TW202140704A

TW202140704A - Grinding composition capable of achieving both excellent stability and a high grinding speed of an object to be grinded

Info

Publication number: TW202140704A
Application number: TW110105331A
Authority: TW
Inventors: 篠田敏男
Original assignee: 日商福吉米股份有限公司
Priority date: 2020-03-23
Filing date: 2021-02-17
Publication date: 2021-11-01
Also published as: JP2021152138A

Abstract

This invention provides a grinding composition capable of achieving both excellent stability and a high grinding speed of an object to be ground. The grinding composition of this invention comprises: an abrasive grain having a positive zeta potential in an aqueous solution having a pH of less than 7 and having a number of silanol groups per unit surface area of 2.5 /nm2 or less; and a copolymer of a monomer represented by the following general formula (1) and vinyl ester having a saponification degree of 95 mol% or more, and having a 1,2-diol structure in a side chain; the pH value of the grinding composition has a pH is less than 7.

Description

研磨用組合物Polishing composition

本發明係關於一種研磨用組合物。The present invention relates to a polishing composition.

近年來，隨著LSI(Large Scale Integration，大型積體電路)製造工藝之微細化所帶來之高積體化，以電腦為代表之電子機器逐步實現小型化、多功能化、高速化等高性能化。於伴隨此種LSI高積體化之新的微細加工技術中，使用化學機械研磨(Chemical Mechanical Polishing；CMP)法。CMP法係於LSI製造步驟、尤其是多層配線形成步驟中之層間絕緣膜之平坦化、金屬插塞形成、嵌入配線(鑲嵌配線)形成中被頻繁利用之技術。In recent years, with the high integration brought about by the miniaturization of LSI (Large Scale Integration, large integrated circuit) manufacturing processes, electronic devices represented by computers have gradually achieved miniaturization, multi-functionality, and high speed. Performance. In the new microfabrication technology accompanying such high integration of LSI, chemical mechanical polishing (CMP) method is used. The CMP method is a technique frequently used in the LSI manufacturing process, especially the planarization of the interlayer insulating film, the formation of metal plugs, and the formation of embedded wiring (damascene wiring) in the step of forming multilayer wiring.

近年來，CMP應用於半導體製造之各步驟，作為其一態樣，例如可例舉將其應用至電晶體製作之閘極形成步驟中。In recent years, CMP has been applied to various steps of semiconductor manufacturing. As one aspect, for example, it can be applied to the gate formation step of transistor manufacturing.

於製作電晶體時，有時會對多晶矽(polysilicon)或氧化矽等含Si材料進行研磨，從而要求減少研磨後之金屬污染。例如，於國際公開第2014/84091號(相當於TW 201425559 A)中，提出有一種可抑制研磨粒之凝集並且減少研磨後之被研磨物表面之污染之研磨用組合物，其包含：乙烯酯系單體與乙烯醇之共聚物、有機酸及研磨粒，上述研磨粒係以於pH值2.0以上之溶液中表面之ζ電位為負且不具有等電點之方式，表面進行化學修飾所得。In the production of transistors, sometimes Si-containing materials such as polysilicon or silicon oxide are polished, which requires the reduction of metal pollution after polishing. For example, in International Publication No. 2014/84091 (equivalent to TW 201425559 A), there is proposed a polishing composition that can inhibit the aggregation of abrasive grains and reduce the contamination of the surface of the polished object after polishing, which contains: vinyl ester It is a copolymer of monomer and vinyl alcohol, organic acid, and abrasive particles. The above-mentioned abrasive particles are obtained by chemical modification of the surface in a solution with a pH value of 2.0 or higher in a way that the zeta potential of the surface is negative and does not have an isoelectric point.

然而，國際公開第2014/84091號(相當於TW 201425559 A)之研磨組合物存在對研磨對象物(尤其是包含氧化矽或多晶矽之研磨對象物)之研磨速度較低之問題。However, the polishing composition of International Publication No. 2014/84091 (equivalent to TW 201425559 A) has a problem that the polishing rate of polishing objects (especially polishing objects containing silicon oxide or polysilicon) is low.

因此，本發明係鑒於上述情況而完成者，其課題在於提供一種可兼顧優異之穩定性及研磨對象物(尤其是包含氧化矽或多晶矽之研磨對象物)之高研磨速度之研磨用組合物。Therefore, the present invention was completed in view of the above circumstances, and its subject is to provide a polishing composition that can achieve both excellent stability and high polishing speed of polishing objects (especially polishing objects containing silicon oxide or polysilicon).

為了解決上述問題，本發明人反覆進行了努力研究。結果發現藉由如下研磨用組合物可解決上述問題，該研磨用組合物含有：研磨粒，其於pH值未達7之水溶液中具有正ζ電位，且每單位表面積之矽烷醇基數為2.5個/nm² 以下；及下述通式(1)所表示之單體與乙烯酯單體之共聚物，其皂化度為95莫耳%以上，且於側鏈具有1,2-二醇結構；且上述研磨用組合物之pH值未達7。In order to solve the above-mentioned problems, the present inventors have made diligent research repeatedly. As a result, it was found that the above-mentioned problems can be solved by the following polishing composition, which contains: abrasive grains, which have a positive zeta potential in an aqueous solution with a pH value of less than 7, and the number of silanol groups per unit surface area is 2.5 /nm ² or less; and a copolymer of the monomer represented by the following general formula (1) and a vinyl ester monomer, with a saponification degree of 95 mol% or more, and having a 1,2-diol structure in the side chain; And the pH value of the above-mentioned polishing composition did not reach 7.

[化1] 通式(1)：

[化1] General formula (1):

上述通式(1)中， R¹ ～R⁶ 分別獨立地為氫原子或有機基， X為單鍵或連結基， R⁷ 及R⁸ 分別獨立地為氫原子或R⁹ -CO-(R⁹ 為烷基)。In the above general formula (1), R ¹ to R ⁶ are each independently a hydrogen atom or an organic group, X is a single bond or a linking group, and R ⁷ and R ⁸ are each independently a hydrogen atom or R ⁹ -CO-(R ⁹ is alkyl).

本發明係一種研磨用組合物，其含有：研磨粒，其於pH值未達7之水溶液中具有正ζ電位，且每單位表面積之矽烷醇基數為2.5個/nm² 以下；及下述通式(1)所表示之單體與乙烯酯單體之共聚物，其皂化度為95莫耳%以上，且於側鏈具有1,2-二醇結構；且上述研磨用組合物之pH值未達7。根據該構成，能夠提供一種新穎之研磨用組合物，其可兼顧優異之穩定性及研磨對象物(尤其是包含氧化矽或多晶矽之研磨對象物)之高研磨速度。The present invention is a polishing composition, which contains: abrasive particles, which have a positive zeta potential in an aqueous solution with a pH value of less than 7, and the number of silanol groups per unit surface area is 2.5 pcs/nm ² or less; and The copolymer of the monomer represented by the formula (1) and the vinyl ester monomer has a saponification degree of 95 mol% or more, and has a 1,2-diol structure in the side chain; and the pH value of the above-mentioned polishing composition Less than 7. According to this structure, it is possible to provide a novel polishing composition which can achieve both excellent stability and high polishing speed of the polishing object (especially the polishing object containing silicon oxide or polysilicon).

[化2] 通式(1)：

[化2] General formula (1):

根據該構成，可於自低溫至高溫之較廣溫度區域(尤其是低溫)內穩定地貯存研磨用組合物而不產生沈澱物(保存穩定性優異)，並且可達成對研磨對象物(尤其是包含氧化矽或多晶矽之研磨對象物)之高研磨速度。此處，藉由本發明之構成發揮上述作用效果之機制推測如下。再者，本發明不限定於下述推測。According to this structure, the polishing composition can be stably stored in a wide temperature range from low temperature to high temperature (especially low temperature) without generating precipitates (excellent storage stability), and the polishing object (especially High polishing speed for polishing objects including silicon oxide or polysilicon. Here, the mechanism for exerting the above-mentioned effects by the structure of the present invention is presumed as follows. In addition, the present invention is not limited to the following guesses.

本發明之研磨用組合物中所含之研磨粒之矽烷醇基數較少(矽烷醇基密度較低)。通常，於研磨粒(例如二氧化矽粒子)表面經由因表面矽烷醇基所產生之氫鍵等形成分散介質分子(例如水分子)之膜。若將矽烷醇基數較少從而被覆研磨粒表面上之分散介質(例如水)較少之研磨粒用於研磨用組合物，則研磨時於研磨粒表面與研磨對象物之間不存在或難以存在分散介質分子膜。因此，對於研磨對象物而言，研磨粒可容易且高效率地(高頻率地)接近研磨對象物，從而可高效率地刮取(研磨)研磨對象物表面。尤其是於包含氧化矽或多晶矽之研磨對象物等包含矽原子之研磨對象物之研磨中，若分散介質分子膜(例如水分子膜)較少，則研磨時研磨粒更容易接近研磨對象物表面。進而，於此種研磨粒與研磨對象物表面之間不僅氫鍵，而且電荷之相互作用亦會起作用。因此，研磨粒表面之矽烷醇基與研磨對象物表面之矽烷醇基更容易牢固地鍵結，可高速且高效率地對研磨對象物表面進行研磨。又，本發明之研磨用組合物中所含之研磨粒於研磨用組合物中具有正(+)ζ電位。由於研磨墊屑一般於酸性條件下ζ電位為正(+)，故而研磨粒彼此之凝集或研磨粒與研磨墊屑之凝集得到抑制，從而更不易形成粗大粒子。因此，可有效地抑制、防止研磨用組合物於保存(貯存)時產生沈澱物(可提昇保存穩定性)。又，亦可有效地減少研磨對象物表面產生刮痕。再者，因陰離子性之矽烷醇基之數量較少，故研磨粒之等電點向較高之側移動。因此，尤其是於強酸性條件(例如pH值＝3以下)下，ζ電位更向正側帶電，藉此可進一步改善研磨粒之分散性(可進一步提昇保存穩定性)。The abrasive particles contained in the polishing composition of the present invention have a small number of silanol groups (the density of silanol groups is lower). Generally, a film of dispersion medium molecules (such as water molecules) is formed on the surface of abrasive particles (such as silicon dioxide particles) through hydrogen bonds generated by surface silanol groups. If abrasive grains with a small number of silanol groups and less dispersion medium (such as water) covering the surface of the abrasive grains are used in the polishing composition, there will be no or hardly presence between the surface of the abrasive grains and the object to be polished during polishing. Dispersion medium molecular film. Therefore, for the polishing object, the abrasive grains can approach the polishing object easily and efficiently (with high frequency), so that the surface of the polishing object can be scraped (polished) efficiently. Especially in the polishing of a polishing object containing silicon atoms, such as a polishing object containing silicon oxide or polycrystalline silicon, if the dispersion medium molecular film (for example, a water molecule film) is small, the abrasive grains are more likely to approach the surface of the polishing object during polishing. . Furthermore, not only the hydrogen bond but also the interaction of the electric charges between the abrasive grains and the surface of the object to be polished work. Therefore, the silanol group on the surface of the abrasive grain and the silanol group on the surface of the object to be polished are more easily bonded firmly, and the surface of the object to be polished can be polished at high speed and with high efficiency. In addition, the abrasive grains contained in the polishing composition of the present invention have a positive (+) zeta potential in the polishing composition. Since polishing pad scraps are generally positive (+) under acidic conditions, the aggregation of abrasive grains or the aggregation of abrasive grains and polishing pad scraps is suppressed, so that it is more difficult to form coarse particles. Therefore, it is possible to effectively suppress and prevent the generation of precipitates during storage (storage) of the polishing composition (storage stability can be improved). In addition, it is also effective to reduce scratches on the surface of the object to be polished. Furthermore, because the number of anionic silanol groups is small, the isoelectric point of the abrasive particles shifts to a higher side. Therefore, especially under strong acid conditions (for example, pH=3 or less), the zeta potential is more positively charged, thereby further improving the dispersibility of the abrasive grains (which can further improve the storage stability).

本發明之研磨用組合物除上述以外，還包含特定結構之共聚物。本發明之共聚物於側鏈具有1,2-二醇結構單元。由於1,2-二醇結構單元為親水性，故而可進一步提昇研磨粒於較廣溫度範圍(尤其是低溫環境)內之分散性，從而抑制研磨粒凝集(更不易形成粗大粒子)。因此，可有效地抑制、防止研磨用組合物於保存(貯存)時產生沈澱物(可提昇保存穩定性、尤其是低溫下之保存穩定性)。又，亦可有效地減少研磨對象物表面產生刮痕。又，共聚物具有源自乙烯酯單體(例如乙烯醇)之結構單元。該結構單元對研磨粒(尤其是膠體二氧化矽)或研磨對象物表面(尤其是包含氧化矽或多晶矽等含矽材料之研磨對象物表面)表現出親和性。因此，藉由添加本發明之共聚物，研磨粒容易與研磨對象物表面接觸，從而作用頻率增加。尤其是，由於側鏈包含1,2-二醇結構單元之共聚物表現出親水性，故而使作為疏水性表面之研磨對象物表面進一步親水化，結果，可提昇研磨速度。In addition to the above, the polishing composition of the present invention also contains a copolymer of a specific structure. The copolymer of the present invention has 1,2-diol structural units in the side chain. Since the 1,2-diol structural unit is hydrophilic, it can further improve the dispersibility of the abrasive grains in a wide temperature range (especially in a low temperature environment), thereby inhibiting the aggregation of the abrasive grains (more difficult to form coarse particles). Therefore, the polishing composition can be effectively suppressed and prevented from generating precipitates during storage (storage) (the storage stability, especially the storage stability at low temperatures can be improved). In addition, it is also effective to reduce scratches on the surface of the object to be polished. In addition, the copolymer has a structural unit derived from a vinyl ester monomer (for example, vinyl alcohol). The structural unit exhibits affinity for abrasive grains (especially colloidal silica) or the surface of the object to be polished (especially the surface of the object to be polished containing silicon-containing materials such as silicon oxide or polysilicon). Therefore, by adding the copolymer of the present invention, the abrasive grains easily come into contact with the surface of the object to be polished, and the frequency of action increases. In particular, since the copolymer containing 1,2-diol structural units in the side chain exhibits hydrophilicity, the surface of the polishing object, which is a hydrophobic surface, is further hydrophilized. As a result, the polishing speed can be increased.

