201011099 六、發明說明： 【發明所屬之技術領域】 本發明係關於主要使用於硏磨半導體積體電路用之矽 單結晶基板之用途的硏磨用組成物及使用其之硏磨方法。 【先前技術】 對於硏磨係單結晶基板之用途中使用之硏磨組成物， φ 係與其他用途中使用之硏磨用組成物相同，爲了縮短硏磨 作業之時間，因此要求具有高的硏磨速度（去除速度）。 其中，對於硏磨在表面上形成有半導體電路之矽單結晶基 板的背面之用途（所謂的背硏磨）中使用之硏磨用組成物 ，並未要求硏磨後之基板之平坦性高等，而代之要求具有 高的硏磨速度，但其他用途中使用之硏磨用組成物則強烈 要求上述。 硏磨矽單結晶基板之用途中使用之硏磨用組成物，過 • 去已知有專利文獻1、2中所述之硏磨用組成物。專利文 獻1之硏磨用組成物含有水、膠體氧化矽、分子量10萬 以上之聚丙烯醯胺等之水溶性高分子、氯化鉀等水溶性鹽 ' 類、及氨等鹼性化合物。專利文獻2之硏磨用組成物含有 氧化矽粒子、水、氨等鹼性物質，及氯化鉀等無機鹽類。 然而，該等過去之硏磨用組成物對於充分的滿足如上述要 求之關於矽單結晶基板之硏磨速度方面尙不足，而有進一 步改善之餘地。 〔專利文獻1〕特開平04-063428號公報 201011099 〔專利文獻2〕國際公開第2005/90511號說明書 【發明內容】 〔發明欲解決之課題〕 因此，本發明之目的係提供一種可更適用於硏磨矽單 結晶基板之用途之硏磨用組成物，及使用其之硏磨方法。 〔用以解決課題之手段〕 爲達成上述目的，本發明之一樣態係提供含有硏磨粒 、哌啶、強電解質鹽及水之硏磨用組成物。相對於硏磨用 組成物中強電解質鹽之哌啶的莫耳比在0.07〜1.2之範圍。 硏磨用組成物中之哌啶含量爲〇.〇2莫耳/升以上，硏磨用 組成物中之強電解質鹽之含量爲〇.〇3莫耳/升以上。 硏磨用組成物之ζ ( Zeta )電位以相較於由與硏磨用 組成物中之硏磨粒同種同量之硏磨粒以及其餘部份之水所 組成之基準漿料的ζ電位高40mV以上較佳。硏磨用組成 物之pH較好在10.3〜11.3之範圍內。硏磨用組成物較好 進而含有螯合劑。硏磨用組成物中所含螯合劑較好爲有機 磺酸系螯合劑。 本發明之另一樣態係提供一種使用上述硏磨用組成物 硏磨矽單結晶基板之硏磨方法。 〔發明效果〕 依據本發明’提供可適於使用於硏磨矽單結晶基板之 -6- 201011099 用途之硏磨用組成物及使用其之硏磨方法。 【實施方式】 以下說明本發明之一實施型態。 本實施型態之硏磨用組成物係將硏磨粒、哌啶及強電 解質鹽混合於水中調製。據此，硏磨用組成物含有硏磨粒 、哌啶、強電解質鹽及水。本實施型態之硏磨用組成物主 φ 要設定爲硏磨矽單結晶基板之用途，尤其是硏磨表面上形 成有半導體電路之矽單結晶基板之背面之用途中使用者。 上述硏磨粒係調配於硏磨用組成物中用以對硏磨組成 物賦予機械硏磨性能。 硏磨用組成物中所含硏磨粒並不限於特定種類者，例 如，可使用如氧化矽或氧化鋁、氧化鈦、氧化錯、氧化鈽 之金屬氧化物粒子。其中，特別適用於硏磨矽單結晶基板 之用途中使用硏磨用組成物時之較佳者爲二氧化矽，其中 〇 尤其爲膠體氧化矽。使用二氧化矽中之膠體氧化矽作爲硏 磨粒時，藉硏磨用組成物硏磨後之矽單結晶基板之刮痕數 尤其可減低。 ' 自硏磨用組成物中所含硏磨粒之BET比表面積計算出 之平均粒徑（平均一次粒徑）以1 〇nm以上較佳，更好爲 30nm以上，又更好爲40nm以上，最好爲50nm以上。就 使硏磨粒之平均一次粒徑增大，可提升硏磨用組成物之矽 單結晶基板之硏磨速度。就該方面而言，硏磨粒之平均一 次粒徑若在l〇nm以上，較好在30nm以上，更好在40nm 201011099 以上，又更好在50nm以上，則可容易地將硏磨組成物對 矽單結晶基板之硏磨速度提升至實用上特別適用之程度。 又，硏磨用組成物中所含硏磨粒之平均一次粒徑較好 爲200nm以下，更好爲lOOnm以下，又更好爲80nm以下 ，最好爲60nm以下。就使硏磨粒之平均一次粒徑變小， 可提升硏磨用組成物中之硏磨粒之分散安定性。就該方面 而言，若硏磨粒之平均一次粒徑爲 2OOnm以下，較好爲 lOOnm以下，更好爲80nm以下，又更好爲60nm以下， 則可容易地將硏磨用組成物中之硏磨粒之分散安定性提升 至實用上特別適用之程度。 硏磨用組成物中所含硏磨粒以動態光散射法求得之平 均粒徑（平均二次粒徑）較好爲20nm以上，更好爲60nm 以上，又更好爲80nm以上，最好爲90nm以上。就使硏 磨粒之平均二次粒徑變大，可提升硏磨用組成物對矽單結 晶基板之硏磨速度。就該方面而言，若硏磨粒之平均二次 粒徑在20nm以上，較好在60nm以上，更好在80nm以上 ，又更好在90nm以上，則可容易地將硏磨用組成物對矽 單結晶基板之硏磨速度提升至實用上特別適用之程度。 又，硏磨用組成物中所含硏磨粒之平均二次粒徑較好 爲400nm以下，更好爲300nm以下，又更好爲200nm以 下，最好爲150nm以下。就使硏磨粒之平均二次粒徑變小 ，可提升硏磨用組成物中之硏磨粒之分散安定性。就該方 面而言，若硏磨粒之平均二次粒徑在4 0 0nm以下，較好在 300nm以下，更好在200nm以下，又更好在I50nm以下 -8 - 201011099 ，則可容易地將硏磨用組成物中之硏磨粒之分散安定性提 升至實用上特別適用之程度。 硏磨用組成物中之硏磨粒含量較好爲〇.5質量％以上 ，更好爲1.0質量％以上，又更好爲1.5質量％以上，最好 爲2.0質量％以上。就使硏磨粒之含量變多，可提升硏磨 用組成物對矽單結晶.基板之硏磨速度。就該方面而言’硏 磨用組成物中之硏磨粒含量若在〇·5質量％以上’較好在 g 1.0質量％以上，更好在1. 5質量％以上，又更好在2 _ 0質 量％以上，則可容易地將硏磨用組成物對矽單結晶基板之 硏磨速度提升至實用上特別適用之程度。 又，硏磨用組成物中之硏磨粒含量較好爲45質量％以 下，更好爲20質量％以下，又更好爲1 〇質量％以下，最 好爲5質量％以下。就使硏磨粒之含量變少，除可降低硏 磨用組成物之材料成本以外，亦可提升硏磨用組成物中之 硏磨粒之分散安定性。就該方面而言’硏磨用組成物中之 φ 硏磨粒含量若在45質量％以下’較好在20質量％以下’ 更好在1 〇質量％以下，又更好在5質量％以下’則可容易 地將硏磨用組成物之硏磨粒之分散安定性提升至實用上特 別適用之程度。 上述哌啶係爲了促進硏磨用組成物對矽單結晶基板之 硏磨而調配於硏磨用組成物中。 硏磨用組成物中之哌啶含量必須在〇.〇2mol/L以上。 硏磨用組成物中之哌啶含量小於0.02mol/L時’硏磨用組 成物對矽單結晶基板之硏磨速度一般來說於實用上不足。 -9- 201011099 爲了將硏磨用組成物對矽單結晶基板之硏磨速度提升至實 用上特別適用之程度，因此硏磨用組成物中之哌啶含量較 好爲0.03 5mol/L以上。 又，硏磨用組成物中之哌啶含量並未特別限制上限， 但較好爲硏磨用組成物中所溶存之最大量以下，例如 1.7mol/L 以下。 上述強電解質鹽係爲了促進硏磨用組成物對矽單結晶 基板之硏磨而調配於硏磨用組成物中。 硏磨用組成物中所含強電解質鹽並不限於特別種類， 可使用例如氯化鉀（KC1 )或氯化鈉（NaCl )、硫酸鉀（ K2S04)、硫酸鈉（Na2S04)之無機鹼金屬鹽。其中，就 可以低成本取得及易溶於水中而言，最適用者爲氯化鉀。 硏磨用組成物中之強電解質鹽含量必須在0.03moI/L 以上。硏磨用組成物中之強電解質鹽含量小於0.03 mol/L 時，硏磨用組成物對矽單結晶基板之硏磨速度一般來說在 實用上不足。爲了將硏磨用組成物對矽單結晶基板之硏磨 速度提升至實用上特別適用之程度，因此硏磨用組成物中 之強電解質鹽含量較好爲 〇.13mol/L以上，更好爲 0.23mol/L 以上。 又，硏磨用組成物中之強電解質鹽含量並未特別限制 上限，但較好爲硏磨用組成物中所溶存之最大量以下，例 如3.4mol/L以下。 對於硏磨用組成物中所含強電解質鹽之哌啶的莫耳比 必須爲0.07〜1.2。該莫耳比超出該範圍時，硏磨用組成物 -10- 201011099 對矽單結晶基板之硏磨速度一般來說在實用上不足。爲了 將硏磨用組成物對矽單結晶之硏磨速度提升至實用上特別 適用之程度，對於強電解質之哌啶的莫耳比較好爲0.13 以上。又基於相同之理由，對於強電解質之哌啶的莫耳比 較好爲0.6以下，更好爲0.26以下，又更好爲0.18以下 〇 硏磨用組成物之ζ ( Zeta)電位爲藉由硏磨用組成物 φ 中含有強電解質鹽，而顯示相較於由與硏磨用組成物中之 硏磨粒同種同量之硏磨粒以及其餘部份爲水所組成之基準 漿料之ζ電位爲較高之値。相對於基準漿料之ζ電位，硏 磨用組成物之ζ ( Zeta)電位差較好爲+40mV以上，更好 爲+50mV以上。若以使該ζ電位差在+40mV以上，較好在 + 5 OmV以上設定硏磨用組成物中之強電解質鹽之含量，則 可容易地將硏磨用組成物對矽單結晶基板之硏磨速度提升 至實用上特別適用之程度。 φ 硏磨用組成物之pH較好在10.3以上，更好在10.5 以上。就使硏磨用組成物之pH變高，硏磨用組成物對矽 單結晶基板之硏磨速度得以提高。就該方面而言，若硏磨 用組成物之pH在10.3以上，較好在10.5以上，則可容 易地將硏磨用組成物對矽單結晶基板之硏磨速度提升至實 用上特別適用之程度。 又，硏磨用組成物之pH較好爲11.3以下，更好爲 10.8以下。若硏磨用組成物之PH爲1 1.3以下，更好爲 10.8以下，則可防止於強鹼領域中引起之硏磨用組成物中 201011099 之硏磨粒溶解。 依據本實施型態可獲得下列之優點。 本實施型態之硏磨用組成物含有硏磨粒、哌啶及 解質鹽，將硏磨用組成物中之哌啶及強電解質鹽之個 量設定在特定之値以上，同時亦將相對於硏磨用組成 之強電解質鹽之哌啶的莫耳比之値設定在特定之範圍 因此，硏磨用組成物可以高的去除速度硏磨矽單結晶 。