TWI658132B - Polishing composition, manufacturing method of polishing composition, and silicon wafer manufacturing method - Google Patents
Polishing composition, manufacturing method of polishing composition, and silicon wafer manufacturing method Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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Abstract
本發明提供一種矽晶圓之研磨中,可一方面抑制對表面品質之影響一方面提高研磨速率之研磨用組成物。依據本發明,提供用於研磨矽晶圓之研磨用組成物。該研磨用組成物包含表面具有複數個突起之二氧化矽粒子作為研磨粒。上述研磨用組成物進一步包含由氨及銨鹽所組成之群選出之無機鹼性化合物(A)。 The invention provides a polishing composition capable of suppressing the influence on the surface quality and improving the polishing rate while polishing a silicon wafer. According to the present invention, a polishing composition for polishing a silicon wafer is provided. The polishing composition includes, as abrasive particles, silicon dioxide particles having a plurality of protrusions on the surface. The polishing composition further contains an inorganic basic compound (A) selected from the group consisting of ammonia and ammonium salts.
Description
本發明係關於用於研磨矽晶圓之研磨用組成物及其製造方法。且關於使用上述研磨用組成物製造矽晶圓之方法。本申請案基於2013年9月26日申請之日本專利申請案2013-200641號主張優先權,其申請之全部內容作為參考併入本說明書中。 The present invention relates to a polishing composition for polishing a silicon wafer and a manufacturing method thereof. The present invention also relates to a method for manufacturing a silicon wafer using the polishing composition. This application claims priority based on Japanese Patent Application No. 2013-200641 filed on September 26, 2013, the entire contents of which are incorporated herein by reference.
作為半導體裝置之構成要件等所用之矽晶圓的表面一般係經過研磨步驟(粗研磨步驟)與拋光步驟(精密研磨步驟)而修飾成高品質之鏡面。上述拋光步驟典型上包含預拋光步驟(預研磨步驟)與最終拋光步驟(最終研磨步驟)。至於上述拋光步驟中之研磨方法,已知有使用含水、研磨粒及研磨促進劑之研磨用組成物之化學機械拋光(CMP)法。關於研磨用組成物之技術文獻列舉專利文獻1及2。 The surface of a silicon wafer used as a constituent element of a semiconductor device or the like is generally modified into a high-quality mirror surface through a polishing step (rough polishing step) and a polishing step (precision polishing step). The above-mentioned polishing step typically includes a pre-polishing step (a pre-polishing step) and a final polishing step (a final polishing step). As the polishing method in the above polishing step, a chemical mechanical polishing (CMP) method using a polishing composition containing water, abrasive particles, and a polishing accelerator is known. Patent documents 1 and 2 are listed in the technical literature about the polishing composition.
[專利文獻1]日本專利申請案公開2008-53415號公報 [Patent Document 1] Japanese Patent Application Publication No. 2008-53415
[專利文獻2]日本專利申請案公開2013-121631號公報 [Patent Document 2] Japanese Patent Application Publication No. 2013-121631
近年來,針對矽晶圓等半導體基板及其他基板,變得要求更高品質之表面。尤其,基於對生產性或成本等之考量,期望不延長拋光步驟所需之總研磨時間(合計研磨時間),即能獲得更高品質之表面。為此其一方法係針對拋光步驟所含之研磨步驟中之比最終拋光步驟更上游之任一研磨步驟,若能一面維持與以該研磨步驟可達到之表面品質同等或其以上之品質,一面能提高該研磨步驟中之研磨速率則為有利。係因為因此可使更下游之研磨步驟(例如最終研磨步驟)可能花費之時間變長,而將研磨對象物研磨成平滑性更高之表面之故。 In recent years, higher-quality surfaces have been required for semiconductor substrates such as silicon wafers and other substrates. In particular, based on considerations of productivity, cost, etc., it is expected that a higher-quality surface can be obtained without extending the total polishing time (total polishing time) required for the polishing step. For this reason, one of the methods is directed to any polishing step upstream of the polishing step included in the polishing step, and if it can maintain a quality equal to or higher than the surface quality achieved by the polishing step, It is advantageous to be able to increase the grinding rate in this grinding step. This is because the time that may be taken for a further downstream polishing step (for example, the final polishing step) can be lengthened, and the object to be polished is polished to a smoother surface.
然而,一般研磨後之表面品質與研磨速率成相反關係,若提高研磨速率則有表面品質下降之傾向。 However, in general, the surface quality after polishing is inversely related to the polishing rate. If the polishing rate is increased, the surface quality tends to decrease.
本發明係鑑於上述情況而完成者,其目的係提供可一方面抑制對表面品質之影響一方面提高研磨速率之研磨用組成物。本發明之另一目的係提供使用該研磨用組成物製造矽晶圓之方法。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a polishing composition that can suppress the influence on the surface quality while increasing the polishing rate. Another object of the present invention is to provide a method for manufacturing a silicon wafer using the polishing composition.
由本說明書,提供用於研磨矽晶圓之研磨用組成物。該研磨用組成物包含表面具有複數個突起之二氧化矽粒子(以下亦稱為「附突起之二氧化矽粒子」)作為研磨粒。上述研磨用組成物進而含有由氨及銨鹽所組成之群選出之無機鹼性化合物(A)。使用此種組成之研磨用組成物進行研磨時,可供給用於下游之研磨步驟之更有效率且更高品質之表面。因此,上述研磨用組成物可使用於例如拋光步驟所含之複數研磨步驟中比最終拋光步驟更上游之任一研磨步驟中,且可有助於提高最終獲得之矽晶圓之表面品質。 This specification provides a polishing composition for polishing a silicon wafer. The polishing composition includes, as abrasive particles, silicon dioxide particles having a plurality of protrusions on the surface (hereinafter also referred to as "silicon dioxide particles with protrusions"). The polishing composition further contains an inorganic basic compound (A) selected from the group consisting of ammonia and ammonium salts. When polishing using such a polishing composition, a more efficient and higher-quality surface can be supplied for a downstream polishing step. Therefore, the above-mentioned polishing composition can be used, for example, in any polishing step upstream of the multiple polishing step included in the polishing step than the final polishing step, and can contribute to improving the surface quality of the finally obtained silicon wafer.
上述附突起之二氧化矽粒子關於研磨用組成物中所含附突起之二氧化矽粒子中之粒徑比其體積平均粒徑大之附突起之二氧化矽粒子,該附突起之二氧化矽粒子之突起高度除以各自相同突起之基部之寬度獲得之值之平均(以下亦稱為「突起度」)較好為0.245以上。藉由上述突起度之平均(以下亦稱為「平均突起度」)為0.245以上之附突起之二氧化矽粒子,可適當發揮提高研磨速率之效果。 The above-mentioned protrusion-added silica particles are protrusion-containing silica particles having a larger particle diameter than the volume average particle diameter of the protrusion-containing silica particles contained in the polishing composition. The average of the values obtained by dividing the projection heights of the particles by the widths of the bases of the same projections (hereinafter also referred to as "projection degree") is preferably 0.245 or more. With the average of the protrusion degrees (hereinafter also referred to as "average protrusion degree") of 0.245 or more, the silica particles with protrusions can appropriately exert the effect of increasing the polishing rate.
