者，且含有平均粒徑（D5Q)為2〇〜15〇 90%粒徑（D90)與10%粒徑（Dl〇)之比（D9〇/Di〇)為J 6〜1〇 〇之氧 化矽粒子、氧化劑及水，且pH值為8 5〜12 〇。[2]如上述 [1]之研磨劑，其中更含有無機鹽及潤滑劑。[3]如上述[2] 之研磨4，其中上述無機鹽係選自由瑞酸卸、硝酸納、硫 心奸、硫酸鈉、麟酸卸及磷酸鈉所組成之群中之至少1 種。[4]如上述[2]之研磨劑，其中上述潤滑劑係具有選自 烷基、芳基及經芳基取代之烷基中之至少丨種碳數6〜2〇之 烴基之胺之至少1種。[5]如上述[4]之研磨劑，其中上述潤 滑劑為選自由辛基胺、十二録胺及聚氧乙烯月桂基胺所 組成之群中之至少1種]6]如上述⑴至[5]中任—項之研磨 劑’其中上述氧化劑為選自由過氧化氫、過硫酸銨及過硫 酸鉀所組成之群中之至少！種。[7]如上述⑴至附任一項 之^劑’其中上述研磨對象物係修正莫氏硬度為10以上 之早晶基板。[8]如上述[7]之研磨劑，其中上述研磨對象 物為碳化矽單晶基板。 又，本發明提供-種包含以下構成之研磨方法。 s 158824,doc 201213522 [9] 一種研磨方法’其係將如上述[丨]至[8]中任一項之 研磨劑供給至研磨墊，使研磨對象物之被研磨面與上述研 磨墊接觸’藉由兩者間之相對運動而進行研磨。 再者，於本發明中，所謂「被研磨面」，係指研磨對象 物被研磨之面，例如為表面。 發明之效果 根據本發明之研磨劑及使用其之研磨方法，可以較高之 研磨速度對如碳化矽（SiC)基板之硬度較高之研磨對象物之 被研磨面進行研磨，從而可獲得平坦且平滑之無劃痕之研 磨後之表面。 【實施方式】 以下’對本發明之實施形態進行說明。 [研磨劑] 本發明之研磨劑係用於對研磨對象物之被研磨面進行研 磨者’且分別包含平均粒控（D5〇)為20〜150 nm且90%粒徑 (D9〇)與10%粒徑（D10)之比（〇9()/1)10)為mo o之氧化矽粒 子、氧化劑及水。而且，研磨劑之pH值成為85〜12〇之範 圍。本發明之研磨劑具有漿料之形狀。 於本發明中，平均粒徑（D5〇)為體積基準累積50〇/。粒徑。 該體積基準累積50%粒徑（D50)係由體積基準求出粒度分 佈，且於總體積設為1〇〇〇/0之累積曲線中，累積值達到5〇% 之點之粒徑。再者，本說明書中，有時將平均粒徑（D5〇)僅 稱為平均粒徑或D50。 同樣地，10%粒徑（D10)及90%粒徑（D90)係體積基準累積 158824.doc 201213522 10〇/〇粒徑及體積基準累積90%粒徑，且於求出之粒产分佈 之總體積設為100%之累積曲線中，表示累積值達到1〇%及 90%之點之粒徑。因此，90%粒徑⑴川）與1〇%粒徑（DM之 比（D9G/D1G)係指表示粒度分佈之寬度之指標。具有隨著 D9〇/D1G之值變大而變寬之粒度分佈。又，具有D^/Di❶越接 近於1則越接近於單分散之粒度分佈。再者，於本發明 中，粒度分佈可由利用雷射散射粒度分佈測定裝置測定之 頻率分佈及累積體積分佈曲線而求出。而且，粒徑之測定 係藉由使氧化矽粒子分散於水介質中，使用例如日機裝公 司製造之Microtrac UPA等測定粒度分佈而進行。 於本發明之研磨劑中，分別含有具有仏^為川〜15〇 11爪且 D9〇/D1(3為1.6〜1〇.〇之寬粒度分佈之氧化矽粒子即研磨粒' 及氧化劑，且具有8.5〜12.0之pH值，因此，可以較高之研 磨速度對如碳化矽（SiC)基板之硬度較高且化學穩定性較高 之研磨對象物進行研磨，從而可獲得平坦且平滑且無劃痕 之研磨後之表面。 尤其，作為研磨粒之氧化矽粒子2D9q/Di()係大於先前一 直使用之研磨粒，且具有較寬之粒度分佈，因此，可獲得 較咼之研磨速度。即，於D9q/Diq接近〗且具有接近單分散 之粒度分佈之粒子係研磨時產生於與研磨對象物之間之研 磨應力相對變小，相對於此，粒徑分佈較寬之粒子係因小 粒徑之粒子進入粒徑大之粒子之間，而使產生於與研磨對 象物之間之研磨應力變大^此，包含具有較寬粒度分佈 之氧化矽粒子之本發明之研磨劑係研磨時較大之研磨應力 J58824.doc 201213522 作用於研磨對象物，因此，可有效對上述硬質材料或難研 磨材料進行研磨。 又’本發明之研磨劑由於具有85〜12〇之阳值故而， 氧化劑有效發揮作用，研磨特性良好，且作為研磨粒之氧 化矽粒子之分散穩定性亦優異。 以下，對本發明之研磨劑之各成分及pH值進行詳細敍 述0 (1)氧化矽粒子 本發明之研磨劑中之氧化矽（矽）粒子係作為研磨粒發揮 作用。作為矽，可使用由公知方法而製造者。例如可使 用藉由利用溶膠-凝膠法將矽酸乙酯、矽酸曱酯等矽烷氧 化物水解而獲得之膠體二氧切^又，可使特料納離 =交換所得之膠體二氧切或四氣切於氧與氫之火焰中 氣相合成之煙熏二氧化石夕。 該等之中，?尤容易㈣粒徑且可獲得高純度品之方面而 吕，較佳為使用膠體二氧化石夕，尤佳為使用將石夕酸納作為 起始原料之膠體二氧化石夕。 本發明之研磨劑所含之氧切粒子係以平均粒徑（D5。)達 到20〜150励且〇90/〇丨。達到！ 6〜1〇〇之方式，調整粒徑及 粒度分佈。於氧化石夕粒子之D5〇未達2〇⑽之情形時無法 獲得充分之研磨速度（研磨效率）。χ，若氧化石夕粒子之〜 超過15〇 nm，則分散穩定性變差，難以獲得均勻之研㈣ 聚料。就研磨特性及分散較性之觀點而言，氧化石夕好 之D5❶更佳為30〜120 nm 〇 158824.doc 201213522A SiC substrate (SiC wafer) is produced as follows. That is, the grown SiC single crystal ingot is cut into a wafer shape, and the thickness is adjusted by a grinder, and then the surface is polished (initial polishing) by an abrasive containing diamond abrasive grains to adjust the flatness of the surface, and then The surface is subjected to finish grinding to produce a substrate (wafer) having a high surface flatness. The finish polishing requires removal of the work-affected layer which is generated on the surface of the substrate in the initial polishing by chemical mechanical polishing, and the surface of the substrate is highly flattened and smoothed after the process of the modified layer is removed. In the fine polishing for determining the quality of the siC substrate, cerium oxide microparticles have been used in the past. However, both SiC and GaN have extremely high hardness and high chemical stability. Therefore, it is difficult to ensure flatness and smoothness while polishing at a high polishing efficiency (polishing speed), resulting in the time required for polishing. Extremely long problem. As an abrasive for fine polishing of a sic substrate, for example, an abrasive containing pH 4 to 9 containing colloidal cerium oxide is not disclosed in the patent document, but the width of the particle size distribution is not described, and the abrasive disclosed in the patent document , Due to the low polishing rate of the Sic substrate, there is a problem that the polishing time becomes long. Further, Patent Document 2 discloses an abrasive containing abrasive grains containing chrome oxide and an oxidizing agent. However, the abrasive contains not only chromium oxide having high environmentally harmful properties but also the surface of the SiC substrate after polishing. The problem of environmental pollution is caused by chrome pollution. Further, in Patent Document 3, an abrasive containing colloidal chlorination, a sulphate, and an oxidizing agent is disclosed. However, when the abrasive is used, there is also a problem that the polishing rate of the SiC substrate is insufficient and The specific amount of grinding is obtained to make the time required for grinding longer. CITATION LIST Patent Literature Patent Literature 1: JP-A-2005-117027 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei No. Hei. Problem to be Solved 158824.doc • 4-201213522 The present invention has been made to solve the above problems, and an object thereof is to provide an object to be polished which has a high hardness and a high chemical stability such as a SiC substrate at a higher speed. An abrasive and a polishing method which are polished by a polished surface and which are excellent in surface flatness and smoothness after polishing. Means for Solving the Problems The present invention provides an abrasive comprising the following constitution. Π] - an abrasive used to chemically grind the surface to be polished, and contains an average particle size (D5Q) of 2〇15〇90% particle size (D90) and 10% The ratio of the particle diameter (Dl〇) (D9〇/Di〇) is cerium oxide particles of J 6 〜1〇〇, oxidizing agent and water, and the pH is 8 5 to 12 〇. [2] The abrasive according to [1] above, which further contains an inorganic salt and a lubricant. [3] The polishing 4 according to the above [2], wherein the inorganic salt is at least one selected from the group consisting of ruthenium sulphate, sodium nitrate, sulphur, sodium sulphate, sulphate, and sodium phosphate. [4] The abrasive according to the above [2], wherein the lubricant is at least an amine selected from the group consisting of an alkyl group, an aryl group, and an aryl group-substituted alkyl group having at least a hydrocarbon group having 6 to 2 carbon atoms. 