據此，本實施型態之硏磨用組成物可在硏磨矽單結 板之用途中被較好地使用。 前述之實施型態亦可如下列般變更。 •上述實施型態之硏磨用組成物亦可進而含有螯 。進而含有螯合劑時，可抑制因硏磨用組成物造成之 單結晶基板之金屬污染。可使用之螯合劑之例舉例爲 胺基羧酸系螯合劑及有機磷酸系螯合劑。胺基羧酸系 劑包含乙二胺四乙酸、乙二胺四乙酸鈉、氮川三乙酸 川三乙酸鈉、氮川三乙酸銨、羥基乙基乙二胺三乙酸 基乙基乙二胺三乙酸鈉、二伸乙三胺五乙酸、二伸乙 胺五乙酸鈉、三伸乙基四胺六乙酸、三伸乙基四胺六 鈉等。有機磷酸系螯合劑包含2-胺基乙基磷酸、1-羥 乙基-1，1-二磷酸、胺基三（亞甲基磷酸）、乙二胺肆 甲基憐酸）、二伸乙基三胺五（亞甲基磷酸）、乙烷 二磷酸、乙烷-1,1,2-三磷酸、乙烷-1-羥基-1,1-二磷 乙院-1-羥基-1,1,2-三磷酸、乙烷-i，2-二羧基-1,2-二 、甲烷羥基磷酸、2-磷醯丁烷- l，2-二羧酸、1-磷醯- 強電 別含 物中 內。 基板 晶基 合劑 對矽 例如 螯合 、氮 、羥 基三 乙酸 基亞 (亞 -1,1- 酸、 磷酸 「烷- 201011099 2,3,4-三羧酸、α-甲基磷醯琥珀酸等。其中，最適用者爲 有機磷系螯合劑，其中以乙二胺肆（亞甲基磷酸）或二伸 乙基三胺五（亞甲基磷酸）較佳，更好爲乙二胺肆（亞甲 基磷酸）。 •上述實施型態之硏磨用組成物亦可依據需要進而含 有水溶性高分子或界面活性劑、pH調整劑、防腐劑、防 黴劑、防銹劑等添加劑。 φ •上述實施型態之硏磨用組成物亦可藉由以水稀釋各 硏磨用組成物之原液而調製。 •上述實施型態之硏磨用組成物可以全部置於一個容 器中儲存並以一劑型供給，亦可以先分開儲存於兩個容器 之二劑型以多劑型供給。爲了長期安定儲存，較好將硏磨 粒與強電解質鹽分開儲存。 接著，列舉實施例及比較例更具體說明本發明。 實施例1〜20係將作爲硏磨粒之膠體氧化矽、哌啶、 Φ 強電解質鹽及螯合劑混合於水中調製硏磨用組成物。比較 例1〜9係使膠體氧化矽與哌啶或取代其之化合物、強電解 質鹽或取代其之化合物、及螯合劑之一種同時與水混合調 ' 製硏磨用組成物。各例之硏磨用組成物中之哌啶或取代其 之化合物、強電解質鹽或取代其之化合物、及螯合劑細節 示於表1。表1顯示測定各例之硏磨用組成物之pH之結 果，求得相對於基準漿料之ζ電位之各硏磨用組成物之ζ 電位之差値之結果。又，實施例1〜20及比較例1〜9之硏 磨用組成物中所含膠體氧化矽其平均一次粒徑均爲52ηιη -13- 201011099 ，平均二次粒徑均爲〗15nm，任一例之硏磨用組成物之情 況下膠體氧化矽含量亦爲2.25質量％。又，實施例1~3、 5~20及比較例2、3、7〜9之硏磨用組成物中之螯合劑之 含量均爲〇.lg/L。 又，表1之“哌啶或取代其之化合物”欄中， · PIP代表哌啶， EDA代表乙二胺， nh3代表氨， _ DAB代表1，4-二胺基丁烷， TMAH代表氫氧化四甲基銨， KOH代表氫氧化鉀。 表1之“強電解質鹽或取代其之化合物”欄中， KC1代表氯化鉀，[Technical Field] The present invention relates to a honing composition mainly used for honing a single crystal substrate for a semiconductor integrated circuit, and a honing method using the same. [Prior Art] The honing composition used in the application of the honing single crystal substrate is the same as the honing composition used in other applications, and is required to have a high enthalpy in order to shorten the honing operation time. Grinding speed (removal speed). Among them, the honing composition used for honing the back surface of the single crystal substrate on which the semiconductor circuit is formed on the surface (so-called back honing) does not require high flatness of the substrate after honing, Instead, it is required to have a high honing speed, but the honing composition used in other applications strongly requires the above. The composition for honing used in the use of the enamel single crystal substrate is known. The honing composition described in Patent Documents 1 and 2 is known. The honing composition of Patent Document 1 contains a water-soluble polymer such as water, colloidal cerium oxide, a polyacrylamide having a molecular weight of 100,000 or more, a water-soluble salt such as potassium chloride, and an alkaline compound such as ammonia. The composition for honing of Patent Document 2 contains an alkaline substance such as cerium oxide particles, water or ammonia, and an inorganic salt such as potassium chloride. However, these past honing compositions are insufficient for sufficiently satisfying the honing speed of the single crystal substrate as described above, and there is room for further improvement. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2005-90511 (Patent Document 2) International Publication No. 2005/90511 [Draft of the Invention] [Problems to be Solved by the Invention] Accordingly, it is an object of the present invention to provide a A honing composition for honing a single crystal substrate, and a honing method using the same. [Means for Solving the Problem] In order to achieve the above object, the present invention provides a honing composition containing honing particles, piperidine, a strong electrolyte salt, and water. The molar ratio of piperidine relative to the strong electrolyte salt in the honing composition is in the range of 0.07 to 1.2. The content of piperidine in the honing composition is 〇.〇2 mol/liter or more, and the content of the strong electrolyte salt in the honing composition is 〇.