上述研磨用組成物亦可進一步包含水溶性聚合物。藉由包含水溶性聚合物之研磨用組成物可提供更高品質之表面。藉此,可一面提高研磨速率,一面有效地抑制表面品質之下降。 The polishing composition may further include a water-soluble polymer. A higher quality surface can be provided by a polishing composition containing a water-soluble polymer. With this, it is possible to effectively suppress the decrease in surface quality while increasing the polishing rate.
本文揭示之技術之較佳一樣態中,上述研磨用組成物中所含之上述水溶性聚合物之量相對於上述研磨粒1kg為5g~50g。該組成中,可較佳地發揮藉由組合含有附突起之二氧化矽粒子及無機鹼性化合物(A)與水溶性聚合物所致之效果。 In a preferred aspect of the technology disclosed herein, the amount of the water-soluble polymer contained in the polishing composition is 5 g to 50 g relative to 1 kg of the polishing particles. In this composition, the effect by combining the silica particle with a processus | protrusion, an inorganic basic compound (A), and a water-soluble polymer can be exhibited favorably.
不過,近年之矽晶圓之製造方法在上述拋光步驟中,大多包含同時研磨矽晶圓兩面之兩面研磨步驟,隨後更精密地研磨該矽晶圓之單面的單面研磨步驟。兩面研磨步驟有時亦稱為1次研磨步驟,一般係將矽晶圓固定在兩面研磨裝置中進行。兩面研磨後之矽晶圓在進行洗淨、乾燥及視需要之邊緣研磨等加工後,固定於單面研磨裝置中供至單面研磨步驟。單面研磨步驟可包含2個以上之研磨步驟。該等2個以上之研磨步驟典型上包含最終研磨步驟,與在最終研磨步驟之前進行之2次研磨步驟。2次研磨步驟有時亦進一步分成複數次之研磨步驟而進行。 However, in recent years, the manufacturing methods of silicon wafers in the above-mentioned polishing steps mostly include a two-side polishing step of simultaneously polishing both sides of the silicon wafer, and then a more precise single-side polishing step of polishing one side of the silicon wafer. The double-sided polishing step is sometimes referred to as a single polishing step. Generally, the silicon wafer is fixed in a double-sided polishing device. The silicon wafers polished on both sides are cleaned, dried, and edge-polished as required, and then fixed in a single-sided polishing device for a single-sided polishing step. The single-side polishing step may include two or more polishing steps. The two or more grinding steps typically include a final grinding step and two grinding steps performed before the final grinding step. The two polishing steps may be further divided into a plurality of polishing steps.
本文揭示之研磨用組成物較好使用於上述單面研磨步驟中之最初研磨步驟(亦即,最初之2次研磨步驟)中。藉由於最初之2次研磨步驟中使用上述研磨用組成物,尤其可良好發揮因該研磨用組成物組合包含附突起之二氧化矽粒子與無機鹼性化合物(A)所致之效果。 The polishing composition disclosed herein is preferably used in the first polishing step (that is, the first two polishing steps) in the single-side polishing step described above. By using the above-mentioned polishing composition in the first two polishing steps, the effect due to the combination of the polishing composition containing the silicon dioxide particles with protrusions and the inorganic basic compound (A) can be exhibited particularly well.
依據該說明書,又提供製造用於研磨矽晶圓之研磨用組成物之方法。該方法之特徵係調製包含下列成分之研磨用組成物:表面具有複數個突起之二氧化矽粒子之研磨粒、及由氨及銨鹽所組成之群組選出之無機鹼性化 合物(A)。依據該方法時,可較好地製造本文揭示之任一種研磨用組成物。 According to the specification, a method for manufacturing a polishing composition for polishing a silicon wafer is provided. The method is characterized by preparing a polishing composition containing the following components: abrasive particles having a plurality of protruding silica particles on the surface, and inorganic alkalinization selected from the group consisting of ammonia and ammonium salts Compound (A). According to this method, any of the polishing compositions disclosed herein can be manufactured well.
依據該說明書時,又提供製造矽晶圓之方法。該方法包含下列步驟:同時研磨矽晶圓之兩面的兩面研磨步驟,更精密地研磨經過上述兩面研磨步驟之矽晶圓之單面的單面研磨步驟。上述單面研磨步驟包含2步驟以上之研磨步驟,該等中之最初研磨步驟中使用本文揭示之任一種研磨用組成物進行研磨。依據該矽晶圓製造方法,藉由於單面研磨步驟中之最初研磨步驟中使用上述研磨用組成物,可更有效地供給高品質之表面用於下游之研磨步驟。據此,最終可製造表面品質更高之矽晶圓。 According to this manual, a method for manufacturing a silicon wafer is provided. The method includes the following steps: a two-sided polishing step of polishing both sides of a silicon wafer at the same time, and a more precise single-sided polishing step of polishing one side of the silicon wafer after the two-sided polishing step. The single-side polishing step includes two or more polishing steps. In the first polishing step among them, any one of the polishing compositions disclosed herein is used for polishing. According to this silicon wafer manufacturing method, since the above-mentioned polishing composition is used in the initial polishing step in the single-side polishing step, a high-quality surface can be more efficiently supplied for the downstream polishing step. According to this, a silicon wafer with higher surface quality can be finally manufactured.
圖1係顯示投影表面具有複數個突起之二氧化矽粒子之外形之輪廓線之示意圖。 FIG. 1 is a schematic diagram showing an outline of an outer shape of a silicon dioxide particle having a plurality of protrusions on a projection surface.
以下,說明本發明之較佳實施形態。又,本說明書中特別提及之事項以外之情況之本發明實施時之必要情況係熟悉該技藝者基於該技術領域中之以往技術能以設計事項而掌握者。本發明可基於本說明書中揭示之內容與該領域中之技術知識而實施。 Hereinafter, preferred embodiments of the present invention will be described. In addition, matters other than the matters specifically mentioned in the present specification are necessary for the implementation of the present invention. Those skilled in the art can grasp design matters based on the conventional technology in the technical field. The present invention can be implemented based on the contents disclosed in this specification and technical knowledge in the field.
本文揭示之研磨用組成物包含表面具有複數個突起之二氧化矽粒子(附突起之二氧化矽粒子)作為研磨粒。該附突起之二氧化矽粒子相較於表面不具有複數個突起之形狀之二氧化矽粒子,對於研磨對象物之表面可發揮更高的機械研磨作用。此處,球狀二氧化矽粒子或花生型之二氧化矽粒子為表面不具有複數個突起之形狀之二氧化矽粒子之概念所包含之典型例。 The polishing composition disclosed herein includes silicon dioxide particles (silicon dioxide particles with projections) on the surface as abrasive particles. The silicon dioxide particles with protrusions have a higher mechanical polishing effect on the surface of the object to be polished than the silicon dioxide particles without a plurality of protrusions on the surface. Here, the spherical silica particles or peanut-type silica particles are typical examples included in the concept of silica particles having a shape without a plurality of protrusions on the surface.