1 species. [5] The abrasive according to the above [4], wherein the lubricant is at least one selected from the group consisting of octylamine, dodecylamine, and polyoxyethylene laurylamine] 6] as described in (1) above [5] The abrasive of the middle item - wherein the oxidizing agent is at least selected from the group consisting of hydrogen peroxide, ammonium persulfate and potassium persulfate! Kind. [7] The agent according to any one of the above (1), wherein the polishing target is an early crystal substrate having a Mohs hardness of 10 or more. [8] The abrasive according to the above [7], wherein the object to be polished is a tantalum carbide single crystal substrate. Further, the present invention provides a polishing method comprising the following constitution. s 158824, doc 201213522 [9] A polishing method for supplying an abrasive according to any one of the above [丨] to [8] to a polishing pad to bring the polished surface of the object to be polished into contact with the polishing pad. Grinding is performed by the relative motion between the two. In the present invention, the "surface to be polished" means a surface on which the object to be polished is polished, for example, a surface. Advantageous Effects of Invention According to the polishing agent of the present invention and the polishing method using the same, it is possible to polish a surface to be polished of a polishing object having a high hardness such as a tantalum carbide (SiC) substrate at a high polishing rate, thereby obtaining flatness and Smooth, scratch-free ground surface. [Embodiment] Hereinafter, embodiments of the present invention will be described. [Abrasion Agent] The abrasive of the present invention is used for polishing a surface to be polished of an object to be polished, and includes an average particle size (D5〇) of 20 to 150 nm and a 90% particle diameter (D9〇) and 10, respectively. The ratio of % particle diameter (D10) (〇9()/1) 10) is cerium oxide particles, oxidizing agent and water of mo o. Further, the pH of the abrasive is in the range of 85 to 12 Å. The abrasive of the present invention has the shape of a slurry. In the present invention, the average particle diameter (D5 〇) is 50 〇 / accumulated on a volume basis. Particle size. The volume-based cumulative 50% particle diameter (D50) is a particle size distribution obtained from a volume basis, and the cumulative value reaches a particle diameter of 5〇% in a cumulative curve in which the total volume is set to 1〇〇〇/0. Further, in the present specification, the average particle diameter (D5〇) may be simply referred to as an average particle diameter or D50. Similarly, 10% particle size (D10) and 90% particle size (D90) are the volume basis accumulation 158824.doc 201213522 10〇/〇 particle size and volume basis cumulative 90% particle size, and the obtained grain distribution distribution The cumulative curve in which the total volume is set to 100% indicates the particle diameter at which the cumulative value reaches 1% and 90%. Therefore, the ratio of 90% of the particle diameter (1) and the particle size of 〇% (DM ratio (D9G/D1G) means an index indicating the width of the particle size distribution. It has a particle size which becomes wider as the value of D9〇/D1G becomes larger. Further, the closer the D^/Di❶ is to 1, the closer it is to the monodisperse particle size distribution. Furthermore, in the present invention, the particle size distribution can be determined by the laser scattering particle size distribution measuring device and the cumulative volume distribution. The measurement of the particle size is carried out by dispersing the cerium oxide particles in an aqueous medium, and measuring the particle size distribution using, for example, Microtrac UPA manufactured by Nikkiso Co., Ltd., in the abrasive of the present invention, respectively. Containing cerium oxide particles having a broad particle size distribution of 仏 为 为 为 〇 〇 〇 〇 且 且 且 且 且 且 为 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 宽 宽 ' ' ' ' ' ' ' ' ' ' ' A polishing object having a high hardness and a high chemical stability such as a tantalum carbide (SiC) substrate can be ground at a higher polishing rate, thereby obtaining a flat, smooth and scratch-free surface after polishing. Oxidized granules as abrasive particles 2D9q/Di() is larger than the abrasive particles which have been used before, and has a wide particle size distribution, so that a relatively high grinding speed can be obtained. That is, particles which are close to D9q/Diq and have a particle size distribution close to monodisperse. In the case of polishing, the polishing stress generated between the object to be polished and the object to be polished is relatively small. On the other hand, particles having a large particle size distribution are caused by particles having a small particle size entering between the particles having a large particle diameter. The polishing stress between the objects to be polished becomes large. Thus, the abrasive of the present invention containing cerium oxide particles having a wide particle size distribution is large in polishing stress during polishing. J58824.doc 201213522 acts on the object to be polished, and therefore, It is effective to grind the above-mentioned hard material or hard-to-grind material. Further, since the abrasive of the present invention has a positive value of 85 to 12 Torr, the oxidizing agent functions effectively, the polishing property is good, and the dispersion of the cerium oxide particles as the abrasive grains is stable. Further, the components and pH of the abrasive of the present invention will be described in detail below. (1) Cerium oxide particles The cerium oxide in the abrasive of the present invention (矽) The particle system functions as an abrasive particle. As the ruthenium, a known method can be used. For example, a colloid obtained by hydrolyzing a decane oxide such as ethyl decanoate or decanoic acid phthalate by a sol-gel method can be used. Dioxo-cutting, in addition, can make the special material to be separated = exchange of colloidal dioxo or four gas cut in the flame of oxygen and hydrogen in the gas phase synthesis of smoked sulfur dioxide eve. (4) In terms of particle size and high purity product, it is preferred to use colloidal silica dioxide, and it is especially preferred to use colloidal silica dioxide which uses sodium alginate as a starting material. The oxygen-containing particles contained 20 to 150 excitations and 〇90/〇丨 with an average particle diameter (D5.). achieve! The particle size and particle size distribution are adjusted in a 6 to 1 way. When the D5 of the oxidized stone particles is less than 2 〇 (10), sufficient polishing speed (grinding efficiency) cannot be obtained. χ If the oxidized stone particles are more than 15 〇 nm, the dispersion stability is deteriorated, and it is difficult to obtain a uniform (four) polymer. From the viewpoint of the polishing property and the dispersion property, the D5 氧化 of the oxidized stone is preferably 30 to 120 nm 〇 158824.doc 201213522