以下，對本發明之實施方式進行說明。再者，本發明並不僅限定於以下實施方式。又，只要無特別說明，則操作及物性等之測定係於室溫(20～25℃)/相對濕度40～50%RH之條件下進行。Hereinafter, embodiments of the present invention will be described. In addition, the present invention is not limited to the following embodiments. In addition, unless otherwise specified, the measurement of operation and physical properties is performed under the conditions of room temperature (20-25°C)/relative humidity 40-50%RH.

[研磨粒] 本發明之研磨用組合物中所含之研磨粒具有對研磨對象物進行機械研磨之作用，使研磨用組合物對研磨對象物之研磨速度提昇。[Abrasive Grain] The abrasive grains contained in the polishing composition of the present invention have the effect of mechanically polishing an object to be polished, so that the polishing rate of the object to be polished by the polishing composition is increased.

本發明之研磨粒於pH值未達7之水溶液中具有正ζ電位，且每單位表面積之矽烷醇基數為2.5個/nm² 以下。此處，「於pH值未達7之水溶液中具有正ζ電位」意指研磨粒於至少包含水之水溶液中具有正ζ電位，其含義與研磨粒於pH值未達7之研磨用組合物中表現出正ζ電位相同。又，其含義與研磨粒之ζ電位為0之等電點處於pH值7以上之範圍內相同。於研磨粒於pH值未達7之水溶液中具有0以下之ζ電位或研磨粒之每單位表面積之矽烷醇基數超過2.5個/nm² 之情形時，較厚之分散介質分子膜於研磨時存在於研磨粒表面與研磨對象物之間，故而研磨粒難以接近研磨對象物，研磨速度會降低(參照下述比較例2、5、6)。pH值未達7之水溶液(研磨用組合物)中之研磨粒之ζ電位較佳為超過5 mV且50 mV以下，更佳為10 mV以上50 mV以下，進而較佳為10 mV以上30 mV以下，進而更佳為13 mV以上20 mV以下，尤佳為13 mV以上且未達20 mV。又，研磨粒之每單位表面積之矽烷醇基數依照2.4個/nm² 以下、未達2.4個/nm² 、2.3個/nm² 以下、2.2個/nm² 以下、2.1個/nm² 以下、2.0個/nm² 以下、1.9個/nm² 以下、1.8個/nm² 以下之順序越來越佳。再者，矽烷醇基數之下限越低則越佳，故而為0個/nm² ，但通常只要為0.2個/nm² 以上即可，較佳為0.4個/nm² 以上，更佳為0.8個nm² 以上。若為具有此種ζ電位及/或矽烷醇基數之研磨粒，則可進一步提昇保存穩定性及研磨速度。再者，於本說明書中，「研磨粒之ζ電位」及「研磨粒之每單位表面積之矽烷醇基數」分別採用藉由下述實施例中之＜ζ電位之測定方法＞及＜矽烷醇基數之算出方法＞中記載之方法所測定之值。The abrasive particles of the present invention have a positive zeta potential in an aqueous solution with a pH value of less than 7, and the number of silanol groups per unit surface area is 2.5 pieces/nm ² or less. Here, "has a positive zeta potential in an aqueous solution with a pH value of less than 7" means that the abrasive grain has a positive zeta potential in an aqueous solution containing at least water, and its meaning is the same as that of the abrasive grain in a polishing composition with a pH value of less than 7 It shows the same positive zeta potential. In addition, its meaning is the same as that the isoelectric point of the abrasive grain with a zeta potential of 0 is in the range of pH 7 or higher. When the abrasive particles have a zeta potential below 0 in an aqueous solution with a pH value of less than 7, or the number of silanol ^{groups per unit surface area of the abrasive particles exceeds 2.5/nm 2} , a thicker dispersion medium molecular film exists during grinding Between the surface of the abrasive grain and the object to be polished, it is difficult for the abrasive grains to approach the object to be polished, and the polishing rate decreases (see Comparative Examples 2, 5, and 6 below). The zeta potential of the abrasive grains in an aqueous solution (polishing composition) with a pH value of less than 7 is preferably more than 5 mV and less than 50 mV, more preferably 10 mV or more and 50 mV or less, and more preferably 10 mV or more and 30 mV Below, more preferably 13 mV or more and 20 mV or less, and particularly preferably 13 mV or more and less than 20 mV. In addition, the number of silanol groups per unit surface area of the abrasive particles is in accordance with 2.4 pieces/nm ² or less, less than 2.4 pieces/nm ² , 2.3 pieces/nm ² or less, 2.2 pieces/nm ² or less, 2.1 pieces/nm ² or less, 2.0 The order of pieces/nm ² or less, 1.9 pieces/nm ² or less, and 1.8 pieces/nm ² or less is getting better. Furthermore, the lower the lower limit of the number of silanol groups, the better, so it is 0/nm ² , but usually it is only 0.2/nm ² or more, preferably 0.4/nm ² or more, more preferably 0.8 nm ² or more. If it is an abrasive grain with such zeta potential and/or silanol group number, storage stability and polishing speed can be further improved. Furthermore, in this specification, "the zeta potential of the abrasive grains" and the "the number of silanol groups per unit surface area of the abrasive grains" are respectively adopted by the following examples of the method of measuring the zeta potential and the number of silanol groups The calculation method> the value measured by the method described in.

本發明之研磨粒之ζ電位可藉由減少研磨粒之矽烷醇基數或對研磨粒之表面進行陽離子修飾來達成。The zeta potential of the abrasive particles of the present invention can be achieved by reducing the number of silanol groups of the abrasive particles or modifying the surface of the abrasive particles with cations.

於本發明之一實施方式中，作為研磨粒之具體例，例如可例舉包含二氧化矽等金屬氧化物之粒子。該研磨粒可單獨使用，或者亦可將2種以上混合使用。又，該研磨粒可使用市售品，亦可使用合成品。該等研磨粒之中，較佳為二氧化矽，更佳為發煙二氧化矽、膠體二氧化矽，尤佳為膠體二氧化矽。作為膠體二氧化矽之製造方法，可例舉矽酸鈉法、溶膠凝膠法，利用任一製造方法製造之膠體二氧化矽均適宜用作本發明之研磨粒。然而，較佳為利用可高純度地進行製造之溶膠凝膠法製造之膠體二氧化矽。In one embodiment of the present invention, as a specific example of the abrasive grains, for example, particles containing metal oxides such as silicon dioxide can be cited. The abrasive grains may be used alone, or two or more types may be mixed and used. In addition, commercially available products can be used for the abrasive grains, or synthetic products can also be used. Among the abrasive grains, silica is preferred, fuming silica and colloidal silica are more preferred, and colloidal silica is particularly preferred. As the manufacturing method of colloidal silica, sodium silicate method and sol-gel method can be exemplified. Colloidal silica manufactured by any of the manufacturing methods can be suitably used as the abrasive grains of the present invention. However, it is preferable to use colloidal silica produced by a sol-gel method that can be produced with high purity.

於本發明之一實施方式中，要想使上述研磨粒之每單位表面積之矽烷醇基數為2.5個/nm² 以下，可藉由研磨粒之製造方法之選擇等來進行控制，例如進行焙燒等熱處理較為適宜。於本發明之一實施方式中，焙燒處理例如係將研磨粒(例如二氧化矽)於120～200℃之環境下保持30分鐘以上。藉由此種熱處理之實施，可使研磨粒表面之矽烷醇基數成為2.5個/nm² 以下等所需數值。除非實施此種特殊之處理，否則研磨粒表面之矽烷醇基數不會成為2.5個/nm² 以下。In one embodiment of the present invention, in order to make the number of silanol groups per unit surface area of the abrasive grains be 2.5/nm ² or less, it can be controlled by the selection of the manufacturing method of the abrasive grains, for example, calcination, etc. Heat treatment is more suitable. In one embodiment of the present invention, the firing treatment is, for example, keeping abrasive grains (for example, silicon dioxide) in an environment of 120 to 200° C. for more than 30 minutes. Through the implementation of this heat treatment, the number of silanol groups on the surface of the abrasive grains can be reduced to a desired value such ^{as 2.5/nm 2 or less.} Unless such a special treatment is implemented, the number of silanol groups on the surface of the abrasive grains will not become 2.5/nm ² or less.

於本發明之一實施方式中，可使用表面經陽離子修飾之研磨粒。此處，作為表面經陽離子修飾之膠體二氧化矽，可較佳地例舉於表面固定化有胺基或四級銨基之膠體二氧化矽。作為此種具有陽離子性基之膠體二氧化矽之製造方法，可例舉如日本專利特開2005-162533號公報中所記載之方法，即，將胺基乙基三甲氧基矽烷、胺基丙基三甲氧基矽烷、胺基乙基三乙氧基矽烷、胺基丙基三乙氧基矽烷、胺基丙基二甲基乙氧基矽烷、胺基丙基甲基二乙氧基矽烷、胺基丁基三乙氧基矽烷等具有胺基之矽烷偶合劑或N-三甲氧基矽烷基丙基-N,N,N-三甲基銨等具有四級銨基之矽烷偶合劑固定化於研磨粒之表面。藉此，可獲得於表面固定化有胺基或四級銨基之膠體二氧化矽。於本發明之一實施方式中，上述研磨粒係使具有胺基之矽烷偶合劑或具有四級銨基之矽烷偶合劑固定化於研磨粒之表面而成。In one embodiment of the present invention, abrasive grains whose surface is modified by cations can be used. Here, as the colloidal silica whose surface is modified by cations, colloidal silica with an amine group or a quaternary ammonium group immobilized on the surface can be preferably exemplified. As a method of producing such a colloidal silica having a cationic group, a method described in Japanese Patent Laid-Open No. 2005-162533 can be exemplified. Trimethoxysilane, aminoethyltriethoxysilane, aminopropyltriethoxysilane, aminopropyldimethylethoxysilane, aminopropylmethyldiethoxysilane, Immobilization of silane coupling agents with amine groups such as aminobutyltriethoxysilane or silane coupling agents with quaternary ammonium groups such as N-trimethoxysilylpropyl-N,N,N-trimethylammonium On the surface of abrasive grains. Thereby, colloidal silica with amine groups or quaternary ammonium groups immobilized on the surface can be obtained. In one embodiment of the present invention, the abrasive particles are formed by immobilizing a silane coupling agent having an amino group or a silane coupling agent having a quaternary ammonium group on the surface of the abrasive particles.

於本發明之一實施方式中，上述研磨粒之平均一次粒徑較佳為10 nm以上，進而較佳為20 nm以上，進而更佳為25 nm以上，尤佳為30 nm以上。於本發明之一實施方式之研磨用組合物中，上述研磨粒之平均一次粒徑較佳為60 nm以下，更佳為55 nm以下，進而較佳為50 nm以下，尤佳為40 nm以下。藉由將上述研磨粒之平均一次粒徑調整為上述範圍，可進一步提昇研磨對象物之研磨速度。再者，於本說明書中，平均一次粒徑採用藉由實施例中記載之方法所測定之值。In one embodiment of the present invention, the average primary particle size of the abrasive grains is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 25 nm or more, and particularly preferably 30 nm or more. In the polishing composition of one embodiment of the present invention, the average primary particle size of the abrasive grains is preferably 60 nm or less, more preferably 55 nm or less, still more preferably 50 nm or less, and particularly preferably 40 nm or less . By adjusting the average primary particle size of the abrasive grains to the above range, the polishing rate of the object to be polished can be further increased. In addition, in this specification, the average primary particle diameter adopts the value measured by the method described in the examples.

上述研磨粒之平均二次粒徑較佳為40 nm以上，更佳為45 nm以上，進而較佳為50 nm以上，進而更佳為55 nm以上，尤佳為60 nm以上。於本發明之一實施方式中，上述研磨粒之平均二次粒徑較佳為110 nm以下，更佳為100 nm以下，進而較佳為90 nm以下，進而更佳為80 nm以下，尤佳為75 nm以下。藉由將上述研磨粒之平均二次粒徑調整為上述範圍，可進一步提昇研磨對象物之研磨速度。再者，於本說明書中，平均二次粒徑採用藉由實施例中記載之方法所測定之值。The average secondary particle size of the abrasive grains is preferably 40 nm or more, more preferably 45 nm or more, still more preferably 50 nm or more, still more preferably 55 nm or more, and particularly preferably 60 nm or more. In one embodiment of the present invention, the average secondary particle size of the abrasive grains is preferably 110 nm or less, more preferably 100 nm or less, still more preferably 90 nm or less, and even more preferably 80 nm or less, especially Below 75 nm. By adjusting the average secondary particle size of the abrasive grains to the above range, the polishing rate of the object to be polished can be further increased. In addition, in this specification, the average secondary particle size adopts the value measured by the method described in the examples.