附突起之二氧化矽粒子中之突起數較好每1粒子平均為2以上,更好為3以上,又更好為5以上。此處所謂突起係相較於二氧化矽粒子之粒徑,具有充分小的高度及寬度者。更具體而言,係指圖1所示之二氧化矽粒子之輪廓線中,自點A經由點C至點B之部分之長度不超過內接於該輪廓線之最大圓(最大內接圓)之圓周長之4分之1的突起。 The number of protrusions in the silicon dioxide particles with protrusions is preferably an average of 2 or more, more preferably 3 or more, and even more preferably 5 or more per particle. Here, the so-called protrusions are those having a sufficiently small height and width compared to the particle diameter of the silica particles. More specifically, it refers to the outline of the silicon dioxide particles shown in FIG. 1. The length from the point A through the point C to the point B does not exceed the largest circle (the largest inscribed circle) inscribed in the outline. ) Of a quarter of the circumference.
又,圖1中,上述點A及點B係表示上述輪廓線中之突起之基點,點C表示突起之頂點。針對本文揭示之技術中之附突起之二氧化矽粒子,所謂突起寬度係指突起之基部中之寬度,在圖1中係表示點A與點B間之距離。且,所謂突起高度係指突起之基部與距其基部最遠距離之突起部位間之距離,圖1中表示為與直線AB正交之線段CD之長度。 In FIG. 1, the points A and B are the base points of the protrusions in the contour line, and the point C is the apex of the protrusions. For the silicon dioxide particles with protrusions in the technology disclosed herein, the so-called protrusion width refers to the width in the base of the protrusions, and the distance between point A and point B is shown in FIG. 1. The height of the protrusion refers to the distance between the base of the protrusion and the protrusion at the farthest distance from the base, and is shown in FIG. 1 as the length of the line segment CD orthogonal to the straight line AB.
本文揭示之技術中,附突起之二氧化矽粒子之平均突起度並無特別限制。例如,可使用平均突起度0.170以上之附突起之二氧化矽粒子。平均突起度較好為 0.200以上,更好為0.220以上,又更好為0.245以上(例如0.255以上)。附突起之二氧化矽粒子之平均突起度變大時,有突起形狀變尖銳之傾向。據此,可更良好發揮提高研磨速率之效果。 In the technique disclosed herein, the average degree of protrusion of the silica particles with protrusions is not particularly limited. For example, silicon dioxide particles with protrusions having an average protrusion degree of 0.170 or more can be used. The average protrusion is better 0.200 or more, more preferably 0.220 or more, and still more preferably 0.245 or more (for example, 0.255 or more). When the average degree of protrusion of the silicon dioxide particles with protrusions increases, the shape of the protrusions tends to become sharp. Accordingly, the effect of increasing the polishing rate can be exhibited more favorably.
平均突起度之上限並無特別限制。就製造容易性或強度之觀點而言,通常可較好地採用平均突起度為0.5以下之附突起之二氧化矽粒子。就獲得更高表面品質之觀點而言,上述平均突起度較好為0.4以下,更好為0.37以下(例如0.35以下)。 The upper limit of the average protrusion degree is not particularly limited. From the viewpoint of ease of production or strength, usually, silicon dioxide particles with protrusions having an average protrusion degree of 0.5 or less can be suitably used. From the viewpoint of obtaining higher surface quality, the average protrusion degree is preferably 0.4 or less, and more preferably 0.37 or less (for example, 0.35 or less).
該說明書中所謂平均突起度係指在研磨用組成物中所含之附突起之二氧化矽粒子中具有比該附突起之二氧化矽粒子之體積平均粒徑大之粒徑之附突起之二氧化矽粒子中,將表面具有之突起之高度設為H,其突起之基部中之寬度設為W時,以H/W表示之值(突起度)之平均值。上述附突起之二氧化矽粒子之各突起之高度H及其基部中之寬度W可使用一般之圖像解析軟體,藉由解析附突起之二氧化矽粒子之掃描型電子顯微鏡像求出。 The term “average degree of protrusion” as used in this specification refers to the second protrusion with a particle diameter larger than the volume average particle diameter of the silica particle with protrusions contained in the polishing composition. In silicon oxide particles, when the height of the protrusions on the surface is set to H and the width of the protrusions at the base is set to W, the average value of the values (degrees of protrusions) expressed in H / W. The height H of each protrusion of the silicon dioxide particles with protrusions and the width W in the base thereof can be obtained by analyzing a scanning electron microscope image of the silicon dioxide particles with protrusions by using general image analysis software.
粒徑比研磨用組成物中所含附突起之二氧化矽粒子中之體積平均粒徑大之附突起之二氧化矽粒子中之突起之平均高度宜為例如3.5nm以上,更好為4.0nm以上。隨著該突起之平均高度變大,有提高研磨速率之效果變大之傾向。上述突起之平均高度上限並無特別限制。就獲得更高表面品質之觀點而言,上述突起之平均高度通常宜為10nm以下,較好為7.0nm以下。 The average height of the protrusions in the silica particles with protrusions whose particle diameter is larger than the volume average among the silica particles with protrusions contained in the polishing composition is preferably, for example, 3.5 nm or more, and more preferably 4.0 nm. the above. As the average height of the protrusions becomes larger, the effect of increasing the polishing rate tends to become larger. The upper limit of the average height of the protrusions is not particularly limited. From the viewpoint of obtaining higher surface quality, the average height of the protrusions is usually preferably 10 nm or less, and preferably 7.0 nm or less.
附突起之二氧化矽粒子可藉例如以下方法製造。亦即,首先,在添加有氨水作為觸媒之甲醇與水之混合溶液中,藉由連續添加烷氧基矽烷進行水解,而獲得含膠體二氧化矽粒子之漿液。加熱所得漿液餾除甲醇及氨。隨後,於漿液中添加有機鹼作為觸媒後,在70℃以上之溫度再度連續添加烷氧基矽烷進行水解,藉此於膠體二氧化矽粒子之表面形成複數個突起。此處可使用之有機鹼之具體例列舉為三乙醇胺等之胺化合物、或氫氧化四甲基銨等四級銨化合物。依據該方法,可容易地獲得金屬雜質之含量為1重量ppm以下之膠體二氧化矽粒子(附突起之二氧化矽粒子)。 The silicon dioxide particles with protrusions can be produced, for example, by the following method. That is, first, in a mixed solution of methanol and water to which ammonia water is added as a catalyst, alkoxysilane is continuously added for hydrolysis to obtain a slurry containing colloidal silica particles. The resulting slurry was distilled to remove methanol and ammonia. Subsequently, after the organic base is added to the slurry as a catalyst, alkoxysilane is continuously added again at a temperature above 70 ° C for hydrolysis, thereby forming a plurality of protrusions on the surface of the colloidal silica particles. Specific examples of the organic base that can be used here include amine compounds such as triethanolamine, and quaternary ammonium compounds such as tetramethylammonium hydroxide. According to this method, colloidal silicon dioxide particles (silicon dioxide particles with protrusions) having a content of metal impurities of 1 weight ppm or less can be easily obtained.