'㈣㈣十之亦可稱為粒度分佈寬度指標之D /D 更佳為1.7〜9.0之範圍，尤# & 90 10 乾固尤佳為1.8〜8·〇之範圍。於 便D50為20〜150 nm ’作ΐ)0Λ/η去、去 1-D9gAD1g未達丨.6之氧化矽粒子之 形時’亦無法獲得較高之研磨速度。χ，亦於氧切粒子 之〜/Dl。超過10.0之情形時’會產生因粒度分佈擴散過大 而導致被研磨面產生劃痕或研磨劑之分散性下降等問題， 從而難以獲得足夠之高研磨速度。 本發明之研磨劑中之氧切粒子之含有比例（濃度）係相 對於研磨劑之總質量為卜㈣量％之範圍，較佳為兼顧研 磨速度、基板面内之研磨速度之均句性、分散穩定性等而 適當設定。更佳為研磨劑總質量之1〇〜3〇質量％之範圍。 若氧化矽粒子之含有比例（濃度）相對於研磨劑總質量未達i 質罝％，則存在無法獲得充分之研磨速度之情形，而若超 過40質量❶/❶，則未能確認到與氧化矽粒子之濃度增加相對 應之研磨速度之提高，又，存在研磨劑之黏性上升或促進 凝膠化之情形。 (2)氧化劑 本發明之研磨劑中之氧化劑係於下述研磨對象物（例如 SiC或GaN等之單晶基板）之被研磨面形成氧化層（皮膜） 者。藉由利用機械力將該氧化層自被研磨面去除，而促進 研磨對象物之研磨。即，SiC或GaN等化合物半導體為非 氧化物且為難研磨材料，但可藉由研磨劑中之氧化劑而於 表面形成氧化層。形成之氧化層係與作為難研磨材料之研 磨對象物相比，硬度低，容易研磨，故可藉由作為研磨粒 3 158824.doc •9· 201213522 之氧化矽粒子而有效去除。其結果，呈現出較高之研磨速 度。 作為氧化劑，較佳為使用選自過氧化氫、碘酸鹽、過碘 酸鹽、次氣酸鹽、㈣酸鹽、過硫酸鹽、過碳酸鹽、過硼 酸鹽及過磷酸鹽中之1種以上。作為碘酸鹽、過碘酸鹽、 氯過氣酸鹽、過硫酸鹽、過碳酸鹽、過棚酸鹽及 過鱗酸鹽，可使用銨鹽或钟鹽等。例如，較佳為過硫酸按 及過硫酸鉀。又，就不含有鹼金屬成分且不產生有害副產 物之方面而言，較佳為過氧化氫。 為獲得研磨速度提高之效果，本發明之研磨劑中之氧化 劑之含有比例（濃度）係相對於研磨劑之總質量為〇1〜2〇質 f/❶之範圍，較佳為兼顧研磨速度等而適當設定。更佳為 研磨劑總質量之〇_5〜15質量％之範圍，尤佳為1〇〜12質量％ 之範圍。 (3) pH值及無機鹽 本發明之研磨劑之pH值係考慮到研磨特性及分散穩定性 之方面而設為8.5〜12.0之範圍。於pH值未達8 5之情形時， 將無法獲得充分之研磨速度。若pH值超過12.0，則作為研 磨粒之氧化發粒子會溶解，而無法獲得充分之研磨速度。 更佳之pH值範圍為9.〇〜u 〇。本發明之研磨劑之pH值係藉 由下述酸及鹼性化合物之添加、調配而調整。 於本發明之研磨劑中，較佳為含有藉由經調配之酸與鹼 性化合物之反應而生成之無機鹽。即，本發明之研磨劑較 佳為不僅含有上述氧化矽粒子及氧化劑，而且含有酸，且 158824.doc 201213522 為將研磨劑之pH值調整為上述特定範圍（8 5〜12〇)，較佳 為添加鹼性化合物。因此，於研磨劑中，含有藉由經調配 之酸與鹼性化合物之反應而生成之無機鹽。再者，於上述 氧化劑亦作為酸發揮功能之情形時，將其視為酸進行處理 而並非氧化劑。 作為酸’較佳為使用選自確酸、硫酸、構酸及鹽酸中之 1種以上之無機酸。較佳為使用硝酸、硫酸及磷酸，其 令’尤佳為使用具有氧化力之含氧酸（oxoacid)且不含有齒 素之硝酸》本發明之研磨劑中之酸之含有比例（濃度）較佳 為相對於研磨劑之總質量為0.01〜5 〇質量％之範圍，更佳 為0.1〜1.0質量％之範圍。可藉由添加酸而進一步提高如 SiC基板之研磨對象物之研磨速度。又，亦可提高研磨劑 之分散穩定性。再者，該酸之濃度係指於藉由與下述鹼性 化合物之反應而成為無機鹽時，假定該鹽分別作為酸及鹼 性化合物而獨立存在時之濃度。 為將本發明之研磨劑調整為上述特定pH值，而與上述酸 併添加驗性化合物。作為驗性化合物’可使用氨氫氧 化鉀、氫氧化鈉、四甲基銨等4級銨，較佳為使用氫氧化 卸、氣氧化鈉。研磨劑中之鹼性化合物之含有比例（濃度） 係設為將研磨劑之PH值調整為特定範圍（pH 8.5〜12.0)之 量。 於本發明之研磨劑中，分別調配上述酸與鹼性化合物之 it形時’藉由酸與驗性化合物之反應而生成之無機鹽將包 含於研磨劑中。作為酸，較佳為使用硝酸、硫酸、磷酸， 158824.doc •11· 201213522 作為驗性化合物，& & λ丄 較佳為使用氫氧化鉀、氫氧化鈉，因 研磨劑中所含之無機鹽較佳為選自蹲酸卸确酸納、 g^酸钟、硫酸熱、鱗酸卸、碟酸納中之1種或2種以上之 ;雔作為本發明之研磨劑中之無機鹽之效果，認為藉由因 又層之壓縮效果而使研磨粒對被研磨物有效接觸，藉此 研磨速度提昇。 酸或驗性化合物亦可於本發明之研磨劑製備之任 、'階段添加°例如’亦於將經酸或驗性化合物處理者用作 研磨劑之成分之情形時，相當於添加上述說明之酸或驗性 化合物。X ’亦可於使所用之酸與鹼性化合物之一部分反 應形成無機鹽之後再進行添加，但就可增加研磨速度之方 面、研磨劑之ΡΗ值易於調節為所期望範圍之方面及操作 面尊而α於本發明中，較佳為分別添加酸與驗性 化合物。 (4)潤滑劑 本發明之研磨劑較佳為含有潤滑劑，可適度調整產生於 與研磨對象物之間之研磨應力，從而進行穩定之研磨。 即’於產生於與研磨對象物之間之研磨應力相對較大之情 形時，存在研磨對象物脫離研磨頭等之保持而自研磨裝置 濺出或研磨對象物中產生劃痕之情形。可藉由使潤滑劑作 用於研磨對象物之被研磨面，而進行穩定且有效之研磨且 不損傷研磨對象物。 作為此種潤滑劑’較佳為使用具有選自碳數6〜2〇之炫 基、碳數6〜20之芳基、院基之Η原子經芳基取代之碳數 158824.doc •12· 201213522 6〜20之經芳基取代之烷基中之烴基之胺。具體而言，例示 辛基胺、十二烷基胺、聚氧乙烯月桂基胺，較佳為使用選 自該等胺中之1種以上。如此之胺不會使研磨劑聚料之分 散性惡化。再者’於本說明書中，胺不僅包含具有1級胺 基之第1胺’亦包含具有2級胺基之第2胺及具有3級胺基之 第3胺。 上述潤滑劑之於研磨劑中之含有比例（濃度）較佳為相對 於研磨劑之總質量為0.001〜5質量％之範圍。更佳為研磨劑 總質里之0.002〜0.5質量％之範圍，尤佳為〇〇〇3〜οι質量％ 之範圍。 (5)水 本發明之研磨劑所含之水係用於使作為研磨粒之氧化矽 粒子穩定地分散，並且將氧化劑及視需要而添加之任意成 分分散、溶解之介質。關於水，並無特別限制，但就對其 他調配成分之影響、雜質之混入、對？11值等之影響而言 較佳為純水或去離子水4於水具有控制研磨劑之流動性 之力月b因此其含畺可結合例如研磨速度之作為目標之 研磨特性而適當設定。例如，水之含有比例較佳為相對於 研磨劑總質量設為40〜90質量％之範圍。若水之含量相對 於研磨劑總質董未達40質量％，則存在研磨劑之黏性變高 而損及流動性之情形’而若超過9()質量％，則存在作為研 磨粒之氧切粒子之漠度變低而無法獲得充分之研磨速度 之情形。 (6)研磨劑之製備及任意成分 158824.doc -13- 201213522 於本發明之研磨劑中，只要不背離本發明之精神，便可 視需要，適當地含有界面活性劑、整合劑、還原劑黏性 賦予劑或黏度調節劑、抗凝聚劑或分散劑、防銹劑等。其 中，於該等添加劑具有氧化劑、潤滑劑酸或鹼性化合物 之功能之情形時，作為氧化劑、满滑劑、酸或驗性化合物 處理。 本發明之研磨劑係以上述特定之含有比例（濃度）含有上 述成刀，且成為氧化矽粒子均勻地分散，除此以外之成分 均勻溶解之混合狀態之方式製備使用。混合時，可採用研 磨劑之製造中通常使用之攪拌混合方法，例如藉由超音波 刀散機均質器等之攪拌混合方法。本發明之研磨劑係無 需預先將構成之研磨材全部混合後供給至研磨現場中。亦 可於供給至研磨現場時，將研磨材料混合，形成研磨劑之 組成。 (7)研磨對象物 作為本發明之研磨劑進行研磨之 限制。具體而言，可列舉··玻璃基板、石夕晶圓 '半導^ 件配線基板、化合物半導體之單晶基板等。於該等之中， 於研磨化合物半導體單晶基板時可獲得更大之效果尤其 可藉由用於修正莫氏硬度為10以上之單晶基板之研磨，而 獲得進一步更高逮研磨之效果。 作為上述修正莫氏硬纟為10以上之I晶基S，具體而 σ可列舉藍寶石（α_Αΐ2〇3)基板(硬度：12)、碳化石夕⑻C) 基板（硬度.13)、氮化鎵（GaN)基板（硬度：13)等。該等之 158824.doc 201213522 中，本發明之研磨劑尤佳用於碳化矽（Sic)基板之研磨。 [研磨方法] 作為使用本發明之研磨劑，對研磨對象物之被研磨面進 行研磨之方法，較佳為如下之研磨方法：一面將研磨劑供 給至研磨墊，一面使研磨對象物之被研磨面與研磨墊接 觸’且藉由兩者間之相對運動而進行研磨。 於上述研磨方法中，作為研磨裝置，可使用先前公知之 研磨裝置。圖1中表示可用於本發明實施形態之研磨裝置 之一例，以下將進行說明，但用於本發明實施形態中之研 磨裝置並不限定於此種構造者。 該研磨裝置10包括：研磨頭2，其保持研磨對象物i ;研 磨板3;研磨墊4,其黏貼於研磨板3之表面；儲罐8,其儲 存研磨劑5 ;及研磨劑供給配管6，其使用研磨劑供給泵7 將研磨劑5自儲罐8供給至研磨墊4。研磨裝置10係構成為 面自研磨劑供給配管6供給研磨劑5，一面使由研磨頭2 保持之研磨對象物1之被研磨面與研磨墊4接觸，使研磨頭 2與研磨板3相對地旋轉運動，從而進行研磨。 可使用此種研磨裝置1〇，對研磨對象物1之被研磨面進 行研磨。此處’圖1所示之研磨裝置1〇係將研磨對象物1之 單面作為被研磨面進行研磨之單面研磨裝置，但例如亦可 使用研磨對象物之上下兩面配置有與圖1之研磨裝置1〇相 同之研磨墊之兩面同時研磨裝置，對研磨對象物之被研磨 面（兩面）同時進行研磨。 研磨頭2不僅可進行旋轉運動，亦可進行直線運動。 158824.doc •15- 201213522 又，研磨板3及研磨墊4可為與研磨對象物1相同程度或其 以下之大小。於該情形時’較佳為，可藉由使研磨頭2與 研磨板3相對地移動而對研磨對象物1之被研磨面之整面進 行研磨。進而，研磨板3及研磨墊4亦可並非進行旋轉運動 者’可為例如利用輸送帶式單向移動者。 如此之研磨裝置10之研磨條件並無特別限制，亦可藉由 對研磨頭2施加負載’按住研磨墊4而進一步提高研磨壓 力’從而提高研磨速度。研磨壓力較佳為1〇〜5〇 kPa& 右，就研磨速度之被研磨面内均勻性、平坦性、防止到痕 等研磨缺陷之觀點而言，更佳為1 〇〜40 kPa左右。研磨板3 及研磨頭2之轉速較佳為50〜500 rpm左右，但並不限定於 此。又’關於研磨劑5之供給量，根據被研磨面之構成材 料或研磨劑之組成、及上述各研磨條件等而適當調整、選 擇。 作為研磨墊4，可使用包含普通之不織布、發泡聚胺基 甲酸酯、多孔質樹脂、非多孔質樹脂等者。又，為促進研 磨劑5對研磨墊4之供給，或於研磨墊4上儲存固定量之研 磨劑5，而可對研磨墊4之表面實施柵格狀、同心圓狀、螺 旋狀等之槽加工。 又，亦可視需要，使研磨塾調節器與研磨塾4之表面接 觸，一面進行研磨墊4表面之調節一面進行研磨。 本發明之研磨劑係供給至研磨墊進行使用。一般而令， 用於研磨之研磨劑係直接廢棄，但亦可循環再利用。即， 亦可將供給至研磨墊用於研磨之研磨劑回收，再次供给至 158824.doc •16- 201213522 研磨塾使用。 使用此種研磨裝置之本發明之研磨方法可較佳地適用於 利用包含金剛石研磨粒之研磨劑進行初研磨之後之SiC基 板等之精研磨。 實施例 以下’藉由實施例及比較例更進一步對本發明進行具體 說明，但本發明並不限定於該等實施例。 (1)研磨劑之製備 (1-1)以如下所示之方式製備實施例卜16之各研磨劑。 首先，將表1所示之酸與潤滑劑添加至水中，攪拌10分 鐘。再者，表1中，潤滑劑F1表示聚氧乙烯月桂基胺，F2 表示十二烷基胺，F3表示辛基胺。繼而，於該溶液中，逐 漸添加使具有表1所示之D1Q ' D5G、D9Q之各粒徑及d9g/Di() 之膠體二氧化矽粒子分散於水中之溶液，進而逐漸添加表 1所示之鹼性化合物即KOH或NaOH，進行PH值調整。其 後，於即將使用前，添加作為氧化劑之過氧化氫水溶液， 攪拌30分鐘，獲得研磨劑。各實施例中使用之各成分之相 對於研磨劑整體之含有比例（濃度、質量％)示於表！中。使 用純水作為水。 (1-2)以如下所示之方式製備比較例之各研磨劑。 於比較例1、比較例4及比較例6中，僅調配使具有表丨所示 之各粒徑（d1q、d5Q、d9Q)及粒度分佈（D9q/Diq)之膠體二氧 化矽粒子分散於水中之溶液，獲得矽粒子之含有比例（濃 度）相對於研磨劑整體為20質量％之研磨劑。於比較例2、 158824.doc •17· 201213522 h 5、7、8中，將具有表丨所示之各粒徑（Di。、^、d9q) 及粒度分佈（D9〇/D1())之作為研磨粒的膠體二氧化發粒子、 作為氧化劑之過氧化氫、酸、鹼性化合物、及潤滑劑以 與實施例1〜16相同之方式添加至水中，進行授拌、混人， 獲得研磨劑。各比較例中使用之各成分之相對於研磨劑整 體之含有比例（濃度；質量％)示於表！中。 再者，實施例1〜16及比較例1〜8中所調配之矽粒子之各 粒控（D丨〇、D50、D90)係藉由Microtrac UPA(日機裝公司製 造）而測定。而且，根據D10與Dm之值求出D9〇/Di〇，作為 粒度分佈之寬度指標。 (2) pH值之測定 使用橫河電機公司製造之PH81-11於25。(：下測定實施例 1〜16及比較例1〜8中所得之研磨劑（漿料）之？11值。測定結 果示於表1中。 (3) 研磨劑之研磨特性之評價 實施例1〜16及比較例1~8中所得之研磨劑係藉由以下方 法進行研磨特性之評價。 (3-1)研磨條件 作為研磨機，使用Nanofactor公司製造之台式研磨裝 置。作為研磨塾’使用 SUBA800-XY-gro〇ve(Nitta Haas公 司製造），研磨前使用MEC100_PH3.5L(三菱综合材料公司 製造）及毛刷進行調節。 