〇3 mol/liter or more. The zeta potential of the honing composition is higher than the zeta potential of the reference slurry composed of the same amount of honing particles and the rest of the water as the honing particles in the honing composition. More preferably 40mV or more. The pH of the honing composition is preferably in the range of 10.3 to 11.3. The honing composition preferably contains a chelating agent. The chelating agent contained in the honing composition is preferably an organic sulfonic acid-based chelating agent. Another aspect of the present invention provides a honing method for honing a single crystal substrate using the above honing composition. [Effect of the Invention] According to the present invention, a honing composition which can be suitably used for honing a single crystal substrate, -6-201011099, and a honing method using the same are provided. [Embodiment] An embodiment of the present invention will be described below. The composition for honing of this embodiment is prepared by mixing honing particles, piperidine and a strong electrolyte salt in water. Accordingly, the honing composition contains honing particles, piperidine, strong electrolyte salts, and water. The honing composition main φ of the present embodiment is set to be used for honing a single crystal substrate, and particularly for use in the use of a back surface of a single crystal substrate having a semiconductor circuit formed on the honing surface. The above honing granules are formulated in the honing composition to impart mechanical honing properties to the honing composition. The honing particles contained in the honing composition are not limited to a specific one. For example, metal oxide particles such as cerium oxide or aluminum oxide, titanium oxide, oxidized erbium or cerium oxide can be used. Among them, cerium oxide is preferable in the case of using the honing composition particularly in the use of the honing single crystal substrate, and cerium is especially colloidal cerium oxide. When the colloidal cerium oxide in the cerium oxide is used as the cerium granule, the number of scratches of the bismuth single crystal substrate honed by the honing composition is particularly reduced. The average particle diameter (average primary particle diameter) calculated from the BET specific surface area of the honing particles contained in the honing composition is preferably 1 〇 nm or more, more preferably 30 nm or more, and still more preferably 40 nm or more. It is preferably 50 nm or more. By increasing the average primary particle size of the honing particles, the honing speed of the 结晶 single crystal substrate of the honing composition can be improved. In this respect, if the average primary particle diameter of the honing particles is more than 10 nm, preferably 30 nm or more, more preferably 40 nm 201011099 or more, and more preferably 50 nm or more, the honing composition can be easily obtained. The honing speed of the single crystal substrate is increased to a practically suitable level. Further, the average primary particle diameter of the honing particles contained in the honing composition is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 80 nm or less, and most preferably 60 nm or less. By making the average primary particle diameter of the honing particles smaller, the dispersion stability of the honing particles in the honing composition can be improved. In this respect, if the average primary particle diameter of the honing particles is 200 nm or less, preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less, the honing composition can be easily used. The dispersion stability of the honing particles is increased to a practically suitable level. The average particle diameter (average secondary particle diameter) obtained by dynamic light scattering of the honing particles contained in the honing composition is preferably 20 nm or more, more preferably 60 nm or more, and still more preferably 80 nm or more. It is 90 nm or more. By increasing the average secondary particle size of the abrasive grains, the honing speed of the honing composition against the single crystal substrate can be improved. In this respect, if the average secondary particle diameter of the honing particles is 20 nm or more, preferably 60 nm or more, more preferably 80 nm or more, and even more preferably 90 nm or more, the honing composition can be easily used. The