又,藉烷氧基矽烷之水解製造膠體二氧化矽之一般方法記載於例如作花濟夫著之「溶凝膠法之科學」之第154~156頁中。又,日本專利申請案公開平11-60232號公報中揭示將矽酸甲酯或矽酸甲酯與甲醇之混合物滴加於水、甲醇及氨或氨與銨鹽所成之混合溶劑中,使矽酸甲酯與水反應而製造之繭型膠體二氧化矽。日本專利申請案公開2001-48520號公報中揭示以酸觸媒使矽酸烷酯水解後,添加鹼觸媒經加熱進行矽酸之聚合使粒子成長而製造之細長形狀之膠體二氧化矽。日本專利申請案公開2007-153732號公報中記載藉使用特定量之特定種類之水解觸媒,以易水解性有機矽酸酯作為原料可製造具有多數小突起之膠體二氧化矽。日本專利申請案公開2002-338232號公報中記載藉由將凝集劑添加於單分散之膠體二氧化矽中 而二次凝聚成球狀。日本專利申請案公開平07-118008號公報及國際公開第2007/018069號中揭示為了獲得細長等之異形膠體二氧化矽,於自矽酸鈉獲得之活性矽酸中添加鈣鹽或鎂鹽。日本專利申請案公開2001-11433號公報中揭示藉由將鈣鹽添加於自矽酸鈉獲得之活性矽酸而獲得念珠狀之膠體二氧化矽。日本專利申請案公開2008-169102號公報中記載藉由於種晶粒子之表面生成及成長微小粒子可製造如金平糖之具有多數小突起之膠體二氧化矽。本說明書中之附突起之二氧化矽粒子可藉單獨使用該等文獻中記載之方法之1種或組合使用2種以上而製造。 In addition, a general method for producing colloidal silica by hydrolysis of alkoxysilane is described in, for example, pages 154 to 156 of "The Science of the Sol Gel Method" by Hua Zifu. Further, Japanese Patent Application Laid-Open No. 11-60232 discloses that methyl silicate or a mixture of methyl silicate and methanol is added dropwise to a mixed solvent of water, methanol, ammonia, or ammonia and an ammonium salt, so that Cocoon-type colloidal silicon dioxide produced by the reaction of methyl silicate with water. Japanese Patent Application Laid-Open No. 2001-48520 discloses an elongated colloidal silicon dioxide produced by hydrolyzing an alkyl silicate with an acid catalyst, adding an alkali catalyst, and heating and polymerizing silicic acid to grow particles. Japanese Patent Application Laid-Open No. 2007-153732 discloses that colloidal silica having a large number of small protrusions can be produced by using a hydrolyzable organosilicate as a raw material by using a specific amount of a specific type of hydrolysis catalyst. Japanese Patent Application Laid-Open No. 2002-338232 discloses adding a coagulant to a monodispersed colloidal silica. And secondary condensation into a spherical shape. Japanese Patent Application Laid-Open No. 07-118008 and International Publication No. 2007/018069 disclose that in order to obtain elongated shaped colloidal silica, calcium or magnesium salts are added to active silicic acid obtained from sodium silicate. Japanese Patent Application Publication No. 2001-11433 discloses that rosary colloidal silica is obtained by adding a calcium salt to active silicic acid obtained from sodium silicate. Japanese Patent Application Laid-Open No. 2008-169102 discloses that colloidal silica having a large number of small protrusions, such as gold flat sugar, can be produced by generating and growing fine particles on the surface of seed particles. The silica particles with protrusions in this specification can be produced by using one of the methods described in these documents alone or in combination of two or more.
本文揭示之研磨用組成物在不會大幅損及本發明效果之範圍內亦可含有附突起之二氧化矽粒子以外之研磨粒。上述附突起之二氧化矽粒子以外之研磨粒(以下亦稱為「任意研磨粒」)可為例如球狀、花生型、繭型等表面不具有複數個突起之形狀之二氧化矽研磨粒。上述任意研磨粒進而亦可為二氧化矽以外之無機粒子、有機粒子、或有機無機複合粒子。無機粒子之具體例列舉為氧化鋁粒子、氧化鈰粒子、氧化鉻粒子、二氧化鈦粒子、氧化鋯粒子、氧化鎂粒子、二氧化錳粒子、氧化鋅粒子、氧化鐵(Bengala)粒子等之氧化物粒子;氮化矽粒子、氮化硼粒子等之氮化物粒子;碳化矽粒子、碳化硼粒子等之碳化物粒子;金剛石粒子;碳酸鈣或碳酸鋇等之碳酸鹽等。有機粒子之具體例列舉為聚甲基丙烯酸甲酯(PMMA)粒子或聚(甲基)丙烯酸粒子(此處,所謂(甲基)丙烯7 意指包括丙烯酸及甲基丙烯酸)、聚丙烯腈粒子等。任意研磨粒可單獨使用1種,亦可組合2種以上使用。 The polishing composition disclosed herein may contain abrasive particles other than the silica particles with protrusions within a range that does not significantly impair the effect of the present invention. The abrasive grains (hereinafter also referred to as "arbitrary abrasive grains") other than the above-mentioned silicon dioxide particles with protrusions may be, for example, spherical, peanut-shaped, or cocoon-shaped silicon dioxide abrasive grains having no shape on the surface. The arbitrary abrasive particles may be inorganic particles, organic particles, or organic-inorganic composite particles other than silicon dioxide. Specific examples of the inorganic particles include oxide particles such as alumina particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconia particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and iron oxide (Bengala) particles. ; Nitride particles such as silicon nitride particles, boron nitride particles; carbide particles such as silicon carbide particles, boron carbide particles; diamond particles; carbonates such as calcium carbonate or barium carbonate; Specific examples of the organic particles are polymethyl methacrylate (PMMA) particles or poly (meth) acrylic particles (here, (meth) acrylic 7 It is meant to include acrylic and methacrylic acid), polyacrylonitrile particles, and the like. The arbitrary abrasive grains may be used singly or in combination of two or more kinds.
任意研磨粒之含量在研磨用組成物中所含研磨粒之總重量中,以例如30重量%以下較適當,較好為20重量%以下,更好為10重量%以下。本文揭示之技術可以使任意研磨粒之含量為研磨用組成物中所含研磨粒之總重量中之5重量%以下之樣態較好地實施。亦可為實質上不含任意研磨粒之研磨用組成物。此處,所謂研磨用組成物實質上不含任意研磨粒係指至少未刻意調配任意研磨粒。 The content of the arbitrary abrasive grains is, for example, 30% by weight or less, more preferably 20% by weight or less, and more preferably 10% by weight or less of the total weight of the abrasive particles contained in the polishing composition. The technique disclosed herein can be implemented in a manner that the content of any abrasive particles is 5% by weight or less of the total weight of the abrasive particles contained in the polishing composition. It may be a polishing composition that does not substantially contain any abrasive particles. Here, when the polishing composition does not substantially contain arbitrary abrasive grains, it means that at least arbitrary abrasive grains are not intentionally prepared.