將研磨劑之供給速度設為25 cm3/分鐘，將研磨板之轉速 s免為90 rpm ’將基板保持部之轉速設為8〇 rprn，將研磨壓 158824.doc -18 -'(4)(4)10 can also be called D/D of the particle size distribution width index, preferably 1.7~9.0 range, especially # & 90 10 dry solid and especially good range of 1.8~8·〇. Therefore, when the D50 is 20 to 150 nm ΐ0Λ/η, and the 1-D9gAD1g is not as large as the ruthenium oxide particle of 丨6, a higher polishing speed cannot be obtained. χ, also in the oxygen cutting particles ~ / Dl. When it exceeds 10.0, there is a problem that the particle size distribution is excessively spread, causing scratches on the surface to be polished or the dispersibility of the polishing agent to be lowered, so that it is difficult to obtain a sufficiently high polishing rate. The content ratio (concentration) of the oxygen-cut particles in the polishing agent of the present invention is in the range of (four)% by mass based on the total mass of the polishing agent, and is preferably a uniformity of both the polishing rate and the polishing rate in the substrate surface. The dispersion stability and the like are appropriately set. More preferably, it is in the range of 1 〇 to 3 〇 mass% of the total mass of the abrasive. If the content ratio (concentration) of the cerium oxide particles is less than i% by mass based on the total mass of the abrasive, there is a case where a sufficient polishing rate cannot be obtained, and if it exceeds 40 mass ❶/❶, the oxidation and the oxidation are not confirmed. The increase in the concentration of the ruthenium particles corresponds to an increase in the polishing rate, and in the case where the viscosity of the abrasive increases or promotes gelation. (2) Oxidizing agent The oxidizing agent in the polishing agent of the present invention is an oxide layer (film) formed on the surface to be polished of the object to be polished (for example, a single crystal substrate such as SiC or GaN). The etching of the object to be polished is promoted by removing the oxide layer from the surface to be polished by mechanical force. That is, a compound semiconductor such as SiC or GaN is a non-oxide and is a difficult-to-polis material, but an oxide layer can be formed on the surface by an oxidizing agent in the polishing agent. The formed oxide layer is lower in hardness and easier to grind than the object to be polished as a hard-to-grind material, and can be effectively removed by cerium oxide particles as abrasive particles 3 158824.doc •9·201213522. As a result, a higher polishing speed is exhibited. As the oxidizing agent, one selected from the group consisting of hydrogen peroxide, iodate, periodate, hypoxanthate, (tetra) acid salt, persulfate salt, percarbonate salt, perborate salt and perphosphate salt is preferably used. the above. As the iodate, periodate, chloroperoxylate, persulfate, percarbonate, persalt, and persalt, an ammonium salt or a clock salt can be used. For example, persulfuric acid and potassium persulfate are preferred. Further, hydrogen peroxide is preferred in that it does not contain an alkali metal component and does not produce harmful by-products. In order to obtain the effect of improving the polishing rate, the content ratio (concentration) of the oxidizing agent in the abrasive of the present invention is in the range of 〇1 to 2 〇 quality f/❶ with respect to the total mass of the polishing agent, preferably in consideration of the polishing rate, etc. And set it properly. More preferably, it is in the range of 〇5 to 15% by mass based on the total mass of the abrasive, and particularly preferably in the range of from 1 Torr to 12% by mass. (3) pH value and inorganic salt The pH of the polishing agent of the present invention is in the range of 8.5 to 12.0 in view of polishing properties and dispersion stability. When the pH is less than 85, sufficient grinding speed will not be obtained. When the pH exceeds 12.0, the oxidized particles as the abrasive grains are dissolved, and a sufficient polishing rate cannot be obtained. A better pH range is 9. 〇~u 〇. The pH of the abrasive of the present invention is adjusted by the addition and blending of the following acids and basic compounds. In the abrasive of the present invention, it is preferred to contain an inorganic salt formed by a reaction of a formulated acid with a basic compound. That is, the polishing agent of the present invention preferably contains not only the above cerium oxide particles and an oxidizing agent but also an acid, and 158824.doc 201213522 is preferably adjusted to a specific range (85 to 12 Å) of the pH of the polishing agent. To add a basic compound. Therefore, the abrasive contains an inorganic salt formed by the reaction of the formulated acid with a basic compound. Further, when the above oxidizing agent also functions as an acid, it is treated as an acid instead of an oxidizing agent. As the acid, it is preferred to use one or more inorganic acids selected from the group consisting of acid, sulfuric acid, acid and hydrochloric acid. It is preferred to use nitric acid, sulfuric acid, and phosphoric acid, which makes it preferable to use an acid having an oxidizing oxoacid and no dentate, and the ratio (concentration) of the acid in the abrasive of the present invention is higher. It is preferably in the range of 0.01 to 5 % by mass, more preferably in the range of 0.1 to 1.0% by mass, based on the total mass of the abrasive. The polishing rate of the object to be polished such as the SiC substrate can be further increased by adding an acid. Further, the dispersion stability of the polishing agent can be improved. In addition, the concentration of the acid refers to a concentration when the inorganic salt is formed by reaction with the following basic compound, and the salt is assumed to exist as an acid and a basic compound, respectively. In order to adjust the abrasive of the present invention to the above specific pH value, an organic compound is added in combination with the above acid. As the test compound, a grade 4 ammonium such as potassium hydroxide, sodium hydroxide or tetramethylammonium can be used, and it is preferred to use a hydroxide to remove sodium oxide. The content ratio (concentration) of the basic compound in the abrasive is adjusted to adjust the pH of the abrasive to a specific range (pH 8.5 to 12.0). In the abrasive of the present invention, the inorganic salt formed by the reaction of the acid with the test compound when the acid and the basic compound are formed in an iterative form, respectively, is contained in the abrasive. As the acid, it is preferred to use nitric acid, sulfuric acid, phosphoric acid, 158824.doc •11·201213522 as the test compound, and && λ丄 is preferably potassium hydroxide or sodium hydroxide, which is contained in the abrasive. The inorganic salt is preferably one or more selected from the group consisting of sodium