於本發明之一實施方式中，研磨用組合物中之研磨粒之平均締合度(平均二次粒徑/平均一次粒徑)之下限較佳為1.5以上，更佳為1.8以上，尤佳為2.0以上。於本發明之一實施方式中，研磨用組合物中之研磨粒之平均締合度之上限較佳為3.5以下，更佳為3.0以下，尤佳為未達2.5。藉由將上述研磨粒之平均締合度調整為上述範圍，可更高速地對研磨對象物進行研磨。In one embodiment of the present invention, the lower limit of the average degree of association (average secondary particle size/average primary particle size) of the abrasive grains in the polishing composition is preferably 1.5 or more, more preferably 1.8 or more, and more preferably 2.0 or more. In one embodiment of the present invention, the upper limit of the average degree of association of the abrasive grains in the polishing composition is preferably 3.5 or less, more preferably 3.0 or less, and particularly preferably less than 2.5. By adjusting the average degree of association of the abrasive grains to the above range, the object to be polished can be polished at a higher speed.

於本發明之一實施方式中，上述研磨用組合物中之上述研磨粒之含量較佳為0.03質量%以上，更佳為0.1質量%以上，進而較佳為0.2質量%以上，進而更佳為0.3質量%以上，進一步更佳為0.9質量%以上，尤佳為2質量%以上。於本發明之一實施方式中，上述研磨用組合物中之上述研磨粒之含量較佳為10質量%以下，更佳為8質量%以下，進而較佳為6質量%以下，進而更佳為5質量%以下，進一步更佳為3質量%以下，尤佳為1質量%以下。若為此種含量，則可更高速地對研磨對象物進行研磨。In one embodiment of the present invention, the content of the abrasive grains in the polishing composition is preferably 0.03% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more, more preferably 0.9% by mass or more, and particularly preferably 2% by mass or more. In one embodiment of the present invention, the content of the abrasive grains in the polishing composition is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, and still more preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. If it is such a content, the object to be polished can be polished at a higher speed.

尤其於對包含氧化矽或多晶矽之研磨對象物等包含矽原子之研磨對象物進行研磨之情形時，將上述研磨用組合物中之上述研磨粒之含量較佳為調整為0.1～10質量%，更佳為調整為1～8質量%，尤佳為調整為2～7質量%。或者，尤其於對包含氧化矽或多晶矽之研磨對象物等包含矽原子之研磨對象物進行研磨之情形時，將上述研磨用組合物中之上述研磨粒之含量較佳為調整為0.1～5質量%，更佳為調整為0.2～3質量%，尤佳為調整為0.3～1質量%。藉由預先調整為此種範圍，可更高速地對研磨對象物進行研磨。再者，本說明書中所揭示之所有下限值上限值之值揭示了所有組合。In particular, when polishing a polishing object containing silicon atoms, such as a polishing object containing silicon oxide or polycrystalline silicon, the content of the abrasive grains in the polishing composition is preferably adjusted to 0.1-10% by mass. It is more preferably adjusted to 1 to 8% by mass, and particularly preferably adjusted to 2 to 7% by mass. Or, especially when polishing a polishing object containing silicon atoms, such as a polishing object containing silicon oxide or polycrystalline silicon, the content of the abrasive grains in the polishing composition is preferably adjusted to 0.1-5 mass %, more preferably adjusted to 0.2 to 3% by mass, particularly preferably adjusted to 0.3 to 1% by mass. By adjusting to such a range in advance, the object to be polished can be polished at a higher speed. Furthermore, all the lower limit and upper limit values disclosed in this specification reveal all combinations.

[共聚物] 於本發明之一實施方式中，研磨用組合物包含下述通式(1)所表示之單體與乙烯酯單體之共聚物，該共聚物之皂化度為95莫耳%以上，且於側鏈具有1,2-二醇結構。再者，於本說明書中，「於側鏈具有1,2-二醇結構」意指共聚物具有下述通式(1)中R⁷ 及R⁸ 兩者均為氫原子之結構單元。[Copolymer] In one embodiment of the present invention, the polishing composition includes a copolymer of a monomer represented by the following general formula (1) and a vinyl ester monomer, and the degree of saponification of the copolymer is 95 mol% Above, it has a 1,2-diol structure in the side chain. Furthermore, in this specification, "having a 1,2-diol structure in the side chain" means that the copolymer has a structural unit in which both ^{R 7} and R ^{8 in the following general formula (1) are hydrogen atoms.}

[化3] 通式(1)：

[化3] General formula (1):

於本發明之一實施方式中，作為構成該共聚物之乙烯酯單體，例如可例舉：甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯酯、特十碳酸乙烯酯等。該等乙烯酯單體可單獨使用，或者亦可將2種以上組合使用。於後者之情形時，各結構單元之配置並無特別限制，可為嵌段狀(嵌段共聚物)，亦可為無規狀(無規共聚物)，還可為交替狀(交替共聚物)。其中，就獲取容易性、與研磨對象物之親和性等觀點而言，較佳為乙酸乙烯酯。上述乙烯酯單體可單獨使用，或者亦可將2種以上組合使用。於後者之情形時，各結構單元之配置並無特別限制，可為嵌段狀(嵌段共聚物)，亦可為無規狀(無規共聚物)，還可為交替狀(交替共聚物)。In one embodiment of the present invention, as the vinyl ester monomer constituting the copolymer, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, isobutyl Vinyl acid, vinyl trimethyl acetate, vinyl decanoate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl decanoate, etc. These vinyl ester monomers may be used alone or in combination of two or more kinds. In the latter case, the configuration of each structural unit is not particularly limited. It can be block (block copolymer), random (random copolymer), or alternating (alternating copolymer). ). Among them, vinyl acetate is preferred from the viewpoints of ease of availability and affinity with the object to be polished. The above-mentioned vinyl ester monomers may be used alone or in combination of two or more kinds. In the latter case, the configuration of each structural unit is not particularly limited. It can be block (block copolymer), random (random copolymer), or alternating (alternating copolymer). ).

於本發明之一實施方式中，與該乙烯酯單體構成共聚物之單體由上述通式(1)所表示。此處，通式(1)之單體可單獨使用，或者亦可將2種以上組合使用。於後者之情形時，各結構單元之配置並無特別限制，可為嵌段狀(嵌段共聚物)，亦可為無規狀(無規共聚物)，還可為交替狀(交替共聚物)。In one embodiment of the present invention, the monomer constituting the copolymer with the vinyl ester monomer is represented by the above-mentioned general formula (1). Here, the monomer of the general formula (1) may be used alone or in combination of two or more kinds. In the latter case, the configuration of each structural unit is not particularly limited. It can be block (block copolymer), random (random copolymer), or alternating (alternating copolymer). ).

於上述通式(1)中，R¹ ～R⁶ 為氫原子或有機基。此時，R¹ ～R⁶ 可彼此相同，或者亦可互不相同。又，作為R¹ ～R⁶ 為有機基之情形時之有機基，可例舉碳數1以上8以下之直鏈或分支之烷基等。作為碳數1以上8以下之烷基，例如可例舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第三戊基、新戊基、1,2-二甲基丙基、正己基、異己基、1,3-二甲基丁基、1-異丙基丙基、1,2-二甲基丁基、正庚基、1,4-二甲基戊基、3-乙基戊基、2-甲基-1-異丙基丙基、1-乙基-3-甲基丁基、正辛基、2-乙基己基、3-甲基-1-異丙基丁基、2-甲基-1-異丙基、1-第三丁基-2-甲基丙基等。In the above general formula (1), R ¹ to R ⁶ are hydrogen atoms or organic groups. At this time, R ¹ to R ⁶ may be the same as each other, or may be different from each other. Moreover, as the ^{organic group in the case where R 1} to R ⁶ are an organic group, a linear or branched alkyl group having a carbon number of 1 or more and 8 or less can be exemplified. Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, and n-pentyl. Base, isopentyl, tertiary pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1 ,2-Dimethylbutyl, n-heptyl, 1,4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3- Methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropylbutyl, 2-methyl-1-isopropyl, 1-tert-butyl-2-methyl Propyl and so on.

再者，上述有機基之至少1個氫原子可被取代基取代。此處，作為取代基，可例舉：鹵素原子(氟原子、氯原子、溴原子、碘原子)、羥烷基、烷氧基烷基、烷氧基、環烷氧基、胺基、烷氧羰基、芳氧羰基、羥基(-OH)、羧基(-COOH)、硫醇基(-SH)、氰基(-CN)、磺酸基等。Furthermore, at least one hydrogen atom of the above-mentioned organic group may be substituted by a substituent. Here, as the substituent, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a cycloalkoxy group, an amino group, an alkane Oxycarbonyl, aryloxycarbonyl, hydroxy (-OH), carboxy (-COOH), thiol (-SH), cyano (-CN), sulfonic acid, etc.

其中，R¹ ～R⁶ 較佳為氫原子或碳數1以上4以下之直鏈或分支之烷基，更佳為氫原子或碳數1以上3以下之直鏈之烷基，尤佳為R¹ ～R⁶ 均為氫原子。Among them, R ¹ to R ^{6 are} preferably a hydrogen atom or a linear or branched alkyl group with a carbon number of 1 to 4, more preferably a hydrogen atom or a linear alkyl group with a carbon number of 1 to 3, and particularly preferably R ¹ to R ⁶ are all hydrogen atoms.

於上述通式(1)中，X為單鍵或連結基。此處，作為連結基，可例舉：伸烷基(例如亞甲基、伸乙基、三亞甲基、伸丙基)、伸烯基(例如伸乙烯基、1-伸丙烯基、伸烯丙基)、伸苯基、伸萘基、氧原子(-O-)、氧伸烷基[-(CH₂ O)_m -；m＝1～3]、-(OCH₂ )_m -(m＝1～3)、-(CH₂ O)_m CH₂ -(m＝1～3)、-CO-、-COCO-、-CO(CH₂ )_m CO-(m＝1～3)、-CO(C₆ H₄ )CO-、-S-、-CS-、-SO-、-SO₂ -、-NR-、-CONR-、-NRCO-、-CSNR-、-NRCS-、-NRNR-、-HPO₄ -、-Si(OR)₂ -、-OSi(OR)₂ -、-OSi(OR)₂ O-、-Ti(OR)₂ -、-OTi(OR)₂ -、-OTi(OR)₂ O-、-Al(OR)-、-OAl(OR)-、-OAl(OR)O-(R分別獨立地為任意取代基(較佳為氫原子或烷基))等。再者，上述連結基亦可至少1個氫原子被與上述有機基同樣之取代基取代。In the above general formula (1), X is a single bond or a linking group. Here, as the linking group, an alkylene group (e.g., methylene, ethylene, trimethylene, propylene group), an alkenylene group (e.g., vinylene group, 1-propylene group, vinylene group) may be mentioned as the linking group. Propyl), phenylene, naphthylene, oxygen atom (-O-), oxyalkylene [-(CH ₂ O) _m -; m=1～3], -(OCH ₂ ) _m -(m =1～3), -(CH ₂ O) _m CH ₂ -(m=1～3), _{-CO-, -COCO-, -CO(CH 2} ) _m CO-(m=1～3),- CO(C ₆ H ₄ )CO-, -S- _{, -CS-, -SO-, -SO 2} -, -NR-, -CONR-, -NRCO-, -CSNR-, -NRCS-, -NRNR- _{, -HPO 4 -, - Si (} OR) 2 -, - OSi (OR) 2 -, - OSi (OR) 2 O -, - Ti (OR) 2 -, - OTi (OR) 2 -, - OTi ( OR) ₂ O-, -Al(OR)-, -OAl(OR)-, -OAl(OR)O- (R each independently is an optional substituent (preferably a hydrogen atom or an alkyl group)) and the like. In addition, at least one hydrogen atom of the above-mentioned linking group may be substituted with the same substituent as the above-mentioned organic group.

其中，就進一步提昇保存穩定性之效果之觀點而言，X較佳為單鍵或亞甲基，更佳為單鍵。Among them, from the viewpoint of the effect of further improving storage stability, X is preferably a single bond or a methylene group, and more preferably a single bond.

R⁷ 及R⁸ 分別獨立地為氫原子或R⁹ -CO-(R⁹ 為烷基)。此時，R⁷ 及R⁸ 彼此可相同，或者亦可不同。又，R⁹ 為烷基之情形時之烷基係碳數1以上8以下之直鏈或分支之烷基，具體例與上述R¹ ～R⁶ 之例示相同。其中，R⁷ 及R⁸ 各自獨立地較佳為氫原子或碳數1以上3以下之直鏈或分支之烷基，更佳為氫原子、甲基或乙基，尤佳為氫原子或甲基。R ⁷ and R ⁸ are each independently a hydrogen atom or R ⁹ -CO- (R ⁹ is an alkyl group). In this case, R ⁷ and R ⁸ may be the same or different from each other. In addition, when R ⁹ is an alkyl group, the alkyl group is a linear or branched alkyl group having a carbon number of 1 or more and 8 or less. The specific examples are the same as the above-mentioned examples of R ¹ to R ⁶ . Among them, R ⁷ and R ⁸ are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom or a methyl group. base.

即，於本發明之較佳之形態中，上述通式(1)之單體較佳為，R¹ ～R⁶ 為氫原子，X為單鍵，R⁷ ～R⁸ 為R⁹ -CO-，此時R⁹ 為碳數1以上3以下之直鏈或分支之烷基的上述通式(1)之單體，更佳為，R¹ ～R⁶ 為氫原子，X為單鍵，R⁷ 及R⁸ 為氫原子之(3,4-二羥基-1-丁烯)或R⁷ 及R⁸ 為CH₃ -CO-之(3,4-二乙醯氧基-1-丁烯)。That is, in a preferred embodiment of the present invention, the monomer of the general formula (1) is preferably that R ¹ to R ⁶ are hydrogen atoms, X is a single bond, and R ⁷ to R ⁸ are R ⁹ -CO-, In this case, R ⁹ is a monomer of the general formula (1) in which a linear or branched alkyl group having a carbon number of 1 or more and 3 or less, more preferably, R ¹ to R ⁶ are hydrogen atoms, X is a single bond, and R ⁷ And R ⁸ is a hydrogen atom (3,4-dihydroxy-1-butene) or R ⁷ and R ⁸ are CH ₃ -CO- (3,4-diethoxy-1-butene).