研磨用組成物中之研磨粒之平均一次粒徑DP1並無特別限制。研磨粒之平均一次粒徑DP1基於研磨效率等之觀點,較好為10nm以上,更好為15nm以上,又更好為20nm以上。此外,基於容易獲得平滑性更高之表面的觀點,研磨粒之平均一次粒徑DP1較好為100nm以下,更好為50nm以下,又更好為40nm以下。 The average primary particle diameter D P1 of the abrasive particles in the polishing composition is not particularly limited. From the viewpoint of polishing efficiency and the like, the average primary particle diameter D P1 of the abrasive particles is preferably 10 nm or more, more preferably 15 nm or more, and still more preferably 20 nm or more. In addition, from the viewpoint of easily obtaining a smoother surface, the average primary particle diameter D P1 of the abrasive grains is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.
又,研磨粒之平均一次粒徑DP1可由例如以BET法測定之比表面積S(m2/g),以平均一次粒徑DP1(nm)=2727/S之式算出。研磨粒之比表面積的測定可使用例如Micromeritics公司製之表面積測定裝置,商品名「Flow Sorb II 2300」進行。 The average primary particle diameter D P1 of the abrasive particles can be calculated from the specific surface area S (m 2 / g) measured by the BET method, for example, using the formula of the average primary particle diameter D P1 (nm) = 2727 / S. The measurement of the specific surface area of the abrasive grains can be performed using, for example, a surface area measuring device manufactured by Micromeritics, trade name "Flow Sorb II 2300".
研磨用組成物中之研磨粒之平均二次粒徑DP2並無特別限制,但基於研磨效率等之觀點,較好為20nm以上,更好為30nm以上,又更好為40nm以上。此外, 基於研磨用組成物之沉降安定性(分散安定性)之觀點,研磨粒之平均二次粒徑DP2宜為300nm以下,典型為200nm以下,較好為150nm以下,更好為100nm以下。另外,基於表面品質之觀點,研磨粒之平均二次粒徑DP2較好為90nm以下,更好為80nm以下,又更好為70nm以下(例如65nm以下)。 The average secondary particle diameter D P2 of the abrasive particles in the polishing composition is not particularly limited, but from the viewpoint of polishing efficiency and the like, it is preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more. In addition, from the viewpoint of the sedimentation stability (dispersion stability) of the polishing composition, the average secondary particle diameter D P2 of the abrasive particles is preferably 300 nm or less, typically 200 nm or less, preferably 150 nm or less, and more preferably 100 nm or less. . From the viewpoint of surface quality, the average secondary particle diameter D P2 of the abrasive particles is preferably 90 nm or less, more preferably 80 nm or less, and still more preferably 70 nm or less (for example, 65 nm or less).
又,研磨粒之平均二次粒徑DP2可使用例如日機裝股份有限公司製之型號「UPA-UT151」,藉由動態光散射法作為體積平均粒徑加以測定。研磨粒之體積平均粒徑係等於藉由以動態光散射法測定之粒徑之自小的研磨粒依序累積研磨粒之體積至達到研磨用組成物中之全部研磨粒之累積體積之50%時最後之累積之研磨粒之粒徑。 The average secondary particle diameter D P2 of the abrasive particles can be measured as a volume average particle diameter by a dynamic light scattering method using a model "UPA-UT151" manufactured by Nikkiso Co., Ltd., for example. The volume average particle size of the abrasive grains is equal to the cumulative volume of the abrasive grains in order from the small abrasive grains measured by the dynamic light scattering method to 50% of the cumulative volume of all the abrasive grains in the polishing composition. The last cumulative particle size of the abrasive particles.
研磨用組成物中之研磨粒之體積基準95%粒徑(D95值)較好為500nm以下,更好為400nm以下。隨著研磨粒之體積基準95%粒徑減小,會有提高研磨用組成物之沉降安定性(分散安定性)之傾向。且,會有容易使利用研磨用組成物研磨後之研磨對象物之表面粗糙度變小之傾向。研磨粒之體積基準95%粒徑等於自以動態光散亂法測定之粒徑之小的研磨粒依序累積研磨粒之體積至達到研磨用組成物中之全部研磨粒之體積累積95%時最後之累積研磨粒之粒徑。 The volume-based 95% particle diameter (D95 value) of the abrasive particles in the polishing composition is preferably 500 nm or less, and more preferably 400 nm or less. As the volume-based 95% particle size of the abrasive particles decreases, the settling stability (dispersion stability) of the polishing composition tends to be improved. In addition, there is a tendency that the surface roughness of the object to be polished after polishing with the polishing composition tends to be small. The basis volume of 95% of the abrasive particles is equal to the accumulation of the volume of the abrasive particles in order from the small abrasive particles with a particle size measured by the dynamic light scattering method until the cumulative volume of all the abrasive particles in the polishing composition reaches 95%. The final cumulative abrasive particle size.
本文揭示之研磨用組成物中所含研磨粒之鈉、鉀、鈣、硼、鋁、鈦、鋯、錳、鐵、鈷、銅、鋅、銀、鉛等金屬雜質之含量較好分別為1重量ppm以下, 該等金屬雜質之合計含量更好為1重量ppm以下。金屬雜質之含量可利用例如IC重量分析裝置測定。 The content of the metal particles such as sodium, potassium, calcium, boron, aluminum, titanium, zirconium, manganese, iron, cobalt, copper, zinc, silver, lead and the like contained in the abrasive composition disclosed herein is preferably 1 respectively. Weight ppm or less, The total content of these metal impurities is more preferably 1 ppm by weight or less. The content of metal impurities can be measured using, for example, an IC gravimetric analyzer.
本文揭示之研磨用組成物包含由氨及銨鹽所組成之群選出之至少1種無機鹼性化合物(A)。上述銨鹽之具體例列舉為碳酸氫銨、碳酸銨、氯化銨、氯酸銨等。該等可單獨使用1種或組合2種以上使用。較好為至少包含氨作為無機鹼性化合物(A)之研磨用組成物。 The polishing composition disclosed herein includes at least one inorganic basic compound (A) selected from the group consisting of ammonia and ammonium salts. Specific examples of the ammonium salt include ammonium bicarbonate, ammonium carbonate, ammonium chloride, and ammonium chlorate. These can be used individually by 1 type or in combination of 2 or more types. The polishing composition preferably contains at least ammonia as the inorganic basic compound (A).
雖無特別限制,但研磨用組成物中所含無機鹼性化合物(A)之量以該研磨用組成物之每1kg研磨粒,可為例如0.1莫耳以上,通常以0.5莫耳以上較適當。基於獲得更大效果之觀點,每1kg研磨粒之無機鹼性化合物(A)之量較好為1莫耳以上,更好為2莫耳以上,又更好為3莫耳以上(典型為4莫耳以上,例如5莫耳以上)。每1kg研磨粒之無機鹼性化合物(A)之量之上限並無特別限制,通常以50莫耳以下較適當,較好為30莫耳以下,更好為20莫耳以下(例如10莫耳以下)。 Although not particularly limited, the amount of the inorganic basic compound (A) contained in the polishing composition may be, for example, 0.1 mol or more per 1 kg of the polishing composition, and usually 0.5 mol or more is appropriate. . From the viewpoint of obtaining greater effects, the amount of the inorganic basic compound (A) per 1 kg of the abrasive grains is preferably 1 mol or more, more preferably 2 mol or more, and still more preferably 3 mol or more (typically 4 mols). Molar or more, such as 5 Moore or more). The upper limit of the amount of the inorganic basic compound (A) per 1 kg of the abrasive grains is not particularly limited, and generally it is more appropriate to be 50 mol or less, preferably 30 mol or less, and more preferably 20 mol or less (for example, 10 mol the following).