phthalate, g-acid clock, sulfuric acid heat, sulphate, and sodium sulphate; and yttrium as an inorganic salt in the abrasive of the present invention. The effect is considered to be that the polishing particles are effectively contacted by the abrasive particles due to the compression effect of the further layer, whereby the polishing speed is improved. The acid or the test compound may also be used in the preparation of the abrasive of the present invention, and the 'stage addition, for example, when the acid or the test compound is used as the component of the abrasive, is equivalent to adding the above description. Acid or test compound. X ' can also be added after the acid used is partially reacted with a basic compound to form an inorganic salt, but the aspect of the polishing speed can be increased, the enthalpy of the abrasive can be easily adjusted to a desired range, and the operation surface can be respected. Wherein α is preferably added to the acid and the test compound, respectively. (4) Lubricant The abrasive of the present invention preferably contains a lubricant, and the grinding stress generated between the object to be polished can be appropriately adjusted to perform stable polishing. In other words, when the polishing stress generated between the object to be polished is relatively large, the object to be polished may be detached from the polishing head or the like, and may be scratched from the polishing device or scratched in the object to be polished. By using the lubricant as the surface to be polished of the object to be polished, stable and effective polishing can be performed without damaging the object to be polished. As such a lubricant, it is preferred to use a carbon number of 158,824.doc •12, which has an aryl group having a carbon number of 6 to 2 fluorene, an aryl group having a carbon number of 6 to 20, and an anthracene group. 201213522 6 to 20 of an amine in the alkyl group substituted by an aryl group. Specifically, octylamine, dodecylamine, and polyoxyethylene laurylamine are preferably used, and one or more selected from the above amines are preferably used. Such an amine does not deteriorate the dispersibility of the abrasive concentrate. Further, in the present specification, the amine includes not only the first amine having a first-order amine group but also a second amine having a second-order amine group and a third amine having a tertiary amino group. The content ratio (concentration) of the lubricant in the abrasive is preferably in the range of 0.001 to 5% by mass based on the total mass of the abrasive. More preferably, it is in the range of 0.002 to 0.5% by mass in the total mass of the abrasive, and particularly preferably in the range of 〇〇〇3 to οι% by mass. (5) Water The water contained in the polishing agent of the present invention is a medium for dispersing and dissolving an oxidizing agent and optionally adding an oxidizing agent as a fine particle of the abrasive particles. There is no particular restriction on water, but the effect of other blending ingredients, the incorporation of impurities, and the right? In the case of the influence of the value of 11 or the like, it is preferred that the pure water or the deionized water 4 has a force month b for controlling the fluidity of the abrasive in water, so that the ruthenium contained therein can be appropriately set in combination with, for example, the polishing property as the target of the polishing rate. For example, the water content ratio is preferably in the range of 40 to 90% by mass based on the total mass of the abrasive. If the content of the water is less than 40% by mass based on the total mass of the abrasive, the viscosity of the abrasive becomes high and the fluidity is impaired. If it exceeds 9 (% by mass), the oxygen-cut particles as abrasive grains are present. The situation where the indifference becomes low and the full grinding speed cannot be obtained. (6) Preparation and optional components of the abrasive 158824.doc -13- 201213522 In the abrasive of the present invention, as long as the spirit of the present invention is not deviated, the surfactant, the integrator and the reducing agent may be appropriately contained as needed. A sex-imparting agent or a viscosity adjusting agent, an anti-agglomerating agent or a dispersing agent, a rust preventive agent, and the like. In the case where the additives have the function of an oxidizing agent, a lubricant acid or a basic compound, they are treated as an oxidizing agent, a slip agent, an acid or an organic compound. The polishing agent of the present invention is prepared by containing the above-mentioned forming ratio in the specific content ratio (concentration) and uniformly dispersing the cerium oxide particles and uniformly dissolving the components. When mixing, a stirring mixing method which is usually used in the manufacture of a grinding agent, for example, a stirring mixing method by an ultrasonic knife homogenizer or the like can be employed. The abrasive of the present invention does not need to previously mix all of the constituent abrasive materials and supply them to the polishing site. It is also possible to mix the abrasive materials to form the composition of the abrasive when supplied to the grinding site. (7) Object to be polished The polishing agent of the present invention is limited in polishing. Specifically, a glass substrate, a Shihwa wafer 'semiconductor wiring board, a single crystal substrate of a compound semiconductor, and the like are mentioned. Among these, a larger effect can be obtained in polishing a compound semiconductor single crystal substrate, and in particular, by grinding for a single crystal substrate having a Mohs hardness of 10 or more, a further higher grinding effect can be obtained. The above-described modified Mohs hard 纟 is an I crystal base S of 10 or more. Specifically, σ includes a sapphire (α_Αΐ2〇3) substrate (hardness: 12), a carbonized stone (8) C) substrate (hardness: 13), and gallium nitride ( GaN) substrate (hardness: 13) or the like. In the above-mentioned 158824.doc 201213522, the abrasive of the present invention is particularly preferably used for the grinding of a tantalum carbide (Sic) substrate. [Polishing method] As a method of polishing the surface to be polished of the object to be polished, the polishing method of the present invention is preferably a polishing method in which the polishing object is polished while being supplied to