honing speed of the 矽 single crystal substrate is increased to a practically suitable level. Further, the average secondary particle diameter of the honing particles contained in the honing composition is preferably 400 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and most preferably 150 nm or less. The average secondary particle diameter of the honing particles is made small, and the dispersion stability of the honing particles in the honing composition can be improved. In this respect, if the average secondary particle diameter of the honing particles is below 400 nm, preferably below 300 nm, more preferably below 200 nm, and even better below I50 nm -8 - 201011099, it can be easily The dispersion stability of the honing particles in the honing composition is increased to a practically suitable level. The content of the honing particles in the honing composition is preferably 5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and most preferably 2.0% by mass or more. By increasing the content of the honing particles, the honing speed of the honing composition against the single crystal substrate can be improved. 5质量质量的更优选在2。 In this aspect, the content of the honing agent in the composition of the honing agent is preferably 5% by mass or more, preferably more than 1.0% by mass, more preferably 1.5% by mass or more, and even more preferably 2 When the amount is _0% by mass or more, the honing speed of the honing composition for the single crystal substrate can be easily increased to a practically suitable level. Further, the content of the honing particles in the honing composition is preferably 45% by mass or less, more preferably 20% by mass or less, still more preferably 1% by mass or less, and most preferably 5% by mass or less. In addition to reducing the material cost of the honing composition, the dispersion stability of the honing particles in the honing composition can be improved. In this respect, the φ honing agent content in the honing composition is preferably 45 mass% or less, preferably 20 mass% or less, more preferably 1 mass% or less, and even more preferably 5 mass% or less. 'The dispersion stability of the honing particles of the honing composition can be easily increased to a practically suitable level. The above piperidine is formulated in the honing composition in order to promote the honing composition to honing the single crystal substrate. The content of piperidine in the honing composition must be 〇.〇2 mol/L or more. When the piperidine content in the honing composition is less than 0.02 mol/L, the honing speed of the honing composition for the 矽 single crystal substrate is generally insufficient in practical use. -9- 201011099 In order to increase the honing speed of the honing composition to the single crystal substrate to a practical extent, the content of piperidine in the honing composition is preferably 0.03 5 mol/L or more. Further, the piperidine content in the honing composition is not particularly limited to the upper limit, but is preferably not more than the maximum amount dissolved in the honing composition, for example, 1.7 mol/L or less. The above-mentioned strong electrolyte salt is formulated in the honing composition in order to promote the honing composition to honing the single crystal substrate. The strong electrolyte salt contained in the honing composition is not limited to a specific type, and an inorganic alkali metal salt such as potassium chloride (KC1) or sodium chloride (NaCl), potassium sulfate (K2S04), or sodium sulfate (Na2S04) can be used. . Among them, it can be obtained at low cost and is easily soluble in water, and the most suitable one is potassium chloride. The strong electrolyte salt content in the honing composition must be above 0.03 mol/L. When the content of the strong electrolyte salt in the honing composition is less than 0.03 mol/L, the honing speed of the honing composition for the single crystal substrate is generally insufficient in practical use. In order to increase the honing speed of the honing composition to the single crystal substrate to a practically suitable extent, the