當實施本文揭示之技術時,藉由組合含有附突起之二氧化矽研磨粒與無機鹼性化合物(A)之研磨用組成物可解決上述課題之理由未必清楚,但認為例如如下。 When the technology disclosed herein is implemented, the reason why the above-mentioned problem can be solved by combining a polishing composition containing silicon dioxide abrasive particles with protrusions and an inorganic basic compound (A) is not necessarily clear, but it is considered as follows, for example.
亦即,研磨對象物的矽晶圓表面可藉該矽晶圓之氧化 生成之氧化膜薄薄地被覆。例如,單面研磨步驟中最初研磨步驟(亦即,最初之2次研磨步驟)開始時之矽晶圓表面可在兩面研磨後之洗淨、或單面研磨步驟開始前之間存在因矽晶圓之表面與空氣直接接觸而自然氧化等所生成之氧化膜。處於以該氧化膜被覆之表面狀態之矽晶圓即使為例如1nm左右(例如0.5nm~2nm左右)之薄的氧化膜,研磨去除該氧化膜至到達原先研磨對象的矽(典型為單結晶矽)表面需花費時間之結果,會使包含去除該氧化膜之時間在內之整體的研磨速率變低。另一方面,以KOH等無機強鹼作為研磨促進劑之研磨用組成物對於氧化膜雖可顯示高的研磨速率,但該研磨用組成物由於對矽之化學研磨作用強,故如上述,與提高研磨速率相反,處於研磨後之表面品質下降之傾向。 That is, the silicon wafer surface of the polishing object can be oxidized by the silicon wafer. The resulting oxide film is thinly covered. For example, the surface of the silicon wafer at the beginning of the first polishing step (that is, the first 2 polishing steps) in the single-sided polishing step may be cleaned after the two-sided polishing, or there may be a silicon crystal between before the start of the single-sided polishing step. An oxide film formed by the round surface in direct contact with air and natural oxidation. Even if the silicon wafer in the surface state covered with the oxide film is a thin oxide film of, for example, about 1 nm (for example, about 0.5 nm to 2 nm), the oxide film is polished and removed until it reaches the original silicon (typically, single crystal silicon) As a result of the time required for the surface, the overall polishing rate including the time for removing the oxide film becomes low. On the other hand, although a polishing composition using an inorganic strong alkali such as KOH as a polishing accelerator can exhibit a high polishing rate for an oxide film, the polishing composition has a strong chemical polishing effect on silicon, so as described above, and Increasing the polishing rate, on the contrary, tends to reduce the surface quality after polishing.
本發明人等與為了迅速去除氧化膜而利用專用化學研磨作用之技術思想偏離,而針對一方面利用矽之研磨中可實現高的表面品質之研磨促進劑,一方面在氧化膜之去除時主要利用研磨粒之機械研磨作用而積極檢討之結果,因而完成本發明。依據本文揭示之研磨用組成物,藉由組合含有由氨及銨鹽所組成之群選出之無機鹼性化合物(A)與附突起之二氧化矽粒子,而活用附突起之二氧化矽粒子之機械研磨作用而有效地去除氧化膜,且可藉無機鹼性化合物(A)之效果維持高的表面品質。附突起之二氧化矽粒子亦能有效提高矽之研磨速率。據此,在例如單面研磨步驟中最初之研磨步驟開始時,即使表面以薄的 氧化膜被覆之矽晶圓,認為仍可獲得一方面維持表面品質一方面提高研磨速率之效果者。 The present inventors deviated from the technical idea of using a dedicated chemical polishing effect in order to quickly remove the oxide film, and aimed at a polishing accelerator that can achieve high surface quality in polishing using silicon on the one hand, and on the other hand, it is mainly used in the removal of the oxide film As a result of actively reviewing the mechanical polishing action of the abrasive particles, the present invention has been completed. According to the polishing composition disclosed herein, the inorganic basic compound (A) selected from the group consisting of ammonia and ammonium salt is combined with the silicon dioxide particles with protrusions, and the silicon dioxide particles with protrusions are utilized. The mechanical polishing action effectively removes the oxide film and maintains high surface quality by the effect of the inorganic basic compound (A). Silicon dioxide particles with protrusions can also effectively improve the polishing rate of silicon. Accordingly, when, for example, the first grinding step in the single-side grinding step is started, An oxide film-coated silicon wafer is considered to have the effect of maintaining the surface quality while improving the polishing rate.
本文揭示之研磨用組成物較好包含水。上述研磨用組成物中所含之水較好使用離子交換水(去離子水)、純水、超純水、蒸餾水等。為了儘可能地避免阻礙研磨用組成物中所含有之其他成分之作用,使用之水較好為例如過渡金屬離子之合計含量為100ppb以下。例如,可藉離子交換樹脂去除雜質離子、藉過濾去除異物、藉蒸餾等操作提高水之純度。 The polishing composition disclosed herein preferably contains water. The water contained in the polishing composition is preferably ion-exchanged water (deionized water), pure water, ultrapure water, distilled water, or the like. In order to avoid as much as possible hindering the effects of other components contained in the polishing composition, the water used is preferably, for example, a total content of transition metal ions of 100 ppb or less. For example, ion exchange resin can be used to remove impurity ions, filtering can be used to remove foreign matter, and distillation can be used to improve the purity of water.
本文中揭示之研磨用組成物亦可視需要進一步含有可與水均勻混合之有機溶劑(低級醇、低級酮等)。通常,較好研磨用組成物中所含之溶劑的90體積%以上為水,更好95體積%以上(典型上為99~100體積%)為水。 The polishing composition disclosed herein may optionally further contain an organic solvent (lower alcohol, lower ketone, etc.) that can be mixed with water uniformly. Generally, it is preferred that 90% by volume or more of the solvent contained in the polishing composition is water, and more preferably 95% by volume or more (typically 99 to 100% by volume) is water.
本文揭示之研磨用組成物(典型上為漿液狀之組成物)可較好地以例如其固體成分含量(非揮發性成分(non-volatile content);NV)為0.01重量%~50重量%,其餘部分為水系溶劑(水或水與上述有機溶劑之混合溶劑)之形態,或其餘部分為水系溶劑及揮發性化合物(例如氨)之形態實施。更好為上述NV為0.05重量%~40重量%之形態。又,上述固體成分含量(NV)係自使研磨用組成物在105℃乾燥24小時後之殘留物於上述研磨用組成物中所佔之重量之比例求出。 The polishing composition disclosed herein (typically a slurry-like composition) may preferably have, for example, a solid content (non-volatile content; NV) of 0.01% to 50% by weight, The remaining part is implemented in the form of an aqueous solvent (water or a mixed solvent of water and the above-mentioned organic solvent), or the remaining part is in the form of an aqueous solvent and a volatile compound (such as ammonia). More preferably, the NV is in a form of 0.05% to 40% by weight. The solid content (NV) was determined from the weight ratio of the residue in the polishing composition after the polishing composition was dried at 105 ° C. for 24 hours.