the polishing pad. The face is in contact with the polishing pad' and is ground by relative motion between the two. In the above polishing method, as the polishing apparatus, a conventionally known polishing apparatus can be used. Fig. 1 shows an example of a polishing apparatus which can be used in the embodiment of the present invention, and will be described below. However, the polishing apparatus used in the embodiment of the present invention is not limited to such a structure. The polishing apparatus 10 includes a polishing head 2 that holds an object to be polished i, a polishing plate 3, a polishing pad 4 that adheres to the surface of the polishing plate 3, a storage tank 8 that stores the abrasive 5, and an abrasive supply pipe 6 The abrasive 5 is supplied from the storage tank 8 to the polishing pad 4 using the abrasive supply pump 7. In the polishing apparatus 10, the polishing material 5 is supplied from the polishing agent supply pipe 6, and the polishing surface of the polishing object 1 held by the polishing head 2 is brought into contact with the polishing pad 4, so that the polishing head 2 and the polishing plate 3 face each other. Rotate motion to grind. The surface to be polished of the object 1 to be polished can be polished by using such a polishing apparatus. Here, the polishing apparatus 1 shown in FIG. 1 is a single-surface polishing apparatus in which one surface of the object 1 to be polished is polished as a surface to be polished. For example, the polishing object may be disposed on the upper and lower surfaces of the object to be polished. The polishing apparatus 1 simultaneously grinds the both surfaces of the same polishing pad, and simultaneously grinds the polished surface (both sides) of the object to be polished. The polishing head 2 can perform not only a rotary motion but also a linear motion. 158824.doc •15-201213522 Further, the polishing plate 3 and the polishing pad 4 may have the same size as or smaller than the object 1 to be polished. In this case, it is preferable that the entire surface of the object to be polished 1 to be polished is polished by moving the polishing head 2 relative to the polishing plate 3. Further, the polishing plate 3 and the polishing pad 4 may not be rotated, and may be, for example, a conveyor-type one-way mover. The polishing conditions of the polishing apparatus 10 are not particularly limited, and the polishing speed can be further increased by applying a load to the polishing head 2 to hold the polishing pad 4 to further increase the polishing pressure. The polishing pressure is preferably from 1 Torr to 5 kPa kPa. The right side is preferably about 1 〇 to 40 kPa from the viewpoint of the polishing surface uniformity, flatness, and prevention of polishing defects such as marks. The rotation speed of the polishing plate 3 and the polishing head 2 is preferably about 50 to 500 rpm, but is not limited thereto. Further, the amount of the polishing agent 5 to be supplied is appropriately adjusted and selected depending on the constituent material of the surface to be polished, the composition of the polishing agent, and the respective polishing conditions described above. As the polishing pad 4, a general non-woven fabric, a foamed polyurethane, a porous resin, a non-porous resin or the like can be used. Further, in order to promote the supply of the polishing material 5 to the polishing pad 4 or to store a fixed amount of the polishing agent 5 on the polishing pad 4, the surface of the polishing pad 4 may be grooved in a grid shape, a concentric shape, or a spiral shape. machining. Further, if necessary, the polishing crucible adjuster is brought into contact with the surface of the polishing crucible 4, and polishing is performed while adjusting the surface of the polishing pad 4. The abrasive of the present invention is supplied to a polishing pad for use. Generally, the abrasive used for polishing is directly discarded, but it can also be recycled. That is, the abrasive supplied to the polishing pad for polishing may be recovered and supplied again to the 158824.doc •16-201213522 polishing crucible. The polishing method of the present invention using such a polishing apparatus can be preferably applied to finish polishing of a SiC substrate or the like after preliminary polishing using an abrasive containing diamond abrasive grains. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples. (1) Preparation of abrasive (1-1) Each of the abrasives of Example 16 was prepared in the following manner. First, the acid and lubricant shown in Table 1 were added to water and stirred for 10 minutes. Further, in Table 1, the lubricant F1 represents polyoxyethylene laurylamine, F2 represents dodecylamine, and F3 represents octylamine. Then, in the solution, a solution obtained by dispersing the colloidal cerium oxide particles having the respective particle diameters of D1Q 'D5G and D9Q shown in Table 1 and d9g/Di() in water was gradually added, and then gradually added as shown in Table 1. The basic compound, KOH or NaOH, is adjusted for pH. Thereafter, an aqueous hydrogen peroxide solution as an oxidizing agent was added just before use, and the mixture was stirred for 30 minutes to obtain an abrasive. The content ratio (concentration, mass %) of each component used in each of the examples with respect to the entire abrasive is shown in the table! in. Use pure water as water. (1-2) Each of the abrasives of the comparative examples was prepared in the following manner. In Comparative Example 1, Comparative Example 4, and Comparative Example 6, only colloidal cerium oxide particles having respective particle diameters (d1q, d5Q, d9Q) and particle size distribution (D9q/Diq) shown in Table 分散 were dispersed in water. In the solution, an abrasive having a ratio (concentration) of the cerium particles of 20% by mass based on the entire abrasive was obtained. In Comparative Example 2, 158824.doc •17·201213522 h 5, 7, and 8, each particle diameter (Di., ^, d9q) and particle size distribution (D9〇/D1()) shown in Table 将 are used. Colloidal oxidized hair particles as abrasive particles, hydrogen peroxide as an oxidizing agent, an acid, a basic compound, and a lubricant are added to water in the same manner as in Examples 1 to 16, and are mixed and mixed to obtain an abrasive. . The content ratio (concentration; mass %) of each component used in each comparative example with respect to the entire abrasive is shown in the