本發明之一實施方式之共聚物必須包含源自下述通式(1)所表示之單體之結構單元及源自乙烯酯單體之結構單元，亦可進而具有其他結構單元(源自其他單體之結構單元)。此處，作為其他單體，可例舉：乙烯、丙烯等α-烯烴；3-丁烯-1-醇、4-戊烯-1-醇等具有羥基之烯烴及其醯化物；亞甲基丁二酸、順丁烯二酸、丙烯酸等不飽和酸或者其鹽或烷基酯化物(單,二-烷基酯化物)；丙烯腈、甲基丙烯腈等腈；丙烯醯胺、甲基丙烯醯胺、二丙酮丙烯醯胺等醯胺；乙烯基磺酸、烯丙基磺酸、甲代烯丙基磺酸等烯烴磺酸或其鹽；烷基乙烯基醚、二甲基烯丙基乙烯基酮、N-乙烯基吡咯啶酮、氯乙烯、碳酸乙烯基伸乙酯、2,2-二烷基-4-乙烯基-1,3-二氧戊環、甘油單烯丙基醚、3,4-二乙醯氧基-1-丁烯等乙烯系化合物；乙酸異丙烯酯、乙酸1-甲氧基乙烯酯等取代乙酸乙烯酯；偏二氯乙烯；1,4-二乙醯氧基-2-丁烯；碳酸伸乙烯酯等。共聚物較佳為實質上由源自下述通式(1)所表示之單體之結構單元及源自乙烯酯單體之結構單元構成(源自其他單體之結構單元之含量相對於全部結構單元未達5莫耳%)，更佳為由源自下述通式(1)所表示之單體之結構單元及源自乙烯酯單體之結構單元構成(源自其他單體之結構單元之含量相對於全部結構單元為0莫耳%)。The copolymer of one embodiment of the present invention must contain structural units derived from the monomer represented by the following general formula (1) and structural units derived from vinyl ester monomers, and may further have other structural units (derived from other The structural unit of the monomer). Here, examples of other monomers include α-olefins such as ethylene and propylene; olefins having hydroxyl groups such as 3-buten-1-ol and 4-penten-1-ol and their aldehydes; methylene groups Unsaturated acids such as succinic acid, maleic acid and acrylic acid or their salts or alkyl esters (mono-, di-alkyl esters); nitriles such as acrylonitrile and methacrylonitrile; acrylamide, methyl Amines such as acrylamide and diacetone acrylamide; olefin sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid or their salts; alkyl vinyl ether, dimethyl allyl Vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, glycerol monoallyl ether , 3,4-Diethyloxy-1-butene and other vinyl compounds; isopropenyl acetate, 1-methoxyvinyl acetate and other substituted vinyl acetates; vinylidene chloride; 1,4-diethyl Oxyoxy-2-butene; vinylene carbonate, etc. The copolymer is preferably substantially composed of structural units derived from the monomer represented by the following general formula (1) and structural units derived from vinyl ester monomers (the content of structural units derived from other monomers is relative to all The structural unit is less than 5 mol%), and is more preferably composed of structural units derived from monomers represented by the following general formula (1) and structural units derived from vinyl ester monomers (structures derived from other monomers) The content of the unit relative to all structural units is 0 mol%).

本發明之一實施方式之共聚物之製造方法可應用與公知方法相同之方法或適當修飾公知方法後進行應用。例如，共聚係藉由如下方式進行：於自由基聚合起始劑或觸媒之存在下，利用塊狀聚合法、溶液聚合法、沈澱聚合法、乳化聚合法、懸浮聚合法或塊狀-懸浮聚合法等先前公知之方法進行共聚。例如，藉由如下方式進行：於自由基聚合起始劑之存在下，並於視需要使用之溶劑中，利用塊狀聚合法、溶液聚合法、沈澱聚合法、乳化聚合法、懸浮聚合法或塊狀-懸浮聚合法等先前公知之方法，將乙烯酯單體、上述通式(1)所表示之單體及視需要使用之上述其他單體共聚。此處，作為自由基聚合起始劑(觸媒)，例如可使用：偶氮二異丁腈、過氧化乙醯、過氧化苯甲醯、過氧化月桂醯、偶氮雙二甲基戊腈、偶氮雙甲氧基二甲基戊腈等。又，共聚條件具體視所使用之溶劑或壓力等其他條件而定，例如於35～150℃下進行共聚，較佳為於40～100℃之範圍下進行共聚。The method for producing the copolymer of one embodiment of the present invention can be applied by applying the same method as the known method or by appropriately modifying the known method. For example, the copolymerization is carried out by the following method: in the presence of a radical polymerization initiator or catalyst, a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk-suspension method is used Copolymerization is carried out by a previously known method such as a polymerization method. For example, it is carried out by the following method: in the presence of a radical polymerization initiator and in a solvent used as needed, using a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, an emulsion polymerization method, a suspension polymerization method, or A previously known method such as a bulk-suspension polymerization method is to copolymerize a vinyl ester monomer, the monomer represented by the above-mentioned general formula (1), and the above-mentioned other monomers as necessary. Here, as the radical polymerization initiator (catalyst), for example, azobisisobutyronitrile, acetyl peroxide, benzyl peroxide, laurel peroxide, azobisdimethylvaleronitrile can be used , Azobismethoxydimethylvaleronitrile, etc. In addition, the copolymerization conditions specifically depend on other conditions such as the solvent or pressure used. For example, the copolymerization is carried out at 35 to 150°C, and the copolymerization is preferably carried out in the range of 40 to 100°C.

本發明之一實施方式之共聚物具有95莫耳%以上之皂化度，且於側鏈具有1,2-二醇結構。因此，為了形成上述結構，亦可對上述共聚物實施皂化處理。此處，若共聚物之皂化度未達95莫耳%，則親水性不充分，研磨粒會凝集(保存穩定性較低)(參照下述比較例7)。於本發明之一實施方式中，皂化度較佳為超過95(95.0)莫耳%，更佳為98(98.0)莫耳%以上(上限：100莫耳%)。再者，於本說明書中，「皂化度」採用依據JIS K6726-1994測定之值。The copolymer of one embodiment of the present invention has a saponification degree of 95 mol% or more, and has a 1,2-diol structure in the side chain. Therefore, in order to form the above-mentioned structure, the above-mentioned copolymer may be subjected to a saponification treatment. Here, if the degree of saponification of the copolymer is less than 95 mol%, the hydrophilicity is insufficient, and the abrasive grains are aggregated (the storage stability is low) (refer to Comparative Example 7 below). In one embodiment of the present invention, the degree of saponification is preferably more than 95 (95.0) mol%, more preferably 98 (98.0) mol% or more (upper limit: 100 mol%). In addition, in this specification, the "degree of saponification" adopts the value measured in accordance with JIS K6726-1994.

即，於本發明之較佳之形態中，研磨用組合物中所含之本發明之一實施方式之共聚物係乙酸乙烯酯與上述通式(1)之單體之共聚物之皂化處理物，上述通式(1)中，R¹ ～R⁶ 為氫原子，X為單鍵，R⁷ ～R⁸ 為R⁹ -CO-(R⁹ ＝碳數1以上3以下之直鏈或分支之烷基)。於本發明之更佳之形態中，研磨用組合物中所含之本發明之一實施方式之共聚物係乙酸乙烯酯與3,4-二乙醯氧基-1-丁烯之共聚物之皂化處理物(具有源自乙烯醇之結構單元及源自3,4-二羥基-1-丁烯之結構單元)。That is, in a preferred embodiment of the present invention, the copolymer of one embodiment of the present invention contained in the polishing composition is a saponified product of a copolymer of vinyl acetate and the monomer of the general formula (1), In the above general formula (1), R ¹ to R ⁶ are hydrogen atoms, X is a single bond, and R ⁷ to R ⁸ are R ⁹ -CO- (R ⁹ = linear or branched alkane with 1 to 3 carbon atoms base). In a more preferable aspect of the present invention, the copolymer of one embodiment of the present invention contained in the polishing composition is the saponification of a copolymer of vinyl acetate and 3,4-diethoxy-1-butene Treatment (having a structural unit derived from vinyl alcohol and a structural unit derived from 3,4-dihydroxy-1-butene).

此處，例如可使藉由如上所述之共聚所獲得之共聚物溶解於溶劑中，並利用鹼觸媒或酸觸媒而進行皂化處理。此處，作為上述溶劑，可使用甲醇、乙醇、丙醇、第三丁醇等醇。又，作為於皂化處理中可使用之鹼觸媒，可使用氫氧化鈉、氫氧化鉀、甲醇鈉、乙醇鈉、甲醇鉀、甲醇鋰等鹼金屬之氫氧化物或醇化物等。又，作為皂化處理中可使用之酸觸媒，可使用硫酸、鹽酸、硝酸、甲磺酸、沸石、陽離子交換樹脂等。皂化處理反應之反應溫度並無特別限定，較佳為10～60℃，更佳為20～50℃。Here, for example, the copolymer obtained by the above-mentioned copolymerization can be dissolved in a solvent and subjected to a saponification treatment using an alkali catalyst or an acid catalyst. Here, as the above-mentioned solvent, alcohols such as methanol, ethanol, propanol, and tert-butanol can be used. In addition, as the alkali catalyst that can be used in the saponification treatment, hydroxides or alcoholates of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, lithium methoxide, and the like can be used. In addition, as the acid catalyst that can be used in the saponification treatment, sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid, zeolite, cation exchange resin, etc. can be used. The reaction temperature of the saponification treatment reaction is not particularly limited, but is preferably 10 to 60°C, more preferably 20 to 50°C.

本發明之一實施方式之共聚物具有50～3000之聚合度。本發明之一實施方式之共聚物具有300～1200之聚合度。本發明之一實施方式之共聚物具有400～800之聚合度。藉由為此種實施方式，可更加提昇研磨對象物之保存穩定性。又，可進一步提昇保存穩定性與研磨對象物之研磨速度之平衡。The copolymer of one embodiment of the present invention has a degree of polymerization of 50 to 3000. The copolymer of one embodiment of the present invention has a degree of polymerization of 300 to 1200. The copolymer of one embodiment of the present invention has a degree of polymerization of 400-800. With this embodiment, the storage stability of the polishing object can be further improved. In addition, the balance between storage stability and polishing speed of the polishing object can be further improved.

本發明之一實施方式之共聚物具有100℃～230℃之熔點。本發明之一實施方式之共聚物具有130℃～230℃之熔點。本發明之一實施方式之共聚物具有160℃以上且未達190℃之熔點。藉由為此種實施方式，可更加提昇研磨對象物之保存穩定性。又，可進一步提昇保存穩定性與研磨對象物之研磨速度之平衡。再者，於本說明書中，「熔點」採用藉由示差掃描熱量測定(DSC)所測定之值。The copolymer of one embodiment of the present invention has a melting point of 100°C to 230°C. The copolymer of one embodiment of the present invention has a melting point of 130°C to 230°C. The copolymer of one embodiment of the present invention has a melting point of 160°C or higher and less than 190°C. With this embodiment, the storage stability of the polishing object can be further improved. In addition, the balance between storage stability and polishing speed of the polishing object can be further improved. Furthermore, in this specification, the "melting point" is a value measured by differential scanning calorimetry (DSC).

本發明之一實施方式之共聚物可以上述方式進行合成，或亦可使用市售品。作為市售品，可使用三菱化學股份有限公司製造之Nichigo G-Polymer^TM 系列(將由乙酸乙烯酯與3,4-二乙醯氧基-1-丁烯之反應所獲得者水解而獲得之丁烯二醇乙烯醇共聚物)等。The copolymer of one embodiment of the present invention can be synthesized in the above-mentioned manner, or a commercially available product can also be used. As a commercially available product, the Nichigo G-Polymer ^TM series manufactured by Mitsubishi Chemical Co., Ltd. can be used (butane obtained by the hydrolysis of vinyl acetate and 3,4-diethoxy-1-butene). Ethylene glycol vinyl alcohol copolymer) and so on.

於本發明之一實施方式中，上述研磨用組合物中之上述共聚物之含量較佳為0.01質量%以上，更佳為0.03質量%以上，進而較佳為0.05質量%以上，進而更佳為0.1質量%以上，尤佳為超過0.1質量%。於本發明之一實施方式中，上述研磨用組合物中之上述共聚物之含量較佳為10質量%以下，更佳為5質量%以下，進而較佳為未達2質量%，尤佳為未達1質量%。若為此種含量，則可更加提昇研磨對象物之保存穩定性。又，可進一步提昇保存穩定性與研磨對象物之研磨速度之平衡。In one embodiment of the present invention, the content of the copolymer in the polishing composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, and more preferably more than 0.1% by mass. In one embodiment of the present invention, the content of the copolymer in the polishing composition is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably less than 2% by mass, and particularly preferably Less than 1% by mass. If it is such a content, the storage stability of the polishing object can be further improved. In addition, the balance between storage stability and polishing speed of the polishing object can be further improved.