content of the strong electrolyte salt in the honing composition is preferably 〇13 mol/L or more, more preferably 0.23 mol/L or more. Further, the content of the strong electrolyte salt in the honing composition is not particularly limited to the upper limit, but is preferably not more than the maximum amount dissolved in the honing composition, for example, 3.4 mol/L or less. The molar ratio of piperidine which is a strong electrolyte salt contained in the honing composition must be 0.07 to 1.2. When the molar ratio is outside the range, the honing composition -10- 201011099 is generally insufficient in practical use for the honing speed of the single crystal substrate. In order to increase the honing speed of the honing composition to the single crystal, it is particularly suitable for practical use, and the molarity of the piperidine of the strong electrolyte is preferably 0.13 or more. For the same reason, the molarity of the piperidine for the strong electrolyte is preferably 0.6 or less, more preferably 0.26 or less, and even more preferably 0.18 or less. The Zeta potential of the honing composition is honed. The composition φ contains a strong electrolyte salt, and the zeta potential of the reference slurry composed of the same amount of honing particles and the rest of the water as the honing granules in the honing composition is Higher. The zeta potential difference of the composition for honing is preferably +40 mV or more, more preferably +50 mV or more, with respect to the zeta potential of the reference slurry. If the zeta potential difference is +40 mV or more, and it is preferable to set the content of the strong electrolyte salt in the honing composition above +5 OmV, the honing composition can be easily honed on the single crystal substrate. The speed is increased to a practically applicable level. The pH of the φ honing composition is preferably at least 10.3, more preferably at least 10.5. When the pH of the honing composition is made high, the honing composition is improved in the honing speed of the 矽 single crystal substrate. In this respect, when the pH of the honing composition is 10.3 or more, preferably 10.5 or more, the honing speed of the honing composition to the single crystal substrate can be easily raised to practically suitable. degree. Further, the pH of the composition for honing is preferably 11.3 or less, more preferably 10.8 or less. When the pH of the honing composition is 1 1.3 or less, more preferably 10.8 or less, dissolution of the honing particles of 201011099 in the honing composition caused by the strong alkali field can be prevented. According to this embodiment, the following advantages can be obtained. The honing composition of the present embodiment contains honing particles, piperidine and a cleavage salt, and the amount of piperidine and strong electrolyte salt in the honing composition is set to a specific amount or more, and will also be relatively The enthalpy ratio of the piperidine of the strong electrolyte salt of the composition is set to a specific range. Therefore, the honing composition can honing the single crystal at a high removal rate. Accordingly, the honing composition of the present embodiment can be preferably used in the application of honing a single-junction plate. The foregoing embodiment can also be modified as follows. • The honing composition of the above embodiment may further contain a chelating agent. Further, when the chelating agent is contained, metal contamination of the single crystal substrate due to the composition for honing can be suppressed. Examples of the chelating agent which can be used are, for example, an aminocarboxylic acid-based chelating agent and an organic phosphoric acid-based chelating agent. The aminocarboxylic acid-based agent comprises ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, ammonium nitrilotriacetate, hydroxyethylethylenediaminetriacetateethylethylenediamine Sodium acetate, diethylenetriamine pentaacetic acid, sodium diethylammonium pentaacetate, tri-extension ethyltetraamine hexaacetic acid, tris-ethyltetraamine hexasodium, and the like. The