table! in. Further, the respective particle sizes (D丨〇, D50, D90) of the ruthenium particles prepared in Examples 1 to 16 and Comparative Examples 1 to 8 were measured by Microtrac UPA (manufactured by Nikkiso Co., Ltd.). Further, D9 〇 / Di 求出 is obtained from the values of D10 and Dm as the width index of the particle size distribution. (2) Measurement of pH value PH81-11 manufactured by Yokogawa Electric Corporation was used at 25. (The values of ?11 of the polishing agents (slurry) obtained in Examples 1 to 16 and Comparative Examples 1 to 8 were measured. The measurement results are shown in Table 1. (3) Evaluation of polishing properties of the abrasive Example 1 In the polishing agent obtained in the above-mentioned method, the polishing agent was evaluated by the following method. (3-1) Polishing conditions As a polishing machine, a table polishing device manufactured by Nanofactor Co., Ltd. was used. As a polishing crucible, SUBA800 was used. -XY-gro〇ve (manufactured by Nitta Haas Co., Ltd.), adjusted by MEC100_PH3.5L (manufactured by Mitsubishi Materials Corporation) and a brush before grinding. The feed rate of the abrasive was set to 25 cm3/min, and the rotation speed of the plate was adjusted. s free for 90 rpm 'set the substrate holding speed to 8 〇rprn, the grinding pressure 158824.doc -18 -
201213522 力設為5 psi(34.5 kPa)，進行60分鐘研磨β (3-2)被研磨物 作為被研磨物’使用2英吋直徑之sic晶圓。傾斜角為8 度，對Si面側進行研磨評價。使用利用金剛石研磨粒進行 初研磨後之厚度為380 μηι之晶圓。 (3-3)研磨速度之評價 研磨速度係藉由每一單位時間内之基板（晶圓）之厚度之 變化量（nm/hr)而評價β具體而言，測定厚度已知的未研磨 基板之質量與經過各時間研磨後之基板質量，並根據其差 求出質量變化。繼而，使用下式算出由該質量變化求出之 基板厚度之每一單位時間的變化。研磨速度之算出結果示 於表1。（研磨速度（V)之計算式）、V=Am/m()x T0x60/t(式中，Διπα)表示研磨前後之質量變化，^(^“表 不未研磨基板之初始質量，mi (g)表示研磨後基板之質 量，V表示研磨速度（nrn/hr)，TO表示未研磨基板之厚度 (nm)，t表示研磨時間（min)。） (3-4)研磨後之表面觀察 目視觀察由實施例1〜16及比較例1〜8之研磨劑研磨後之 基板（SiC晶圓）之表面’分析有無明顯之劃痕’結果未發現 研磨造成之劃痕。又，藉由原子力顯微鏡（AFM，Atomic Foixe Microscope)觀察研磨後之基板（Sic晶圓）表面，並測 定表面粗糙度，藉此評價平滑性。由實施例卜16及比較例 1〜8之研磨劑研磨後之基板表面之表面粗糙度Ra均為〇1 nm ’與研磨前之Ra〇.4 nm相比，平滑性提高。 158824.doc -19- 201213522 (4)研磨劑之分散穩定性 將研磨劑於室溫下保管1個月後，分析作為研磨粒之矽 粒子之分散性，結果實施例1〜16及比較例1〜8之研磨劑之 任一者中均未觀察到凝膠化或沈澱等顯著變化。 15S824.doc 20- 201213522 158824.doc201213522 The force was set to 5 psi (34.5 kPa), and the β (3-2) object to be polished was polished for 60 minutes. As a workpiece, a 2 inch diameter sic wafer was used. The inclination angle was 8 degrees, and the Si side was polished. A wafer having a thickness of 380 μm after initial polishing using diamond abrasive grains was used. (3-3) Evaluation of polishing rate The polishing rate is evaluated by the amount of change (nm/hr) of the thickness of the substrate (wafer) per unit time. Specifically, the unpolished substrate having a known thickness is measured. The mass is the mass of the substrate after being polished at each time, and the quality change is obtained based on the difference. Then, the change in the thickness per unit time of the substrate thickness determined from the change in mass was calculated using the following formula. The calculation results of the polishing rate are shown in Table 1. (calculation formula of polishing rate (V)), V=Am/m()x T0x60/t (where Διπα) indicates the mass change before and after polishing, ^(^" indicates the initial mass of the unpolished substrate, mi ( g) indicates the quality of the substrate after polishing, V indicates the polishing rate (nrn/hr), TO indicates the thickness (nm) of the unpolished substrate, and t indicates the polishing time (min). (3-4) Surface observation after polishing The surface of the substrate (SiC wafer) polished by the polishing agents of Examples 1 to 16 and Comparative Examples 1 to 8 was observed for "obvious scratches", and no scratches due to polishing were observed. Further, by atomic force microscopy (AFM, Atomic Foixe Microscope) The surface of the substrate after the polishing (Sic wafer) was observed, and the surface roughness was measured to evaluate the smoothness. The surface of the substrate after polishing by the abrasives of Example 16 and Comparative Examples 1 to 8 The surface roughness Ra is 〇1 nm', and the smoothness is improved compared with Ra〇.4 nm before grinding. 158824.doc -19- 201213522 (4) Dispersion stability of the abrasive. The abrasive is at room temperature. After storage for 1 month, the dispersibility of the particles as the abrasive grains was analyzed, and as a result, Examples 1 to 16 were obtained. No significant changes such as gelation or precipitation were observed in any of the abrasives of Comparative Examples 1 to 8. 15S824.doc 20-201213522 158824.doc
SiC研磨速 度(nm/h) »η 250 230 260 220 270 200 1 ο 230 S cs 230 230 m ο tN >n 00 § ο § 漿料 pH值 10.5 〇 〇\ 〇 〇\ ο 〇\ ο 〇\ ο 〇\ ο 〇\ ο Os ο 〇\ o O\ 〇 C3S ο σί 10.0 Ο 〇s 10.5 Ο Os ο 〇\ 10.5 p 〇 Os ο 00 ο ON 濃度 (質量％) 1 0,005 0.005 0.005 0.005 1 0.005 0.05 0.05 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 I 0.005 0.005 1 0.005 ι 0.005 0.005 潤滑劑 磲 bu m Ξ： tu ε 碟 Ξ E 难 磲 U4 濃度 (質量％) 1 | pH值調整量| pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量 pH值調整量| | pH值調整量1 1 f pH值調整量1 pH值調整量 1 pH值調整量 I pH值調整量 pH值調整量 鹼性 化合物 难 K0H K0H NaOH ：K0H KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH 璁 KOH KOH KOH KOH KOH 濃度 (質量％) 1 〇 Ο c> ο 卜 ο 〇 tn O «η ο 卜 ο *n o ο ο »ri 1 tn ο o 1 «Ί I Ο Ο I硝酸 硝酸 硝酸 1硫酸 磷酸ι 硝酸 1硝酸1 硝酸1 硝酸 硝酸 硝酸 硝酸 1硝酸1 硝酸 1硝酸1 碟 硝酸 硝酸 碟 硝酸 碟 硝酸 硝酸 濃度 (質量％) 〇 •o CN r-^ ο \r\ Ό I m 1 1 ΙΟ »η 氧化劑 過氧化氫 過氧化氫 1過氧化氫I 過氧化氫 1過氧化氫 過氧化氫 過氧化氫 1過氧化氫I 1過氧化氫1 過氧化氩 1過氧化氫I 過氧化氫 1過氧化氫I 1過氧化氩I 過氧化氫 1過氧化氫I m 過氧化氫 I過氧化氫ι 碟 1過氧化氫I 磲 過氧化氫 I過氧化氫 〇9〇/〇10 tN V) 〇〇 m CN CN <s rn m cn CN »η <s <s m m 对 a\ cs Os w^* w-i «η fS OS VO «η r4 寸· 〇ϊ CN Os ΓΊ Os CN On s ΙΛ m <s 〇\ <s 〇\ <s Ό\ v〇 m S s 00 00 m 00 <S OS iS ο 00 (N Os 〇 Ω 1 ΓΊ VO <Ν Ό - fN v〇 <N νώ s ν〇 ν〇 V£) iS v〇 <s cn 寸 s W-i «η On is v〇 CvJ cs vo 00 卜 ΓΟ 卜 m Γ- ΓΠ ro •η r^t Γ*** CO 卜 m 卜 寸 <N 00 卜 心 On v£> ON 卜 ΠΊ 卜 ΓΟ 卜 卜 m 卜 濃度 (質量％> νο CS so cs v〇 cs 氧化物 粒子 實施例1 |實施例2 I 實施例3 |實施例4 1 1實施例5 1 |實施例6 1 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 1實施例15 1 |實施例16 比較例1 1比較例2 1 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 -21 · s 201213522 由表1可知，於使用含有050為20~15〇11111且〇90/〇10處於 1.6〜10.0之範圍内之矽粒子及氧化劑且pH值處於85〜丨2 〇 之範圍内之實施例1〜16之研磨劑之情形時，與使用比較例 1〜8之研磨劑之情形相比，碳化矽（SiC)基板之研磨逮度變 高，可實現高速研磨。又’研磨對象物之被研磨面上未產 生研磨造成之劃痕’可獲得平坦性及平滑性優異之研磨後 之表面。 與此相對’於使用比較例1〜8之研磨劑之情形時，碳化 矽（SiC)基板之研磨速度均較低，無法獲得充分之研磨速 度。即，比較例1之研磨劑係僅含有作為研磨粒之矽粒子 而不含氧化劑之研磨劑，且為conip〇i8〇(商品名，Fu」.imi Incorporated製造）。比較例丨之研磨劑含有〇9〇/Ε)ι〇未達i 6 且粒度分佈較窄之矽粒子而不含氧化劑，因此無法獲得較 高之研磨速度。 又，比較例2、比較例3及比較例8之研磨劑均含有氡化 劑，且pH值處於特定範圍（pH8 5〜12 〇)内，但含有以❶ 未達1·6且粒度分佈窄之矽粒子，作為研磨粒，因此研磨 速度變低。 