尤其於對包含氧化矽或多晶矽之研磨對象物等包含矽原子之研磨對象物進行研磨之情形時，將上述研磨用組合物中之上述共聚物之含量較佳為調整為0.001～10質量%，更佳為調整為超過0.05質量%且未達10質量%，尤佳為調整為超過0.1質量%且7質量%以下。或者，尤其於對包含氧化矽或多晶矽之研磨對象物等包含矽原子之研磨對象物進行研磨之情形時，將上述研磨用組合物中之上述共聚物之含量較佳為調整為0.01～5質量%，更佳為調整為0.03質量%以上且未達2質量%，尤佳為調整為0.05質量%以上且未達1質量%。藉由預先調整為此種範圍，可更加提昇研磨對象物之保存穩定性。又，可進一步提昇保存穩定性與研磨對象物之研磨速度之平衡。再者，本說明書中所揭示之所有下限值上限值之值揭示了所有組合。Especially when polishing a polishing object containing silicon atoms, such as a polishing object containing silicon oxide or polysilicon, the content of the copolymer in the polishing composition is preferably adjusted to 0.001 to 10% by mass. It is more preferable to adjust to more than 0.05% by mass and less than 10% by mass, and it is particularly preferable to adjust to more than 0.1% by mass and 7% by mass or less. Or, especially when polishing a polishing object containing silicon atoms, such as a polishing object containing silicon oxide or polycrystalline silicon, the content of the copolymer in the polishing composition is preferably adjusted to 0.01-5 mass %, more preferably adjusted to 0.03% by mass or more and less than 2% by mass, and particularly preferably adjusted to be 0.05% by mass or more and less than 1% by mass. By adjusting to this range in advance, the storage stability of the polishing object can be further improved. In addition, the balance between storage stability and polishing speed of the polishing object can be further improved. Furthermore, all the lower limit and upper limit values disclosed in this specification reveal all combinations.

[研磨用組合物之pH值] 根據本發明之一實施方式，研磨用組合物之pH值未達7.0。藉由為該實施方式，可更有效地使研磨粒之ζ電位帶正電。根據本發明之一實施方式，研磨用組合物之pH值為6.0以下。根據本發明之一實施方式，研磨用組合物之pH值為3.0以下。根據本發明之一實施方式，研磨用組合物之pH值為2.5以下。藉由為此種實施方式，可高速且高效率地對研磨對象物之表面進行研磨。根據本發明之一實施方式，研磨用組合物之pH值為1.0以上。根據本發明之一實施方式，研磨用組合物之pH值為1.6以上。根據本發明之一實施方式，研磨用組合物之pH值為2.0以上。藉由為此種實施方式，可高速且高效率地對研磨對象物之表面進行研磨。[PH value of polishing composition] According to one embodiment of the present invention, the pH value of the polishing composition does not reach 7.0. With this embodiment, the zeta potential of the abrasive grains can be more effectively positively charged. According to one embodiment of the present invention, the pH of the polishing composition is 6.0 or less. According to one embodiment of the present invention, the pH of the polishing composition is 3.0 or less. According to one embodiment of the present invention, the pH of the polishing composition is 2.5 or less. With this embodiment, the surface of the object to be polished can be polished at high speed and efficiently. According to one embodiment of the present invention, the pH of the polishing composition is 1.0 or more. According to one embodiment of the present invention, the pH of the polishing composition is 1.6 or higher. According to one embodiment of the present invention, the pH of the polishing composition is 2.0 or more. With this embodiment, the surface of the object to be polished can be polished at high speed and efficiently.

根據本發明之一實施方式，研磨用組合物之pH值為1.0以上3.0以下。根據本發明之一實施方式，研磨用組合物之pH值為1.6以上2.5以下。藉由為該實施方式，可高速且高效率地對研磨對象物(尤其是包含氧化矽或多晶矽之研磨對象物)之表面進行研磨。因此，上述實施方式於對包含氧化矽或多晶矽之研磨對象物等包含矽原子之研磨對象物進行研磨時尤其有效。再者，若研磨用組合物之pH值未達1.5，則有時無法有效率地發揮本發明之所期望之效果。根據本發明之一實施方式，研磨用組合物之pH值超過1.5且未達3.0，超過2.0且為2.5以下。藉由為該實施方式，可更高速且更高效率地對研磨對象物(尤其是包含氧化矽或多晶矽之研磨對象物)之表面進行研磨。According to one embodiment of the present invention, the pH of the polishing composition is 1.0 or more and 3.0 or less. According to one embodiment of the present invention, the pH of the polishing composition is 1.6 or more and 2.5 or less. With this embodiment, the surface of the polishing object (especially the polishing object including silicon oxide or polysilicon) can be polished at high speed and efficiently. Therefore, the above-mentioned embodiment is particularly effective when polishing a polishing target including silicon atoms, such as a polishing target including silicon oxide or polysilicon. Furthermore, if the pH of the polishing composition does not reach 1.5, the desired effect of the present invention may not be effectively exhibited. According to an embodiment of the present invention, the pH value of the polishing composition exceeds 1.5 and does not reach 3.0, and exceeds 2.0 and is 2.5 or less. With this embodiment, the surface of the polishing object (especially the polishing object including silicon oxide or polysilicon) can be polished at a higher speed and with higher efficiency.

根據本發明之一實施方式，研磨用組合物包含pH值調整劑。根據本發明之一實施方式，pH值調整劑只要使研磨用組合物之pH值處於所需範圍內，則酸及鹼均可，又，無機化合物及有機化合物均可。較佳為，pH值調整劑為酸。According to an embodiment of the present invention, the polishing composition includes a pH adjusting agent. According to one embodiment of the present invention, as long as the pH adjuster keeps the pH of the polishing composition within a desired range, it can be an acid or a base, and it can be an inorganic compound or an organic compound. Preferably, the pH adjusting agent is an acid.

作為鹼之具體例，可例舉：乙醇胺、2-胺基-2-乙基-1,3-丙二醇等脂肪族胺、芳香族胺等胺、氫氧化四級銨等有機鹼、氫氧化鉀等鹼金屬之氫氧化物、鹼土金屬之氫氧化物、四甲基銨及四乙基銨等四級銨鹽、氨等。Specific examples of the base include: aliphatic amines such as ethanolamine, 2-amino-2-ethyl-1,3-propanediol, amines such as aromatic amines, organic bases such as quaternary ammonium hydroxide, potassium hydroxide Alkali metal hydroxides, alkaline earth metal hydroxides, quaternary ammonium salts such as tetramethylammonium and tetraethylammonium, ammonia, etc.

作為酸之具體例，可例舉：鹽酸、硫酸、硝酸、氫氟酸、硼酸、碳酸、次磷酸、亞磷酸及磷酸等無機酸、或甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正戊酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、甘醇酸、水楊酸、甘油酸、乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、順丁烯二酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸、乳酸、二甘醇酸、2-呋喃羧酸、2,5-呋喃二羧酸、3-呋喃羧酸、2-四氫呋喃羧酸、甲氧乙酸、甲氧基苯乙酸、苯氧乙酸及依替膦酸(1-羥基乙烷-1,1-二膦酸，HEDP)等有機酸。Specific examples of acids include: hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, phosphoric acid and other inorganic acids, or formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2 -Methylbutanoic acid, n-hexanoic acid, 3,3-dimethylbutanoic acid, 2-ethylbutanoic acid, 4-methylvaleric acid, n-valeric acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethyl Caproic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid Dicarboxylic acid, malic acid, tartaric acid, citric acid, lactic acid, diglycolic acid, 2-furan carboxylic acid, 2,5-furandicarboxylic acid, 3-furan carboxylic acid, 2-tetrahydrofuran carboxylic acid, methoxyacetic acid, methane Organic acids such as oxyphenylacetic acid, phenoxyacetic acid and etidronic acid (1-hydroxyethane-1,1-diphosphonic acid, HEDP).

[液體載體] 於本發明之一實施方式中，研磨用組合物亦可進而包含液體載體。根據本發明之一實施方式，有機溶劑、水(尤其是純水)可被視為液體載體。要想阻礙研磨對象物之污染或其他成分之作用，較佳為儘可能不含雜質之水。具體而言，較佳為利用離子交換樹脂去除雜質離子後利用過濾器去除異物所得之純水、超純水或蒸餾水。[Liquid Carrier] In one embodiment of the present invention, the polishing composition may further include a liquid carrier. According to an embodiment of the present invention, organic solvents and water (especially pure water) can be regarded as liquid carriers. In order to hinder the contamination of the object to be polished or the effects of other components, it is preferable to use water that does not contain impurities as much as possible. Specifically, it is preferably pure water, ultrapure water, or distilled water obtained by removing impurity ions with an ion exchange resin and removing foreign substances with a filter.

[其他成分] 根據本發明之一實施方式，研磨用組合物亦可進而包含氧化劑、金屬防蝕劑、防腐劑、防黴劑、用以溶解難溶性有機物之有機溶劑等其他成分。[Other ingredients] According to an embodiment of the present invention, the polishing composition may further include other components such as an oxidizing agent, a metal anticorrosion agent, an antiseptic, an antifungal agent, and an organic solvent for dissolving insoluble organic matter.

(氧化劑) 根據根據本發明之一實施方式，氧化劑可例舉：過氧化氫、過氧化鈉、過氧化鋇、臭氧水、銀(II)鹽、鐵(III)鹽、過錳酸、鉻酸、重鉻酸、過氧二硫酸、過氧磷酸、過氧硫酸、過氧硼酸、過氧甲酸、過氧乙酸、過氧苯甲酸、過氧鄰苯二甲酸、次氯酸、次溴酸、次碘酸、氯酸、亞氯酸、過氯酸、溴酸、碘酸、過碘酸、過硫酸、二氯異三聚氰酸等。該氧化劑可單獨使用，或者亦可將2種以上混合使用。又，該氧化劑可使用市售品，亦可使用合成品。(Oxidant) According to an embodiment of the present invention, the oxidizing agent can be exemplified by hydrogen peroxide, sodium peroxide, barium peroxide, ozone water, silver (II) salt, iron (III) salt, permanganic acid, chromic acid, dichromium Acid, peroxydisulfuric acid, peroxyphosphoric acid, peroxysulfuric acid, peroxyboric acid, peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, peroxyphthalic acid, hypochlorous acid, hypobromous acid, hypoiodic acid , Chloric acid, chlorous acid, perchloric acid, bromic acid, iodic acid, periodic acid, persulfuric acid, dichloroisocyanuric acid, etc. The oxidizing agent may be used alone or in combination of two or more kinds. In addition, as the oxidizing agent, a commercially available product may be used, or a synthetic product may be used.

根據本發明之一實施方式，研磨用組合物實質上不含氧化劑。根據本發明之一實施方式，研磨用組合物實質上不含如下氧化劑：過氧化氫、過氧化鈉、過氧化鋇、臭氧水、銀(II)鹽、鐵(III)鹽、過錳酸、鉻酸、重鉻酸、過氧二硫酸、過氧磷酸、過氧硫酸、過氧硼酸、過氧甲酸、過氧乙酸、過氧苯甲酸、過氧鄰苯二甲酸、次氯酸、次溴酸、次碘酸、氯酸、亞氯酸、過氯酸、溴酸、碘酸、過碘酸、過硫酸或二氯異三聚氰酸。又，根據本發明之一實施方式，研磨用組合物實質上不含雙[(1-苯并***基)甲基]膦酸。再者，本說明書中，「實質上不含」，除研磨用組合物中完全不包含之概念以外，還包括研磨用組合物中包含0.0001 g/L以下之情形。According to one embodiment of the present invention, the polishing composition does not substantially contain an oxidizing agent. According to one embodiment of the present invention, the polishing composition does not substantially contain the following oxidizing agents: hydrogen peroxide, sodium peroxide, barium peroxide, ozone water, silver (II) salt, iron (III) salt, permanganic acid, Chromic acid, dichromic acid, peroxydisulfuric acid, peroxyphosphoric acid, peroxysulfuric acid, peroxyboric acid, peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, peroxyphthalic acid, hypochlorous acid, hypobromide Acid, hypoiodic acid, chloric acid, chlorous acid, perchloric acid, bromic acid, iodic acid, periodic acid, persulfuric acid or dichloroisocyanuric acid. Furthermore, according to one embodiment of the present invention, the polishing composition does not substantially contain bis[(1-benzotriazolyl)methyl]phosphonic acid. In addition, in this specification, the term "substantially free" includes not only the concept not included in the polishing composition at all, but also the case where the polishing composition contains 0.0001 g/L or less.

根據本發明之一實施方式，研磨用組合物中之氧化劑之含量較佳為0.1 g/L以上，更佳為1 g/L以上，進而較佳為3 g/L以上。隨著氧化劑之含量增多，研磨用組合物對研磨對象物之研磨速度更加提昇。又，研磨用組合物中之氧化劑之含量較佳為200 g/L以下，更佳為100 g/L以下，進而較佳為40 g/L以下。隨著氧化劑之含量減少，可抑制研磨用組合物之材料成本，此外，亦可減輕研磨使用後之研磨用組合物之處理、即廢液處理之負擔。又，亦可減少由氧化劑引起研磨對象物表面發生過度氧化之擔憂。According to one embodiment of the present invention, the content of the oxidizing agent in the polishing composition is preferably 0.1 g/L or more, more preferably 1 g/L or more, and still more preferably 3 g/L or more. As the content of the oxidizing agent increases, the polishing rate of the polishing composition for the polishing object is further increased. In addition, the content of the oxidizing agent in the polishing composition is preferably 200 g/L or less, more preferably 100 g/L or less, and still more preferably 40 g/L or less. As the content of the oxidizing agent decreases, the material cost of the polishing composition can be suppressed, and in addition, the burden of the treatment of the polishing composition after polishing use, that is, the treatment of waste liquid can also be reduced. In addition, it is also possible to reduce the fear of excessive oxidation of the surface of the object to be polished by the oxidizing agent.