organic phosphate chelating agent comprises 2-aminoethylphosphoric acid, 1-hydroxyethyl-1,1-diphosphonic acid, aminotris(methylenephosphoric acid), ethylenediamine oxime methyl pity acid) Triamine penta (methylene phosphate), ethane diphosphate, ethane-1,1,2-triphosphate, ethane-1-hydroxy-1,1-diphosphophenyl-1-hydroxy-1, 1,2-trisphosphate, ethane-i,2-dicarboxy-1,2-di, methane hydroxyphosphoric acid, 2-phosphonium butane-l,2-dicarboxylic acid, 1-phosphonium-strong Inside. The substrate crystal matrix is chelating, for example, chelating, nitrogen, or hydroxytriacetic acid (sub-1,1-acid, phosphoric acid "alkane-201011099 2,3,4-tricarboxylic acid, α-methylphosphonium succinic acid, etc. Among them, the most suitable one is an organophosphorus chelating agent, wherein ethylenediamine oxime (methylenephosphonic acid) or di-ethyltriamine penta (methylene phosphate) is preferred, more preferably ethylenediamine oxime ( Methylene phosphate). The honing composition of the above embodiment may further contain an additive such as a water-soluble polymer or a surfactant, a pH adjuster, a preservative, a mold inhibitor, or a rust preventive agent as needed. • The honing composition of the above embodiment can also be prepared by diluting the stock solution of each honing composition with water. • The honing composition of the above embodiment can be stored in a single container and stored For one-dose supply, it is also possible to separately supply the two dosage forms stored in two containers in multiple dosage forms. For long-term stable storage, it is better to store the honing particles separately from the strong electrolyte salt. Next, the examples and comparative examples are more specifically described. The present invention. Embodiments 1 to 20 will serve as The colloidal cerium oxide, piperidine, Φ strong electrolyte salt and chelating agent are mixed in water to prepare a honing composition. Comparative examples 1 to 9 are colloidal cerium oxide and piperidine or a compound thereof, strong electrolyte salt Or a compound which is substituted for the same, and a chelating agent, which is mixed with water to adjust the composition of the honing agent. The piperidine in the honing composition of each example or a compound substituted therefor, a strong electrolyte salt or a compound substituted therewith The details of the chelating agent and the chelating agent are shown in Table 1. Table 1 shows the results of measuring the pH of the honing composition of each example, and the difference in the ζ potential of each honing composition with respect to the zeta potential of the reference slurry was determined. Further, the colloidal cerium oxide contained in the honing compositions of Examples 1 to 20 and Comparative Examples 1 to 9 had an average primary particle diameter of 52 ηηη -13 - 201011099 and an average secondary particle diameter of 15 nm. In the case of the honing composition of any of the examples, the colloidal cerium oxide content is also 2.25 mass%. Further, in the honing compositions of Examples 1 to 3, 5 to 20, and Comparative Examples 2, 3, and 7 to 9 The content of the chelating agent is 〇.lg / L. Also, the piperidine of Table 1 or replace it In the column of "Compound", PIP stands for piperidine, EDA stands for ethylenediamine, nh3 stands for ammonia, _DAB stands for 1,4-diaminobutane, TMAH stands for tetramethylammonium hydroxide, and KOH stands for potassium hydroxide. In the column of "strong electrolyte salt or compound substituted" in Table 1, KC1 represents potassium chloride,