比較例4之研磨劑含有1^()/1)1()為1 6以上且粒度分佈寬之 石夕粒子作為研磨粒’且ρΗ值處於85〜12 〇之範圍内，但不 含氧化劑，因此研磨速度變低。 比較例5之研磨劑含有D9q/Dig為16以上且粒度分佈寬之 石夕粒子且含有氧化劑’但PH值為3.0,脫離特定範圍，因 此研磨速度變低。 158824.doc •22- 201213522 比較例6之研磨劑不含氧化劑，因此研磨速度變低。 比較例7之研磨劑含有D9G/Dl()為ι·6以上且粒度分佈寬之 矽粒子作為研磨粒，但pH值處於8.5~12.0之範圍外，因此 研磨速度變低。 已詳細地且參照特定之實施態樣對本發明進行了說明， 但業者應當明白只要不脫離本發明之範圍及精神，則可添 加各種修正或變更。 本申請案係基於2010年9月15曰申請之曰本專利申請案 2010-206500者，其内容以參照之形式併入本文中。 產業上之可利用性 卜 …4 儿丹诙化矽（Sic)基 板、氮化鎵（GaN)基板等硬度高之化合物半導體之單晶美 板之高速研磨，且可獲得無劃痕、平坦性及平滑性優= 研磨後之表面。因此’可有助於提高該等基板 。 【圖式簡單說明】 圖！係表示可用財發明之研磨方法之研磨裝置之 的圖。 【主要元件符號說明】 研磨對象物 研磨頭 研磨板 研磨墊 研磨劑 研磨劑供給配管 158824.doc -23- 201213522 7 研磨劑供給泵 8 儲罐 10 研磨裝置 158824.doc -24-SiC grinding speed (nm/h) »η 250 230 260 220 270 200 1 ο 230 S cs 230 230 m ο tN >n 00 § ο § Slurry pH 10.5 〇〇\ 〇〇\ ο 〇\ ο 〇\ ο 〇 ο 〇 ο ο ο ο ο ο ο ο ο ο ο ο ο 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 I 0.005 0.005 1 0.005 ι 0.005 0.005 Lubricant 磲bu m Ξ: tu ε Ξ E difficult U4 concentration (% by mass) 1 | pH adjustment amount | pH adjustment pH adjustment pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount pH adjustment amount | | pH adjustment Amount 1 1 f pH adjustment amount 1 pH adjustment amount 1 pH adjustment amount I pH adjustment amount pH adjustment amount Basic compound difficulty K0H K0H NaOH : K0H KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH concentration (% by mass) 1 〇Ο c> ο 卜ο 〇tn O «η ο ο *no ο ο »ri 1 tn ο o 1 «Ί I Ο Ο I nitric acid nitric acid nitric acid 1 sulfuric acid phosphoric acid 1 nitric acid 1 nitric acid 1 nitric acid 1 nitric acid nitric acid nitric acid 1 nitric acid 1 nitric acid 1 nitric acid 1 dish nitric acid nitric acid dish nitric acid dish nitric acid nitric acid concentration (% by mass) 〇•o CN r-^ ο \r\ Ό I m 1 1 ΙΟ »η oxidant hydrogen peroxide hydrogen peroxide 1 hydrogen peroxide I hydrogen peroxide 1 hydrogen peroxide hydrogen peroxide hydrogen peroxide 1 Hydrogen peroxide I 1 hydrogen peroxide 1 argon peroxide 1 hydrogen peroxide I hydrogen peroxide 1 hydrogen peroxide I 1 argon peroxide I hydrogen peroxide 1 hydrogen peroxide I m hydrogen peroxide I hydrogen peroxide 1 dish 1 peroxidation Hydrogen I 磲hydrogen peroxide I hydrogen peroxide 〇9〇/〇10 tN V) 〇〇m CN CN <s rn m cn CN »η <s <smm for a\ cs Os w^* wi «η fS OS VO «η r4 inch · 〇ϊ CN Os ΓΊ Os CN On s ΙΛ m <s 〇\ <s 〇\ <s Ό\ v〇m S s 00 00 m 00 <S OS iS ο 00 (N Os 〇Ω 1 ΓΊ VO <Ν Ό - fN v〇<N νώ s ν〇ν〇V£) iS v〇<s cn inch s Wi «η On is v〇CvJ cs vo 00卜m Γ- ΓΠ r o •η r^t Γ*** CO 卜m 卜寸<N 00 卜心On v£> ON ΠΊ ΠΊ ΓΟ 卜 卜 ( ( (% by mass > νο CS so cs v〇cs oxide Particles Example 1 | Example 2 I Example 3 | Example 4 1 1 Example 5 1 | Example 6 1 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 1 14 1 Example 15 1 | Example 16 Comparative Example 1 1 Comparative Example 2 1 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 - 21 · s 201213522 As can be seen from Table 1, the use of 050 In the case of the abrasives of Examples 1 to 16 in the range of from 15 to 15 〇 11111 and 〇 90/〇 10 in the range of from 1.6 to 10.0 and having a pH in the range of 85 to 丨 2 ,, In the case of using the abrasives of Comparative Examples 1 to 8, the polishing of the cerium carbide (SiC) substrate was increased, and high-speed polishing was possible. Further, the scratch on the surface to be polished of the object to be polished is not scratched, and the surface after polishing which is excellent in flatness and smoothness can be obtained. On the other hand, in the case of using the abrasives of Comparative Examples 1 to 8, the polishing rate of the ruthenium carbide (SiC) substrate was low, and a sufficient polishing rate could not be obtained. In other words, the polishing agent of Comparative Example 1 contains only an abrasive which is an antimony particle of the abrasive grains and does not contain an oxidizing agent, and is conip〇i8〇 (trade name, manufactured by Fu. imi Incorporated). The polishing agent of the comparative example contains ruthenium particles having a narrow particle size distribution and not containing an oxidizing agent, and thus a higher polishing rate cannot be obtained. Further, the polishing agents of Comparative Example 2, Comparative Example 3, and Comparative Example 8 all contained a hydrating agent, and the pH was in a specific range (pH 8 5 to 12 Torr), but contained ❶ not up to 1.6 and a narrow particle size distribution. Since the particles are used as the abrasive grains, the polishing rate is lowered. The polishing agent of Comparative Example 4 contains 1^()/1)1() which is 16 or more and has a wide particle size distribution as the abrasive particles and the pH value is in the range of 85 to 12 Torr, but does not contain an oxidizing agent. Therefore, the grinding speed becomes low. The polishing agent of Comparative Example 5 contained the cerium particles having a D9q/Dig of 16 or more and having a large particle size distribution and containing an oxidizing agent. However, the pH was 3.0, which was out of the specific range, and thus the polishing rate was lowered. 158824.doc •22- 201213522 The abrasive of Comparative Example 6 contains no oxidizing agent, so the grinding speed becomes low. The abrasive of Comparative Example 7 contained ruthenium particles having a D9G/Dl() of 1 or more and having a large particle size distribution as the abrasive particles, but the pH was outside the range of 8.5 to 12.0, so that the polishing rate was low. The present invention has been described in detail with reference to the specific embodiments thereof, and it is understood that various modifications and changes may be added without departing from the scope and spirit of the invention. The present application is based on the present patent application No. 2010-206500 filed on Sep. 2010, the content of which is hereby incorporated by reference. Industrial Applicability... 4 High-speed polishing of single crystals of compound semiconductors with high hardness such as Sic substrate and gallium nitride (GaN) substrate, and scratch-free and flatness can be obtained. And smoothness = surface after grinding. Therefore, it can contribute to the improvement of the substrates. [Simple diagram of the diagram] Figure! It is a diagram showing a grinding apparatus which can be used in the grinding method of the invention. [Explanation of main component symbols] Grinding object Grinding head Grinding plate Grinding pad Abrasive agent Abrasive supply pipe 158824.doc -23- 201213522 7 Abrasive supply pump 8 Storage tank 10 Grinding device 158824.doc -24-