(金屬防蝕劑) 藉由向研磨用組合物中添加金屬防蝕劑，可更加抑制於使用研磨用組合物之研磨中在配線之側邊產生凹陷。又，可更加抑制於使用研磨用組合物進行研磨後在研磨對象物之表面產生淺碟型凹陷(dishing)。(Metal corrosion inhibitor) By adding a metal corrosion inhibitor to the polishing composition, it is possible to more suppress the generation of dents on the side of the wiring during polishing using the polishing composition. In addition, it is possible to further suppress the occurrence of shallow dishing (dishing) on the surface of the polishing object after polishing with the polishing composition.

根據本發明之一實施方式，金屬防蝕劑為雜環式化合物或界面活性劑。雜環式化合物中之雜環之元數並無特別限定。又，雜環式化合物可為單環化合物，亦可為具有縮合環之多環化合物。該金屬防蝕劑可單獨使用，或者亦可將2種以上混合使用。又，該金屬防蝕劑可使用市售品，亦可使用合成品。According to an embodiment of the present invention, the metal corrosion inhibitor is a heterocyclic compound or a surfactant. The number of members of the heterocyclic ring in the heterocyclic compound is not particularly limited. In addition, the heterocyclic compound may be a monocyclic compound or a polycyclic compound having a condensed ring. The metal corrosion inhibitor can be used alone, or two or more of them can be mixed and used. In addition, as the metal corrosion inhibitor, a commercially available product can be used, or a synthetic product can also be used.

根據本發明之一實施方式，作為上述雜環化合物之具體例，例如可例舉：吡咯化合物、吡唑化合物、咪唑化合物、***化合物、四唑化合物、吡啶化合物、吡𠯤化合物、嗒𠯤化合物、4-氮茚化合物、吲哚嗪化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、喹

化合物、喹啉化合物、異喹啉化合物、㖠啶化合物、呔𠯤化合物、喹㗁啉化合物、喹唑啉化合物、㖕啉化合物、蝶啶化合物、噻唑化合物、異噻唑化合物、㗁唑化合物、異㗁唑化合物、呋呫化合物等含氮雜環化合物。According to one embodiment of the present invention, as specific examples of the above heterocyclic compounds, for example, pyrrole compounds, pyrazole compounds, imidazole compounds, triazole compounds, tetrazole compounds, pyridine compounds, pyridine compounds, and pyridine compounds may be mentioned. , 4-Benzene compounds, indoleazine compounds, indole compounds, isoindole compounds, indazole compounds, purine compounds, quinine

Compounds, quinoline compounds, isoquinoline compounds, pyridine compounds, quinazoline compounds, quinazoline compounds, quinazoline compounds, oxoline compounds, pteridine compounds, thiazole compounds, isothiazole compounds, azole compounds, isooxane Nitrogen-containing heterocyclic compounds such as azole compounds and furoxane compounds.

(防腐劑及防黴劑) 根據本發明之一實施方式，作為防腐劑及防黴劑，例如可例舉：2-甲基-4-異噻唑啉-3-酮或5-氯-2-甲基-4-異噻唑啉-3-酮等異噻唑啉系防腐劑、對羥基苯甲酸酯類及苯氧乙醇等。該等防腐劑及防黴劑可單獨使用，或者亦可將2種以上混合使用。(Preservatives and antifungal agents) According to an embodiment of the present invention, as an antiseptic and antifungal agent, for example, 2-methyl-4-isothiazolin-3-one or 5-chloro-2-methyl-4-isothiazolin can be mentioned Isothiazoline preservatives such as -3-one, parabens, phenoxyethanol, etc. These preservatives and antifungal agents may be used alone, or two or more of them may be mixed and used.

[研磨用組合物之製造方法] 根據本發明之一實施方式，研磨用組合物之製造方法並無特別限制，例如，可藉由將上述特定研磨粒、上述特定共聚物及視需要使用之pH值調整劑於液體載體中攪拌混合而獲得研磨用組合物。又，根據本發明之一實施方式，關於研磨用組合物之製造方法，可藉由如下方式獲得研磨用組合物，即，選擇於pH值未達7之水溶液中具有正ζ電位且每單位表面積之矽烷醇基數為2.5個/nm² 以下之研磨粒，將上述研磨粒與上述特定共聚物及視需要使用之pH值調整劑於液體載體中攪拌混合。將各成分混合時之溫度並無特別限制，較佳為10～40℃，亦可進行加熱用以提昇溶解速度。又，混合時間亦無特別限制。[Method for manufacturing polishing composition] According to one embodiment of the present invention, the method for manufacturing polishing composition is not particularly limited. For example, the above-mentioned specific abrasive grains, the above-mentioned specific copolymer, and the pH The value adjuster is stirred and mixed in the liquid carrier to obtain a polishing composition. In addition, according to one embodiment of the present invention, with regard to the manufacturing method of the polishing composition, the polishing composition can be obtained by selecting an aqueous solution with a pH value of less than 7 to have a positive zeta potential and per unit surface area For abrasive grains with a number of silanol groups of 2.5/nm ² or less, the abrasive grains are mixed with the above-mentioned specific copolymer and a pH adjuster if necessary in a liquid carrier. The temperature when mixing the components is not particularly limited, and is preferably 10 to 40°C, and heating may also be performed to increase the dissolution rate. In addition, the mixing time is not particularly limited.

[研磨方法] 本發明亦提供一種研磨方法，其包括使用本發明之研磨用組合物對研磨對象物進行研磨之步驟。研磨用組合物適宜用於氧化矽及多晶矽之研磨。[Grinding method] The present invention also provides a polishing method, which includes the step of polishing an object to be polished using the polishing composition of the present invention. The polishing composition is suitable for polishing silicon oxide and polysilicon.

根據本發明之一實施方式，氧化矽之研磨速度為190 Å/分鐘以上2000 Å/分鐘以下。根據本發明之一實施方式，氧化矽之研磨速度超過200 Å/分鐘且為1500 Å/分鐘以下。根據本發明之一實施方式，氧化矽之研磨速度為240 Å/分鐘以上1000 Å/分鐘以下。根據本發明之一實施方式，氧化矽之研磨速度為500 Å/分鐘以上800 Å/分鐘以下。藉由應用本發明之實施方式之研磨用組合物，可實現此種研磨速度。又，於本發明之實施方式中，亦可進一步調整研磨用組合物之組成，以便能夠達到此種研磨速度。再者，於本說明書中，「氧化矽之研磨速度」採用下述實施例中之＜研磨試驗＞中之「對TEOS(氧化矽)膜之研磨速度」。According to one embodiment of the present invention, the polishing rate of silicon oxide is 190 Å/min or more and 2000 Å/min or less. According to one embodiment of the present invention, the polishing rate of silicon oxide exceeds 200 Å/min and is less than 1500 Å/min. According to one embodiment of the present invention, the polishing rate of silicon oxide is 240 Å/min or more and 1000 Å/min or less. According to an embodiment of the present invention, the polishing rate of silicon oxide is 500 Å/min or more and 800 Å/min or less. Such a polishing speed can be achieved by applying the polishing composition of the embodiment of the present invention. Moreover, in the embodiment of the present invention, the composition of the polishing composition can be further adjusted so as to be able to achieve such a polishing speed. Furthermore, in this specification, the "polishing rate of silicon oxide" adopts the "polishing rate of TEOS (silicon oxide) film" in the "polishing test" in the following examples.

根據本發明之一實施方式，多晶矽(polysilicon)之研磨速度為210 Å/分鐘以上2000 Å/分鐘以下。根據本發明之一實施方式，多晶矽(polysilicon)之研磨速度超過260 Å/分鐘且為1500 Å/分鐘以下。根據本發明之一實施方式，多晶矽之研磨速度為280 Å/分鐘以上1000 Å/分鐘以下。根據本發明之一實施方式，多晶矽之研磨速度為300 Å/分鐘以上500 Å/分鐘以下。藉由應用本發明之實施方式之研磨用組合物，可實現此種研磨速度。又，於本發明之實施方式中，亦可進一步調整研磨用組合物之組成，以便能夠達到此種研磨速度。再者，於本說明書中，「多晶矽之研磨速度」採用下述實施例中之＜研磨試驗＞中之「對多晶矽基板之研磨速度」。According to an embodiment of the present invention, the grinding speed of polysilicon is more than 210 Å/min and less than 2000 Å/min. According to an embodiment of the present invention, the polishing speed of polysilicon (polysilicon) exceeds 260 Å/min and is below 1500 Å/min. According to an embodiment of the present invention, the polishing rate of polysilicon is 280 Å/min or more and 1000 Å/min or less. According to one embodiment of the present invention, the polishing speed of polysilicon is 300 Å/min or more and 500 Å/min or less. Such a polishing speed can be achieved by applying the polishing composition of the embodiment of the present invention. Moreover, in the embodiment of the present invention, the composition of the polishing composition can be further adjusted so as to be able to achieve such a polishing speed. Furthermore, in this specification, the "polishing rate of polycrystalline silicon" adopts the "polishing rate of polycrystalline silicon substrate" in the "polishing test" in the following examples.

[研磨對象物] 本發明之研磨對象物並無特別限制，可根據用途適當選擇。具體而言，可例舉：以多晶矽(polysilicon)、單晶矽、原矽酸四乙酯(Tetraethyl Orthosilicate；TEOS)為原料成膜所得之氧化矽膜、包含非晶矽(amorphous silicon)、氮化矽、碳氮化矽(SiCN)、金屬、SiGe等之膜或基板、HDP(High Density Plasma，高密度電漿)膜、USG(Undoped Silicate Glass，無摻雜矽玻璃)膜、PSG(Phosphorus Silicate Glass，磷矽酸鹽玻璃)膜、BPSG(Boron-Phospho Silicate Glass，硼磷矽酸鹽玻璃)膜、RTO(Rapid Thermal Oxidation，快速熱氧化)膜等氧化矽膜等。其中，較佳為對包含氧化矽(尤其是以TEOS作為原料之膜)或多晶矽之研磨對象物應用本發明之實施方式之研磨用組合物。根據該形態，可於自低溫至高溫之較廣溫度區域(尤其是低溫)內穩定地貯存研磨用組合物而不產生沈澱物(穩定性優異)，並且可以高速對該等研磨對象物進行研磨。因此，根據本發明之一實施方式，研磨用組合物用於對包含氧化矽及多晶矽(polysilicon)中之至少一者之研磨對象物(例如氧化矽膜、多晶矽基板或多晶矽膜)進行研磨之用途。或者，根據本發明之一實施方式，研磨方法具有如下步驟：使用上述研磨用組合物，或者，藉由上述製造方法獲得研磨用組合物並使用該研磨用組合物，對包含氧化矽及多晶矽(polysilicon)中之至少一者之研磨對象物(例如氧化矽膜、多晶矽基板或多晶矽膜)進行研磨。[Object to be polished] The object to be polished in the present invention is not particularly limited, and can be appropriately selected according to the application. Specifically, examples include: silicon oxide films formed from polysilicon, single crystal silicon, and tetraethyl orthosilicate (TEOS) as raw materials, including amorphous silicon, nitrogen Silicon, silicon carbonitride (SiCN), metal, SiGe, etc. films or substrates, HDP (High Density Plasma) film, USG (Undoped Silicate Glass) film, PSG (Phosphorus) Silicate Glass (phosphosilicate glass) film, BPSG (Boron-Phospho Silicate Glass, borophosphosilicate glass) film, RTO (Rapid Thermal Oxidation, rapid thermal oxidation) film and other silicon oxide films. Among them, it is preferable to apply the polishing composition of the embodiment of the present invention to a polishing object containing silicon oxide (especially a film using TEOS as a raw material) or polycrystalline silicon. According to this form, the polishing composition can be stably stored in a wide temperature range from low temperature to high temperature (especially low temperature) without generating deposits (excellent stability), and the polishing objects can be polished at high speed . Therefore, according to an embodiment of the present invention, the polishing composition is used for polishing an object to be polished (such as a silicon oxide film, a polysilicon substrate, or a polysilicon film) containing at least one of silicon oxide and polysilicon (polysilicon) . Alternatively, according to one embodiment of the present invention, the polishing method has the following steps: using the above-mentioned polishing composition, or obtaining a polishing composition by the above-mentioned manufacturing method and using the polishing composition, to the composition containing silicon oxide and polycrystalline silicon ( The polishing target (for example, a silicon oxide film, a polysilicon substrate, or a polysilicon film) of at least one of the polysilicon) is polished.

作為研磨裝置，可使用一般的研磨裝置，其安裝有保持具有研磨對象物之基板等之保持器及可變更轉速之馬達等，且具有可貼附研磨墊(研磨布)之研磨壓盤。As the polishing device, a general polishing device can be used, which is equipped with a holder for holding a substrate with the object to be polished, a motor whose rotation speed can be changed, and the like, and a polishing platen to which a polishing pad (polishing cloth) can be attached.

作為上述研磨墊，可無特別限制地使用一般的不織布、聚胺基甲酸酯及多孔質氟樹脂等。對研磨墊施以使研磨用組合物積存之溝槽加工較佳。As the above-mentioned polishing pad, general nonwoven fabric, polyurethane, porous fluororesin, etc. can be used without particular limitation. It is preferable to apply groove processing to the polishing pad to accumulate the polishing composition.