NaCl代表氫氧化鈉， K2S04代表硫酸鉀， K2C03代表碳酸鉀（弱電解質鹽）。 @ 表1之“螯合劑”欄中， EDTPO代表乙二胺肆（亞甲基磷酸）’ DIPA代表二伸乙基三胺五乙酸， TTHA代表三伸乙基四胺六乙酸。 使用各例之硏磨用組成物，以硏磨前後之基板重量差 爲準求得以表2中所示之條件硏磨矽單結晶基板之表面時 之硏磨速度結果顯示於表1之“硏磨速度”欄中。 以使硏磨用組成物中之銅原子濃度及鎳原子濃度均成 -14- 201011099 爲500ppb之方式將銅及鎳之水溶液添加於各例之硏磨用 組成物中。使用該經金屬污染之各例之硏磨用組成物，以 表2中所示之條件硏磨矽單結晶基板，測定硏磨後之基板 相關之金屬污染度。具體而言，硏磨後之基板經洗淨後， ' 以氣相分解法（VPD )回收基板中之銅原子及鎳原子，且 使用島津製作所股份有限公司製造之電漿發光分析裝置 “ICPS- 1 000IV”定量。基板之每單位面積之銅原子數爲2x Φ l〇1G原子/cm2以下時評價爲〇（良），多於2xl01()原子 /cm2且在5xl013原子/cm2以下時評價爲△(可）、多於5 xlO13原子/cm2時評價爲x (不良），結果列於表丨之“銅 污染”欄中。又，基板之每單位面積之鎳原子數爲3X1 原子/cm2以下時評價爲〇（良），多於3xl01G原子/cm2 且在2xlOM原子/cm2以下時評價爲△(可）、多於2χ1〇ιι 原子/ cm2時評價爲χ(不良），結果列於表1之“鎳污染” 欄中。 -15- 201011099NaCl represents sodium hydroxide, K2S04 represents potassium sulfate, and K2C03 represents potassium carbonate (weak electrolyte salt). @ In the "chelating agent" column of Table 1, EDTPO stands for ethylenediamine oxime (methylene phosphate). 'DIPA stands for di-ethyltriamine pentaacetic acid, and TTHA stands for tri-ethyltetraamine hexaacetic acid. Using the honing composition of each of the examples, the honing speed results obtained by honing the surface of the single crystal substrate under the conditions shown in Table 2, based on the difference in substrate weight before and after honing, are shown in Table 1. Grinding speed" column. An aqueous solution of copper and nickel was added to the honing composition of each example so that the copper atom concentration and the nickel atom concentration in the honing composition were both -14 to 201011099 and 500 ppb. Using the honing composition of each of the metal-contaminated samples, the single crystal substrate was honed under the conditions shown in Table 2, and the degree of metal contamination associated with the substrate after honing was measured. Specifically, after the honed substrate is washed, the copper atom and the nickel atom in the substrate are recovered by a gas phase decomposition method (VPD), and a plasma luminescence analyzer "ICPS- manufactured by Shimadzu Corporation" is used. 1 000 IV" quantification. When the number of copper atoms per unit area of the substrate is 2 x Φ l 〇 1 G atoms/cm 2 or less, it is evaluated as 〇 (good), more than 2 x 10 1 (atoms)/cm 2 , and when it is 5×l 013 atoms/cm 2 or less, it is evaluated as Δ (may), When it is more than 5 xlO13 atoms/cm2, it is evaluated as x (poor), and the results are shown in the "copper contamination" column of the table. Further, when the number of nickel atoms per unit area of the substrate is 3×1 atom/cm 2 or less, it is evaluated as 〇 (good), more than 3×10 1 G atoms/cm 2 , and when it is 2×10 OM atoms/cm 2 or less, it is evaluated as Δ (may), more than 2 χ 1 〇. When ιι atom/cm2 was evaluated as χ (bad), the results are shown in the column "Nickel contamination" in Table 1. -15- 201011099
〔I撇〕[I撇]
鎳污染 〇 〇 〇 X 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < < X 〇 〇 X X X 〇 〇 〇 銅污染 〇 〇 〇 X 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < < X 〇 〇 X X X 〇 〇 〇 硏磨速度 [μπι/min] I 0.60 | [0.62 1 I 0.64 | 1 0.64 1 1 0.66 ] 1 0.66 1 I 0.68 | 1 0.58 1 [0.68 | 1 0.58 | 1 0.61 I 1 0.62 ] I 0.62 | 1 0.64 1 I 0.64 | [0*67 | 0.59 I 0.58 | 1 0,62 | 1 0.62 1 1 0.05 | I 0.50 | [0.52 1 1 0.50 1 10-45 J 1 0.50 1 1 0.56 J ! 0.55 1 0.45 黟細 械1_>会 葙· 靼龚 1_122_I <N + 1_±22_I 1_±72_1 1_________±72___1 1. +72 1 I_±72_I 1_±12_1 1 一 ±22__I | _ +43 」 1+48 I 1 — —+55 1 1_±6〇_1 1 +66_1 i _ m____1 L_— +82______I +73 ί . +74 」 L +72 1 ts O L +72 1 + oo 丨__ +78 」 + 1 .+75_____I +77___1 +68 ffi & I 10.6 | 丨 10.6 1 1 10-7 1 1 10-7 1 1 10.8 1 1 10.8 1 1 10-9 1 1 107 1 1 π_ο 1 | 1—0.7 _| 丨 10.6 1 | 10.6 I 1 10-7 1 1 10.6 1 I 10.7 _l I 10-7 1 1 10.6 1 1 10-7 I 1 10.6 I I 10.6 | V〇 〇\ L 10.5 1 1 10.8 1 1 no 1 OO 丨 10.8 I L』1.5一 1 \UA 1 11.2 1 蝥合劑 I EDPTO | 1 EDPTO 1 I EDPTO | 1 1 EDPTO I 1 EDPTO I I EDPTO | 1 EDPTO | | EDPTO I I EDPTO I I EDPTO I 1 EDPTO I 1 EDPTO | I EDPTO 1 I EDPTO I [EDPTO I 1 EDPTO | 1 EDPTO I I DTPA | I TTHA | 1 1 EDPTO | 1 EDPTO | 1 1 1 1 EDPTO I [EDPTO | 1 EDPTO | •Nt^W 8δ« 要％1啦 1 0.108 J 0.130 I 0.152 J 1 0.152 1 1 0.173 1 1 0.195 I I 0.217 | 1 1.040 J 1 0.260 I I 0.347 I 1 0.260 I 1 0.208 1 I 0.173 | I 0.149 1 I 0.130 I 1 0.087 I 0.102 I 0.076 | 1 0.130 J I 0.130 | 1 I 0.043 | 1 1 3.576 | I 0.041 1 1 1 0.041 I I 0.033 | | 2.333 | & ®4π P s 1 if 4n | 0.268 1 0.268 I 0.268 1 1 0.268 1 I 0.268 I 丨 0.268 1 1 0.268 J I 0.034 1 1 0.268 I I 0.101 1 1 0.134 I I 0.168 I | 0.201 | I 0.235 1 I 0.268 I I 0.403 I 0.342 I 0,460 | I 0.268 J I 0.268 | 1 I 0.268 | 1 1 0.013 | 1 0.360 1 1 I 0.268 | I 0.268 | I 0.015 | 媒 <lwn1 禪 | KC1 1 κα I KC1 I Lkci. J ! kci I 1 KCI I 1 kci i 1 kci I | KCI I 1 KCI I 1 KCI | 1 kci I 1 κα j i KCI 1 1 κα I | KCI 1 I NaCl ] 1 kci j 1 KCI ! 