本文揭示之研磨用組成物較好進一步包含水溶性聚合物。藉由適當使用水溶性聚合物,可更適當地兼具因使用附突起之二氧化矽研磨粒之研磨速率提高效果與良好的表面品質。 The polishing composition disclosed herein preferably further comprises a water-soluble polymer. By appropriately using the water-soluble polymer, it is possible to more appropriately combine the polishing rate improvement effect and the good surface quality due to the use of the silicon dioxide abrasive particles with protrusions.
使用之水溶性聚合物種類並無特別限制,可由研磨用組成物之領域中公知之水溶性聚合物中適當選擇。水溶性聚合物可單獨使用1種或組合2種以上使用。 The kind of water-soluble polymer to be used is not particularly limited, and can be appropriately selected from water-soluble polymers known in the field of polishing compositions. The water-soluble polymer may be used singly or in combination of two or more kinds.
上述水溶性聚合物可為分子中具有選自陽離子性基、陰離子性基及非離子性基之至少一種官能基者。上述水溶性聚合物可為例如分子中具有羥基、羧基、醯氧基、磺基、1級醯胺構造、雜環構造、乙烯基構造、聚氧伸烷基構造等者。基於凝聚物之減低或洗淨性提高等之觀點,可較佳地採用非離子性聚合物作為上述水溶性聚合物。 The water-soluble polymer may have at least one functional group selected from a cationic group, an anionic group, and a nonionic group in the molecule. The water-soluble polymer may be, for example, a hydroxyl group, a carboxyl group, a fluorenyloxy group, a sulfo group, a primary amidine structure, a heterocyclic structure, a vinyl structure, a polyoxyalkylene structure, or the like. From the viewpoints of reduction of aggregates and improvement of detergency, a nonionic polymer can be preferably used as the water-soluble polymer.
本文揭示之研磨用組成物中可較好地使用之水溶性聚合物之例列舉為纖維素衍生物、澱粉衍生物、含氧伸烷基單位之聚合物、含氮原子之聚合物、聚乙烯醇等。 Examples of water-soluble polymers that can be suitably used in the polishing composition disclosed herein include cellulose derivatives, starch derivatives, polymers containing oxygen alkylene units, polymers containing nitrogen atoms, and polyethylene. Alcohol and so on.
纖維素衍生物之具體例列舉為羥基乙基纖維素(HEC)、羥基丙基纖維素、羥基乙基甲基纖維素、羥基丙基甲基纖維素、甲基纖維素、乙基纖維素、乙基羥基乙基纖維素、羧基甲基纖維素等。其中以羥基乙基纖維素 較佳。 Specific examples of the cellulose derivative include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, Ethylhydroxyethyl cellulose, carboxymethyl cellulose, and the like. Hydroxyethyl cellulose Better.
澱粉衍生物之具體例列舉為α化澱粉、普魯藍多糖、環糊精等。其中以普魯藍多糖較佳。 Specific examples of the starch derivative include alpha starch, pullulan, and cyclodextrin. Among them, pullulan polysaccharide is preferred.
含氧伸烷基單位之聚合物例示為聚環氧乙烷(PEO)或環氧乙烷(EO)與環氧丙烷(PO)或環氧丁烷(BO)之嵌段共聚物、EO與PO或BO之無規共聚物等。其中,以EO與PO之嵌段共聚物或EO與PO之無規共聚物較佳。EO與PO之嵌段共聚物可為含PEO嵌段與聚環氧丙烷(PPO)嵌段之二嵌段體、三嵌段體等。上述三嵌段體之例,包含PEO-PPO-PEO型三嵌段體及PPO-PEO-PPO型三嵌段體。通常,更好為PEO-PPO-PEO型三嵌段體。 An example of a polymer containing oxygen alkylene units is a block copolymer of polyethylene oxide (PEO) or ethylene oxide (EO) and propylene oxide (PO) or butylene oxide (BO). Random copolymers of PO or BO, etc. Among them, a block copolymer of EO and PO or a random copolymer of EO and PO is preferred. The block copolymer of EO and PO may be a diblock body, a triblock body, etc. containing a PEO block and a polypropylene oxide (PPO) block. Examples of the triblock include a PEO-PPO-PEO type triblock and a PPO-PEO-PPO type triblock. Generally, it is more preferably a PEO-PPO-PEO type triblock.
EO與PO之嵌段共聚物或無規共聚物中,構成該共聚物之EO與PO之莫耳比(EO/PO),基於對水之溶解性或洗淨性等之觀點,較好大於1,更好為2以上,又更好為3以上(例如5以上)。 Among block copolymers or random copolymers of EO and PO, the molar ratio of EO and PO (EO / PO) constituting the copolymer is preferably greater than the viewpoint of solubility in water or detergency. 1, more preferably 2 or more, and still more preferably 3 or more (for example, 5 or more).
含有氮原子之聚合物可使用主鏈上含有氮原子之聚合物及側鏈官能基(側基)上具有氮原子之聚合物之任一種。主鏈上含有氮原子之聚合物之例列舉為N-醯基伸烷基亞胺型單體之均聚物及共聚物。N-醯基伸烷基亞胺型單體之具體例列舉為N-乙醯基伸乙基亞胺、N-丙醯基伸乙基亞胺等。側基上具有氮原子之聚合物列舉為例如含N-乙烯基型之單體單位之聚合物等。例如,可適當的採用N-乙烯基吡咯啶酮之均聚物及共聚物等。其中較佳 之含氮原子之聚合物例示為聚(N-乙烯基吡咯啶酮)。 As the polymer containing a nitrogen atom, any one of a polymer containing a nitrogen atom in a main chain and a polymer having a nitrogen atom in a side chain functional group (side group) can be used. Examples of polymers containing nitrogen atoms in the main chain include homopolymers and copolymers of N-fluorenylalkyleneimine-type monomers. Specific examples of the N-fluorenylalkyleneimine-type monomer include N-ethylfluorenylethylimine, N-propylfluorenylethylimine, and the like. The polymer having a nitrogen atom in the side group is exemplified by a polymer containing an N-vinyl monomer unit. For example, homopolymers and copolymers of N-vinylpyrrolidone can be suitably used. Which is better The nitrogen atom-containing polymer is exemplified by poly (N-vinylpyrrolidone).