研磨條件亦無特別限制，例如研磨壓盤之轉速較佳為10～500 rpm，研磨頭之轉速(載體轉速)較佳為10～500 rpm，向具有研磨對象物之基板施加之壓力(研磨壓力)較佳為0.1～10 psi。向研磨墊供給研磨用組合物之方法亦無特別限制，例如採用以泵等連續供給之方法。該供給量並無限制，但較佳為研磨墊之表面始終被本發明之研磨用組合物覆蓋。The polishing conditions are also not particularly limited. For example, the rotation speed of the polishing platen is preferably 10 to 500 rpm, the rotation speed of the polishing head (carrier rotation speed) is preferably 10 to 500 rpm, and the pressure applied to the substrate with the polishing object (grinding pressure) ) Is preferably 0.1-10 psi. The method of supplying the polishing composition to the polishing pad is also not particularly limited. For example, a continuous supply method such as a pump is used. The supply amount is not limited, but it is preferable that the surface of the polishing pad is always covered by the polishing composition of the present invention.

[半導體基板之製造方法] 本發明之研磨用組合物之用途無限制，較佳為用於半導體基板。因此，本發明亦提供一種半導體基板之製造方法，其包括藉由上述研磨方法對半導體基板進行研磨之步驟。藉由該實施方式，半導體基板之生產效率提昇。 [實施例][Method of manufacturing semiconductor substrate] The use of the polishing composition of the present invention is not limited, and it is preferably used for semiconductor substrates. Therefore, the present invention also provides a method for manufacturing a semiconductor substrate, which includes the step of polishing the semiconductor substrate by the above-mentioned polishing method. With this embodiment, the production efficiency of the semiconductor substrate is improved. [Example]

利用以下實施例及比較例對本發明更詳細地進行說明。但是，本發明之技術範圍並不僅限制於以下實施例。再者，若無特別說明，則「%」及「份」分別意指「質量%」及「質量份」。又，於下述實施例中，若無特別說明，則操作係於室溫(25℃)/相對濕度40～50%RH之條件下進行。The present invention will be explained in more detail with the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Furthermore, unless otherwise specified, "%" and "parts" mean "mass %" and "parts by mass", respectively. In addition, in the following examples, unless otherwise specified, the operation is performed under the conditions of room temperature (25° C.)/relative humidity of 40 to 50% RH.

＜矽烷醇基數之算出方法＞研磨粒之每單位表面積之矽烷醇基數(單位：個/nm² )係藉由以下測定方法或計算方法測定或算出各參數後，藉由下述方法算出。<Calculation method of the number of silanol groups> The number of silanol groups per unit surface area of the abrasive grains (unit: pcs/nm ² ) is calculated by the following method after measuring or calculating each parameter by the following measurement method or calculation method.

更具體而言，下述式中之C為研磨粒之合計質量，下述式中之S為研磨粒之BET(Brunauer-Emmett-Teller，布厄特)比表面積。進一步具體而言，首先，向200 ml燒杯中採集作為固形物成分之1.50 g之研磨粒，並添加100 ml之純水形成漿料後，添加30 g之氯化鈉使其溶解。繼而，添加1 N鹽酸，將漿料之pH值調整為約3.0～3.5，其後，添加純水直至漿料達到150 ml。對於該漿料，使用自動滴定裝置(平沼產業股份有限公司製造之COM-1700)，於25℃下使用0.1 N氫氧化鈉水溶液，以pH值成為4.0之方式進行調整，進而藉由pH滴定，測定將pH值自4.0提高至9.0所需之0.1 N氫氧化鈉水溶液之體積V[L]。平均矽烷醇基數(平均矽烷醇基密度)(個/nm² )可根據下述式算出。More specifically, C in the following formula is the total mass of the abrasive grains, and S in the following formula is the BET (Brunauer-Emmett-Teller, Buert) specific surface area of the abrasive grains. More specifically, first, 1.50 g of abrasive grains as a solid component were collected in a 200 ml beaker, 100 ml of pure water was added to form a slurry, and 30 g of sodium chloride was added to dissolve it. Then, 1N hydrochloric acid was added to adjust the pH of the slurry to about 3.0-3.5, and then pure water was added until the slurry reached 150 ml. For this slurry, an automatic titration device (COM-1700 manufactured by Hiranuma Sangyo Co., Ltd.) was used, and a 0.1 N sodium hydroxide aqueous solution was used at 25°C to adjust so that the pH value became 4.0, and then by pH titration, Determine the volume V[L] of the 0.1 N sodium hydroxide aqueous solution required to increase the pH value from 4.0 to 9.0. The average number of silanol groups (average silanol group density) (number/nm ² ) can be calculated according to the following formula.

[數1]

[Number 1]

上述式中， ρ表示平均矽烷醇基數(平均矽烷醇基密度)(個/nm² )； c表示滴定中使用之氫氧化鈉水溶液之濃度(mol/L)； V表示將pH值自4.0提高至9.0所需之氫氧化鈉水溶液之體積(L)； N_A 表示亞佛加厥常數(個/mol)； C表示研磨粒之合計質量(固形物成分)(g)； S表示研磨粒之BET比表面積之加權平均值(nm² /g)。In the above formula, ρ represents the average number of silanol groups (average silanol group density) (pieces/nm ² ); c represents the concentration of the sodium hydroxide aqueous solution used in the titration (mol/L); V represents the pH value increased from 4.0 The volume of the sodium hydroxide aqueous solution required to reach 9.0 (L); N _A is the Avogadro constant (pieces/mol); C is the total mass of the abrasive grains (solid content) (g); S is the abrasive grain The weighted average of BET specific surface area (nm ² /g).

＜粒徑之算出方法＞研磨粒之平均一次粒徑根據利用Micromeritics公司製造之“Flow Sorb II 2300”測定之基於BET法之研磨粒之比表面積及研磨粒之密度算出。又，研磨粒之平均二次粒徑藉由日機裝股份有限公司製造之動態光散射式粒徑、粒度分佈裝置UPA-UTI151進行測定。＜Calculation method of particle size＞ The average primary particle size of the abrasive grains is calculated based on the specific surface area of the abrasive grains and the density of the abrasive grains based on the BET method measured by the "Flow Sorb II 2300" manufactured by Micromeritics. In addition, the average secondary particle size of the abrasive grains was measured with a dynamic light scattering particle size and particle size distribution device UPA-UTI151 manufactured by Nikkiso Co., Ltd.

＜pH值之測定方法＞研磨用組合物(液溫：25℃)之pH值藉由pH值計(堀場製作所股份有限公司製造，型號：LAQUA)確認。＜Method of measuring pH value＞ The pH value of the polishing composition (liquid temperature: 25°C) was confirmed with a pH meter (manufactured by Horiba Manufacturing Co., Ltd., model: LAQUA).

＜ζ電位之測定方法＞研磨用組合物中之研磨粒之ζ電位X[mV]可藉由如下方式算出：將研磨用組合物供予大塚電子股份有限公司製造之ELS-Z2，於測定溫度25℃下使用流槽並利用雷射都蔔勒法(電泳光散射測定法)進行測定，利用Smoluchowski式對所獲得之資料進行解析。＜Measurement method of zeta potential＞ The zeta potential X [mV] of the abrasive grains in the polishing composition can be calculated as follows: the polishing composition is supplied to the ELS-Z2 manufactured by Otsuka Electronics Co., Ltd., and the launder is used at a measurement temperature of 25°C. The laser Doppler method (electrophoretic light scattering method) was used for the measurement, and the Smoluchowski formula was used to analyze the obtained data.

[實施例1] (研磨用組合物之製備) 向作為液體載體之純水中，以相對於最終之研磨用組合物100質量%為0.45質量%之量添加作為研磨粒之膠體二氧化矽A(矽烷醇基數：1.8個/nm² ，平均一次粒徑：30 nm，平均二次粒徑：60 nm，平均締合度：2.0)，以相對於最終之研磨用組合物100質量%為0.05質量%之量添加丁烯二醇乙烯醇共聚物(製品名：Nichigo G-Polymer^TM AZF8035W；三菱化學股份有限公司製造；聚合度300；皂化度98.0莫耳%以上，熔點172℃)，並以pH值成為2.5之方式添加作為pH值調整劑之1-羥基乙烷-1,1-二膦酸(HEDP)，藉此製備實施例1之研磨用組合物。該組合物中之膠體二氧化矽A之ζ電位為+11 mV。[Example 1] (Preparation of polishing composition) To pure water as a liquid carrier, colloidal silica A as abrasive particles was added in an amount of 0.45% by mass relative to 100% by mass of the final polishing composition (Number of silanol groups: 1.8/nm ² , average primary particle size: 30 nm, average secondary particle size: 60 nm, average degree of association: 2.0), with respect to the final polishing composition 100% by mass as 0.05 mass Add butene glycol vinyl alcohol copolymer (product name: Nichigo G-Polymer ^TM AZF8035W; manufactured by Mitsubishi Chemical Co., Ltd.; polymerization degree 300; saponification degree above 98.0 mol%, melting point 172℃), and adjust the pH to 1-hydroxyethane-1,1-diphosphonic acid (HEDP) as a pH adjuster was added so that the value became 2.5, thereby preparing the polishing composition of Example 1. The zeta potential of colloidal silica A in the composition is +11 mV.

[實施例2～6及比較例1～7] (研磨用組合物之製備) 如表1所示，變更各成分之種類及含量、以及各研磨用組合物之pH值及各組合物中之研磨粒之ζ電位，除此以外，以與實施例1相同之方式進行操作，製備各研磨用組合物。再者，下述表1中之膠體二氧化矽B、膠體二氧化矽C及膠體二氧化矽D使用下述者。[Examples 2 to 6 and Comparative Examples 1 to 7] (Preparation of polishing composition) As shown in Table 1, the operation was performed in the same manner as in Example 1, except that the type and content of each component, the pH value of each polishing composition and the zeta potential of the abrasive grains in each composition were changed. Each polishing composition was prepared. Furthermore, colloidal silica B, colloidal silica C, and colloidal silica D in Table 1 below use the following.

膠體二氧化矽B：於表面固定化有磺基之膠體二氧化矽(矽烷醇基數1.8個/nm² ，平均一次粒徑30 nm，平均二次粒徑60 nm，平均締合度2.0) 膠體二氧化矽C：於表面固定化有胺基之膠體二氧化矽(矽烷醇基數：1.8個/nm² ，平均一次粒徑：30 nm，平均二次粒徑：60 nm，平均締合度：2.0) 膠體二氧化矽D：膠體二氧化矽(矽烷醇基數5.7個/nm² ，平均一次粒徑35 nm，平均二次粒徑70 nm，平均締合度2.0)。Colloidal silica B: Colloidal silica with sulfo groups immobilized on the surface (the number of silanol groups is 1.8/nm ² , the average primary particle size is 30 nm, the average secondary particle size is 60 nm, and the average degree of association is 2.0). Silica C: Colloidal silica with amine groups immobilized on the surface (number of silanol groups: 1.8/nm ² , average primary particle size: 30 nm, average secondary particle size: 60 nm, average degree of association: 2.0) Colloidal silica D: colloidal silica (the number of silanol groups is 5.7/nm ² , the average primary particle size is 35 nm, the average secondary particle size is 70 nm, and the average degree of association is 2.0).

又，表1中之共聚物之詳情如下所述。In addition, the details of the copolymers in Table 1 are as follows.

OKS1011：丁烯二醇乙烯醇共聚物(製品名：Nichigo G-Polymer^TM OKS-1011；三菱化學股份有限公司製造；聚合度300；皂化度98.0莫耳%以上；熔點206℃) OKS8039：丁烯二醇乙烯醇共聚物(製品名：Nichigo G-Polymer^TM OKS-8039；三菱化學股份有限公司製造；聚合度600；皂化度98.0莫耳%以上；熔點168℃) OKS1028：丁烯二醇乙烯醇共聚物(製品名：Nichigo G-Polymer^TM OKS-1028；三菱化學股份有限公司製造；聚合度600；皂化度98.0莫耳%以上；熔點206℃) OKS1009：丁烯二醇乙烯醇共聚物(製品名：Nichigo G-Polymer^TM OKS-1009；三菱化學股份有限公司製造；聚合度1200；皂化度98.0莫耳%以上；熔點190℃) OKS8096：丁烯二醇乙烯醇共聚物(製品名：Nichigo G-Polymer^TM OKS-8096；三菱化學股份有限公司製造；聚合度450；皂化度93.0莫耳%；熔點168℃) JPR-10HH：聚乙烯醇(製品名：HH型JPR-10HH；JAPAN VAM & POVAL股份有限公司製造；聚合度230；皂化度超過98莫耳%；熔點230℃)。OKS1011: Butylene glycol vinyl alcohol copolymer (product name: Nichigo G-Polymer ^TM OKS-1011; manufactured by Mitsubishi Chemical Co., Ltd.; polymerization degree 300; saponification degree 98.0 mol% or more; melting point 206°C) OKS8039: butene Glycol vinyl alcohol copolymer (product name: Nichigo G-Polymer ^TM OKS-8039; manufactured by Mitsubishi Chemical Co., Ltd.; polymerization degree 600; saponification degree 98.0 mol% or more; melting point 168°C) OKS1028: butene glycol vinyl alcohol Copolymer (product name: Nichigo G-Polymer ^TM OKS-1028; manufactured by Mitsubishi Chemical Co., Ltd.; polymerization degree 600; saponification degree above 98.0 mol%; melting point 206°C) OKS1009: butene glycol vinyl alcohol copolymer (product Name: Nichigo G-Polymer ^TM OKS-1009; manufactured by Mitsubishi Chemical Co., Ltd.; polymerization degree 1200; saponification degree 98.0 mol% or more; melting point 190℃) OKS8096: butene glycol vinyl alcohol copolymer (product name: Nichigo G -Polymer ^TM OKS-8096; manufactured by Mitsubishi Chemical Corporation; degree of polymerization 450; degree of saponification 93.0 mol%; melting point 168°C) JPR-10HH: polyvinyl alcohol (product name: HH type JPR-10HH; JAPAN VAM & POVAL Manufactured by Co., Ltd.; degree of polymerization 230; degree of saponification exceeding 98 mol%; melting point 230°C).