1 L κα l 1 L kci J 1 kci i 1 L ml 1 kci 1 u (1)哌啶或取代其之化 合物 〇 旦 _ 4〇 I 0.029 I 0.035 | 0.041 I 1 0.041 I 1 0.047 I I 0.052 I I 0.058 I 1 0.035 I I 0.070 1 I 0.035 I I 0.035 I 0.035 I 0.035 I [ 0.035 I I 0.035 I I 0.035 I 0.035 1 0.035 1 I 0.035 ] | 0.035 I 1 I 0.012 | 丨 0.035 1 ! 0.048 | I 0.015 | 1 0.035 | 1 0.011 I [ 0.009 | 丨 0.035 | 駿 tint!1 顆 Ph E K 丨 PIP 1 1 PIP 1 1 PIP 1 PIP 丨 PIP 1 1 PIP 1 1 PIP 1 & cu PIP 1 PIP 1 Pl. E 1 PIP 1 Eu Ph E 1 PIP 1 | —PIP— 1 1 Lpip J Ph I EDA | IDAB I LTMAHl [KOH | 1 pip 1 i 辑 UK fS m m 寸 辑 m 辑 Η o 辑 m 卜 辑 00 辑 Id； Os 辑 o m 辑 辑 IK CN i 闺 cn ί 闺 κ 2 i m m 辑 ί 辑 m 卜 i 握 00 ί 辑 Os 辑 i |B^ m 鎰 a (N 翠 寸 IT) m 鎰 o m aj 卜 m 00 m ON 201011099 _〔表 2〕__ 硏磨機：日本ENGIS股份有限公司製“EJ 硏磨墊：NITTA HAAS股份有限公司製之 壓盤旋轉數：60rpm 硏磨墊旋轉數：50rpm 硏磨壓力：285 gf/cm2 (約 28kPa) 硏磨用組成物之供給速度：50mL/分鐘 硏磨時間：15分鐘 如表1中所示，實施例1〜20之硏磨 速度均比比較例1〜9之硏磨用組成物之硏 由表1中所示之結果可了解，藉由添加螯 磨用組成物對基板之金屬污染。 3 8 0 1N，， ‘SUBA800 組成物之硏磨 速度大。且， 劑，可抑制硏 -17-Nickel pollution 〇〇〇〇〇〇〇〇〇〇〇〇〇〇X 〇〇〇〇〇〇〇〇〇〇〇〇〇〇<< X 〇〇XXX 〇〇〇 copper pollution 〇〇〇X 〇〇〇〇〇〇〇〇〇〇〇〇〇 〇<< X 〇〇XXX honing speed [μπι/min] I 0.60 | [0.62 1 I 0.64 | 1 0.64 1 1 0.66 ] 1 0.66 1 I 0.68 | 1 0.58 1 [0.68 | 1 0.58 | 1 0.61 I 1 0.62 ] I 0.62 | 1 0.64 1 I 0.64 | [0*67 | 0.59 I 0.58 | 1 0,62 | 1 0.62 1 1 0.05 | I 0.50 | [0.52 1 1 0.50 1 10-45 J 1 0.50 1 1 0.56 J ! 0.55 1 0.45 黟Mechanical 1_>Meeting 靼·靼龚1_122_I <N + 1_±22_I 1_±72_1 1_________±72___1 1. +72 1 I_±72_I 1_±12_1 1 One ±22__I | _ + 43 ” 1+48 I 1 — —+55 1 1_±6〇_1 1 +66_1 i _ m____1 L_— +82______I +73 ί . +74 ” L +72 1 ts OL +72 1 + oo 丨__ + 78 ” + 1 .+75_____I +77___1 +68 ffi & I 10.6 | 丨10.6 1 1 10-7 1 1 10-7 1 1 10.8 1 1 10.8 1 1 10-9 1 1 107 1 1 π_ο 1 | 1— 0.7 _| 丨10.6 1 | 10.6 I 1 10-7 1 1 10.6 1 I 10.7 _l I 10-7 1 1 10.6 1 1 10-7 I 1 10.6 II 10 .6 | V〇〇\ L 10.5 1 1 10.8 1 1 no 1 OO 丨10.8 IL』1.5一1 \UA 1 11.2 1 蝥 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I EDPTO | | EDPTO II EDPTO II EDPTO I 1 EDPTO I 1 EDPTO | I EDPTO 1 I EDPTO I [EDPTO I 1 EDPTO | 1 EDPTO II DTPA | I TTHA | 1 1 EDPTO | 1 EDPTO | 1 1 1 1 EDPTO I [EDPTO | 1 EDPTO | • Nt^W 8δ« To %1 1 1 0.108 J 0.130 I 0.152 J 1 0.152 1 1 0.173 1 1 0.195 II 0.217 | 1 1.040 J 1 0.260 II 0.347 I 1 0.260 I 1 0.208 1 I 0.173 | 0.149 1 I 0.130 I 1 0.087 I 0.102 I 0.076 | 1 0.130 JI 0.130 | 1 I 0.043 | 1 1 3.576 | I 0.041 1 1 1 0.041 II 0.033 | | 2.333 | & ®4π P s 1 if 4n | 0.268 1 0.268 I 0.268 1 1 0.268 1 I 0.268 I 丨0.268 1 1 0.268 JI 0.034 1 1 0.268 II 0.101 1 1 0.134 II 0.168 I | 0.201 | I 0.235 1 I 0.268 II 0.403 I 0.342 I 0,460 | I 0.268 JI 0.268 | 1 I 0.268 1 1 0.013 | 1 0.360 1 1 I 0.268 | I 0.268 | I 0.015 | Medium <lwn1 Zen | KC1 1 κα I KC1 I Lkci. J ! kci I 1 KCI I 1 kci i 1 kci I | KCI I 1 KCI I 1 KCI | 1 kci I 1 κα ji KCI 1 1 κα I | KCI 1 I NaCl ] 1 kci j 1 KCI ! 1 L κα l 1 L kci J 1 kci i 1 L ml 1 kci 1 u (1) Piperidine or Substituting compounds 〇 4 〇 I 0.029 I 0.035 | 0.041 I 1 0.041 I 1 0.047 II 0.052 II 0.058 I 1 0.035 II 0.070 1 I 0.035 II 0.035 I 0.035 I 0.035 I [ 0.035 II 0.035 II 0.035 I 0.035 1 0.035 1 I 0.035 ] | 0.035 I 1 I 0.012 | 丨0.035 1 ! 0.048 | I 0.015 | 1 0.035 | 1 0.011 I [ 0.009 | 丨0.035 | Juntint!1 Ph EK 丨PIP 1 1 PIP 1 1 PIP 1 PIP 丨PIP 1 1 PIP 1 1 PIP 1 & cu PIP 1 PIP 1 Pl. E 1 PIP 1 Eu Ph E 1 PIP 1 | —PIP— 1 1 Lpip J Ph I EDA | IDAB I LTMAHl [KOH | 1 pip 1 i UK fS mm inch series m series Η o series m 00 series Id; Os series om series IK CN i 闺cn ί 闺κ 2 imm series ί 卜 i grip 00 ί Os series i | B^ m 镒a (N 翠寸 IT) m 镒om aj 卜 m 00 m ON 201011099 _[Table 2]__ Honing machine: EJ honing pad manufactured by NENGTA Co., Ltd., Japan: Number of platen rotations made by NITTA HAAS Co., Ltd. :60rp m honing pad rotation number: 50 rpm honing pressure: 285 gf/cm2 (about 28 kPa) Feeding speed of honing composition: 50 mL/min honing time: 15 minutes As shown in Table 1, Examples 1 to 20 The honing speeds were all higher than those of the honing compositions of Comparative Examples 1 to 9. From the results shown in Table 1, it was understood that the metal of the substrate was contaminated by the addition of the composition for chelating. 3 8 0 1N,, ‘SUBA800 composition has a high speed of honing. And, the agent can inhibit 硏 -17-