其次，對於上述所製備之各研磨用組合物，按照下述方法，對研磨速度(Removal Rate)(Å/分鐘)進行評價。將結果一併示於下述表1中。Next, for each polishing composition prepared above, the removal rate (Å/min) was evaluated according to the following method. The results are shown in Table 1 below.

＜研磨試驗＞使用各研磨用組合物，於下述條件下對研磨對象物之表面進行研磨。作為研磨對象物，分別使用直徑300 mm之矽基板表面所形成之膜厚10000 Å之TEOS(氧化矽)膜及膜厚4500 Å之多晶矽基板。再者，於下述表1中，將對矽基板表面所形成之TEOS(氧化矽)膜之研磨速度及對多晶矽基板之研磨速度分別表示為「TEOS」及「poly Si」。＜Grinding test＞ Using each polishing composition, the surface of the polishing object was polished under the following conditions. As the object to be polished, a TEOS (silicon oxide) film with a thickness of 10000 Å formed on the surface of a silicon substrate with a diameter of 300 mm and a polysilicon substrate with a thickness of 4500 Å were used. Furthermore, in Table 1 below, the polishing rate of the TEOS (silicon oxide) film formed on the surface of the silicon substrate and the polishing rate of the polysilicon substrate are denoted as "TEOS" and "poly Si", respectively.

[研磨裝置及研磨條件] 研磨裝置：荏原製作所股份有限公司製造之FREX 300E 研磨墊：IC1000XY-k groove(Nitta Haas股份有限公司製造之聚胺基甲酸酯) 研磨壓力：140 hPa(約2.0 psi) 研磨壓盤之轉速：30 rpm 研磨頭之轉速：30 rpm 研磨用組合物之供給量：200 mL/min 研磨時間：60 sec 原位(In-situ)修整(dressing)。[Grinding equipment and conditions] Grinding device: FREX 300E manufactured by Ebara Manufacturing Co., Ltd. Polishing pad: IC1000XY-k groove (Polyurethane manufactured by Nitta Haas Co., Ltd.) Grinding pressure: 140 hPa (about 2.0 psi) Rotation speed of grinding platen: 30 rpm Rotation speed of grinding head: 30 rpm Supply amount of polishing composition: 200 mL/min Grinding time: 60 sec In-situ dressing.

[評價] 對於各研磨用組合物，測定下述項目並進行評價。[Evaluation] For each polishing composition, the following items were measured and evaluated.

[研磨速度(研磨速率：Removal Rate)之測定] 研磨速度(Å/min)根據下述式(1)進行計算。[Measurement of Grinding Speed (Removal Rate)] The polishing rate (Å/min) is calculated according to the following formula (1).

[數2]

[Number 2]

再者，藉由光干涉式膜厚測定裝置求出各膜厚，將研磨前後之膜厚之差除以研磨時間，藉此對研磨速度進行評價。將評價結果一併示於表1中。Furthermore, each film thickness was obtained by an optical interference type film thickness measuring device, and the difference in film thickness before and after polishing was divided by the polishing time to evaluate the polishing rate. The evaluation results are shown in Table 1 together.

＜保存穩定性試驗＞將各研磨用組合物放入至聚丙烯(PP)製容器中，於5℃、25℃及80℃之恆溫室內靜置14天。＜Storage stability test＞ Each polishing composition was put into a polypropylene (PP) container, and it was allowed to stand in a constant temperature room at 5°C, 25°C, and 80°C for 14 days.

[保存穩定性之評價] 對於PP製容器中所包含之樣品，保持著將其放入至容器中之狀態利用目視觀察其底部，確認有無沈澱物，根據沈澱物之產生程度將保存穩定性分類為下述3種結果。再者，於實際使用中可容許及Δ。將評價結果一併示於表1中。[Evaluation of Storage Stability] Regarding the sample contained in the PP container, the bottom of the sample was kept in the container and the bottom was visually observed to confirm the presence or absence of sediment. The storage stability was classified into the following three results according to the degree of sediment generation. Furthermore, and Δ can be tolerated in actual use. The evaluation results are shown in Table 1 together.

：於保管溫度下及恢復至25℃後均亦未觀察到沈澱 Δ：於保管溫度下觀察到沈澱，但當恢復至25℃時再分散從而沈澱物消失 ×：觀察到沈澱，且即便恢復至25℃亦未觀察到沈澱物之消除：No precipitation is observed at the storage temperature and after returning to 25℃ Δ: Precipitation is observed at the storage temperature, but when it is restored to 25°C, it redisperses and the precipitate disappears ×: Precipitation is observed, and no elimination of the precipitate is observed even if it is restored to 25°C

[表1-1] 表1 膠體二氧化矽共聚物 pH值調整劑 ζ電位(mV) 名稱矽烷醇基數(個/nm² ) 平均二次粒徑(nm) 濃度[%] 表面修飾名稱化合物名聚合度皂化度(莫耳%) 熔點(℃) 添加量[%] 名稱 pH值實施例1 A 1.8 60 0.45 無 AZF8035W 共聚物^＊ ¹ 300 ≧98 172 0.05 HEDP 2.5 +11 實施例2 A 1.8 60 0.45 無 OKS1011 共聚物^＊ ¹ 300 ≧98 206 0.05 HEDP 2.5 +11 實施例3 A 1.8 60 0.45 無 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 HEDP 2.5 +11 實施例4 C 1.8 60 0.45 陽離子 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 HEDP 2.5 +20 實施例5 A 1.8 60 0.45 無 OKS1028 共聚物^＊ ¹ 600 ≧98 206 0.05 HEDP 2.5 +11 實施例6 A 1.8 60 0.45 無 OKS1009 共聚物^＊ ¹ 1200 ≧98 190 0.05 HEDP 2.5 +11 比較例1 A 1.8 60 0.45 無 JMR-10HH PVA^＊ ² 230 ＞98 230 0.05 HEDP 2.5 +11 比較例2 B 1.8 60 0.45 陰離子 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 HEDP 2.5 -46 比較例3 C 1.8 60 0.45 陽離子 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 氨 8.0 -43 比較例4 A 1.8 70 0.45 無 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 氨 10.0 -46 比較例5 D 5.7 70 0.45 無 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 氨 10.0 -54 比較例6 D 5.7 70 0.45 無 OKS8039 共聚物^＊ ¹ 600 ≧98 168 0.05 HEDP 2.5 +4 比較例7 A 1.8 60 0.45 無 OKS8096 共聚物^＊ ¹ 450 93 168 0.05 HEDP 2.5 無法測定＊1 共聚物：丁烯二醇乙烯醇共聚物＊2 PVA：聚乙烯醇[Table 1-1] Table 1 Colloidal silica Copolymer pH adjuster Zeta potential (mV) name Number of silanol groups (pcs/nm ² ) Average secondary particle size (nm) concentration[%] Surface Modification name Compound name Degree of polymerization Saponification degree (mol%) Melting point (℃) Add amount [%] name pH value Example 1 A 1.8 60 0.45 none AZF8035W Copolymer ^* ¹ 300 ≧98 172 0.05 HEDP 2.5 +11 Example 2 A 1.8 60 0.45 none OKS1011 Copolymer ^* ¹ 300 ≧98 206 0.05 HEDP 2.5 +11 Example 3 A 1.8 60 0.45 none OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 HEDP 2.5 +11 Example 4 C 1.8 60 0.45 cation OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 HEDP 2.5 +20 Example 5 A 1.8 60 0.45 none OKS1028 Copolymer ^* ¹ 600 ≧98 206 0.05 HEDP 2.5 +11 Example 6 A 1.8 60 0.45 none OKS1009 Copolymer ^* ¹ 1200 ≧98 190 0.05 HEDP 2.5 +11 Comparative example 1 A 1.8 60 0.45 none JMR-10HH PVA ^＊ ² 230 ＞98 230 0.05 HEDP 2.5 +11 Comparative example 2 B 1.8 60 0.45 Anion OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 HEDP 2.5 -46 Comparative example 3 C 1.8 60 0.45 cation OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 ammonia 8.0 -43 Comparative example 4 A 1.8 70 0.45 none OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 ammonia 10.0 -46 Comparative example 5 D 5.7 70 0.45 none OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 ammonia 10.0 -54 Comparative example 6 D 5.7 70 0.45 none OKS8039 Copolymer ^* ¹ 600 ≧98 168 0.05 HEDP 2.5 +4 Comparative example 7 A 1.8 60 0.45 none OKS8096 Copolymer ^* ¹ 450 93 168 0.05 HEDP 2.5 Unable to determine *1 Copolymer: Butenediol vinyl alcohol copolymer *2 PVA: Polyvinyl alcohol

[表1-2] 表1(續) 研磨速度(Å/min) 保存穩定性 TEOS poly Si 5℃×14天 25℃×14天 80℃×14天實施例1 202 278 實施例2 202 272 Δ 實施例3 200 260 實施例4 253 280 實施例5 198 268 Δ 實施例6 193 241 Δ 比較例1 213 208 × 比較例2 10 185 比較例3 25 170 比較例4 5 180 比較例5 4 175 比較例6 89 154 × 比較例7 - - × × × [Table 1-2] Table 1 (continued) Grinding speed (Å/min) Storage stability TEOS poly Si 5℃×14 days 25℃×14 days 80℃×14 days Example 1 202 278 Example 2 202 272 Δ Example 3 200 260 Example 4 253 280 Example 5 198 268 Δ Example 6 193 241 Δ Comparative example 1 213 208 X Comparative example 2 10 185 Comparative example 3 25 170 Comparative example 4 5 180 Comparative example 5 4 175 Comparative example 6 89 154 X Comparative example 7 - - X X X

＜考察＞由上述表1之結果顯示出，根據實施例之研磨用組合物，無論貯存溫度如何均未觀察到沈澱。又，亦顯示出，根據實施例之研磨用組合物，對於氧化矽膜及多晶矽基板兩者均可達到較高之研磨速度。相對於此，比較例之研磨用組合物之保存穩定性或研磨速度較差，無法兼顧這兩者。＜Investigation＞ The results of Table 1 above show that according to the polishing composition of the example, no precipitation was observed regardless of the storage temperature. In addition, it is also shown that the polishing composition according to the embodiment can achieve a higher polishing speed for both the silicon oxide film and the polysilicon substrate. In contrast, the polishing composition of the comparative example has poor storage stability and polishing speed, and cannot achieve both.

Claims

一種研磨用組合物，其含有：研磨粒，其於pH值未達7之水溶液中具有正ζ電位，且每單位表面積之矽烷醇基數為2.5個/nm² 以下；及下述通式(1)所表示之單體與乙烯酯單體之共聚物，其皂化度為95莫耳%以上，且於側鏈具有1,2-二醇結構；且上述研磨用組合物之pH值未達7， [化1] 通式(1)：

上述通式(1)中， R¹ ～R⁶ 分別獨立地為氫原子或有機基， X為單鍵或連結基， R⁷ 及R⁸ 分別獨立地為氫原子或R⁹ -CO-(R⁹ 為烷基)。A polishing composition, which contains: abrasive grains, which have a positive zeta potential in an aqueous solution with a pH value of less than 7, and the number of silanol groups per unit surface area is 2.5/nm ² or less; and the following general formula (1 The copolymer of monomer and vinyl ester monomer represented by) has a saponification degree of 95 mol% or more, and has a 1,2-diol structure in the side chain; and the pH value of the above-mentioned polishing composition does not reach 7 ， [化1] General formula (1):

In the above general formula (1), R ¹ to R ⁶ are each independently a hydrogen atom or an organic group, X is a single bond or a linking group, and R ⁷ and R ⁸ are each independently a hydrogen atom or R ⁹ -CO-(R ⁹ is alkyl).

如請求項1之研磨用組合物，其中上述研磨粒之ζ電位為10 mV以上50 mV以下。The polishing composition of claim 1, wherein the zeta potential of the abrasive grains is 10 mV or more and 50 mV or less.

如請求項1或2之研磨用組合物，其中上述共聚物係乙酸乙烯酯與3,4-二乙醯氧基-1-丁烯之共聚物之皂化處理物。The polishing composition of claim 1 or 2, wherein the above-mentioned copolymer is a saponification treatment product of a copolymer of vinyl acetate and 3,4-diethoxy-1-butene.

如請求項1至3中任一項之研磨用組合物，其中上述研磨粒為膠體二氧化矽。The polishing composition according to any one of claims 1 to 3, wherein the abrasive particles are colloidal silica.

如請求項1至4中任一項之研磨用組合物，其pH值為1.0以上3.0以下。The polishing composition according to any one of claims 1 to 4 has a pH value of 1.0 or more and 3.0 or less.

如請求項1至5中任一項之研磨用組合物，其用於對包含氧化矽及多晶矽中之至少一者之研磨對象物進行研磨之用途。The polishing composition according to any one of claims 1 to 5, which is used for polishing an object to be polished including at least one of silicon oxide and polysilicon.

一種研磨方法，其包括使用如請求項1至6中任一項之研磨用組合物對研磨對象物進行研磨之步驟。A polishing method comprising the step of polishing an object to be polished using the polishing composition according to any one of claims 1 to 6.

如請求項7之方法，其中上述研磨對象物包含氧化矽及多晶矽中之至少一者。The method of claim 7, wherein the polishing object includes at least one of silicon oxide and polysilicon.

一種半導體基板之製造方法，其包括藉由如請求項7或8之研磨方法對半導體基板進行研磨之步驟。A method of manufacturing a semiconductor substrate, which includes the step of polishing the semiconductor substrate by the polishing method of claim 7 or 8.