使用聚乙烯醇(PVA)作為水溶性聚合物時,該聚乙烯醇之皂化度並無特別限制。此外,亦可使用四級銨構造等之具有陽離子性基之陽離子化PVA作為上述PVA。上述陽離子化PVA可為源自例如二烯丙基二烷基銨鹽、N-(甲基)丙烯醯基胺基烷基-N,N,N-三烷基銨鹽等之具有陽離子性基之單體者。 When polyvinyl alcohol (PVA) is used as the water-soluble polymer, the degree of saponification of the polyvinyl alcohol is not particularly limited. In addition, a cationic PVA having a cationic group such as a quaternary ammonium structure may be used as the PVA. The cationized PVA may have a cationic group derived from, for example, diallyl dialkylammonium salt, N- (meth) acrylfluorenylamino alkyl-N, N, N-trialkylammonium salt, and the like. The individual.
本文揭示之研磨用組成物中,水溶性聚合物之分子量並無特別限制。可使用重量平均分子量(Mw)為200×104以下之水溶性聚合物。基於研磨用組成物之過濾性或洗淨性之觀點,較好為Mw在150×104以下之水溶性聚合物。且,基於提高研磨後之表面品質之觀點,水溶性聚合物之Mw較好為1×104以上,更好為2×104以上。 In the polishing composition disclosed herein, the molecular weight of the water-soluble polymer is not particularly limited. Water-soluble polymers having a weight average molecular weight (Mw) of 200 × 10 4 or less can be used. From the viewpoint of the filterability or detergency of the polishing composition, a water-soluble polymer having an Mw of 150 × 10 4 or less is preferred. In addition, from the viewpoint of improving the surface quality after polishing, the Mw of the water-soluble polymer is preferably 1 × 10 4 or more, more preferably 2 × 10 4 or more.
更佳之Mw範圍可隨著水溶性聚合物之種類而異。例如,使用纖維素衍生物(例如HEC)作為水溶性聚合物時,Mw較好為10×104~150×104,更好為15×104~130×104。使用PVA(可為陽離子化PVA)作為水溶性聚合物時,其Mw較好為1×104~10×104,更好為1×104~7×104,又更好為1×104~5×104(例如1×104~3×104)。使用含有氮原子之聚合物作為水溶性聚合物時,其Mw較好為1×104~15×104,更好為1×104~10×104,又更好為2×104~7×104。 A better Mw range may vary depending on the kind of water-soluble polymer. For example, when a cellulose derivative (for example, HEC) is used as the water-soluble polymer, Mw is preferably 10 × 10 4 to 150 × 10 4 , more preferably 15 × 10 4 to 130 × 10 4 . When PVA (which can be cationized PVA) is used as the water-soluble polymer, its Mw is preferably 1 × 10 4 to 10 × 10 4 , more preferably 1 × 10 4 to 7 × 10 4 , and even more preferably 1 × 10 4 to 5 × 10 4 (for example, 1 × 10 4 to 3 × 10 4 ). When a polymer containing a nitrogen atom is used as the water-soluble polymer, its Mw is preferably 1 × 10 4 to 15 × 10 4 , more preferably 1 × 10 4 to 10 × 10 4 , and even more preferably 2 × 10 4 ~ 7 × 10 4 .
水溶性聚合物之重量平均分子量(Mw)與數平均分子量(Mn)之關係並無特別限制。就防止產生凝 聚物等之觀點而言,較好為例如分子量分佈(Mw/Mn)為10.0以下者,更好為7.0以下者。 The relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble polymer is not particularly limited. Prevent condensation From the viewpoint of polymers, for example, those having a molecular weight distribution (Mw / Mn) of 10.0 or less are preferred, and those of 7.0 or less are more preferred.
又,水溶性聚合物之Mw及Mn可採用基於水系之凝膠滲透層析儀(GPC)之值(水系,聚環氧乙烷換算)。 Moreover, the Mw and Mn of a water-soluble polymer can use the value of the water-based gel permeation chromatography (GPC) (water-based, polyethylene oxide conversion).
雖無特別限制,但水溶性聚合物之含量每1kg研磨粒可為例如0.01g以上。與附突起之二氧化矽研磨粒之組合中,基於獲得更良好表面品質之觀點,每1kg研磨粒之水溶性聚合物之含量以超過1g較適當,較好為5g以上,更好為10g以上,又更好為15g以上。且,與無機鹼性化合物(A)之組合中基於獲得良好研磨速率之觀點,水溶性聚合物對於研磨粒1kg之含量通常以50g以下較適當,較好為40g以下,更好為35g以下(例如30g以下)。 Although not particularly limited, the content of the water-soluble polymer may be, for example, 0.01 g or more per 1 kg of abrasive particles. In the combination with the silicon dioxide abrasive particles with protrusions, from the viewpoint of obtaining a better surface quality, the content of the water-soluble polymer per 1 kg of the abrasive particles is more than 1 g, preferably 5 g or more, and more preferably 10 g or more. , And more preferably 15g or more. In addition, from the viewpoint of obtaining a good polishing rate in the combination with the inorganic basic compound (A), the content of the water-soluble polymer for 1 kg of the abrasive particles is generally 50 g or less, preferably 40 g or less, and more preferably 35 g or less ( For example, 30g or less).
本文揭示之研磨用組成物在不大幅損及本發明效果之範圍內,可刻意或非刻意地含有無機鹼性化合物(A)以外之鹼性化合物(B)。作為該任意成分之鹼性化合物(B)可為有機鹼性化合物(B1),亦可為無機鹼性化合物(B2)。鹼性化合物(B)可單獨使用1種或組合2種以上使用。 The polishing composition disclosed herein may contain a basic compound (B) other than the inorganic basic compound (A) intentionally or unintentionally, as long as the effect of the present invention is not significantly impaired. The basic compound (B) as the optional component may be an organic basic compound (B1) or an inorganic basic compound (B2). The basic compound (B) may be used alone or in combination of two or more.
有機鹼性化合物(B1)之例列舉為四烷基銨鹽等四級銨鹽。上述銨鹽中之陰離子可為例如OH-、F-、 Cl-、Br-、I-、ClO4 -、BH4 -等。例如,可適當使用氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨等四級銨鹽。其中以氫氧化四甲基銨較佳。 Examples of the organic basic compound (B1) include a quaternary ammonium salt such as a tetraalkylammonium salt. Ammonium salts of the above anions may be, for example, OH -, F -, Cl - , Br -, I -, ClO 4 -, BH 4 - and the like. For example, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide can be suitably used. Among them, tetramethylammonium hydroxide is preferred.
有機鹼性化合物(B1)之其他例列舉為甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙二胺、單乙醇胺、N-(β-胺基乙基)乙醇胺、六亞甲基二胺、二伸乙基三胺、三伸乙基四胺等胺類;無水哌啶、哌啶六水合物、1-(2-胺基乙基)哌啶、N-甲基哌啶等哌啶類;咪唑或三唑等唑(azole)類;胍等。 Other examples of the organic basic compound (B1) include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, and N- (β-aminoethyl) Amines such as ethanolamine, hexamethylenediamine, diethylene triamine, triethylene tetramine; anhydrous piperidine, piperidine hexahydrate, 1- (2-aminoethyl) piperidine, N -Piperidines such as methylpiperidine; azoles such as imidazole or triazole; guanidine and the like.
無機鹼性化合物(B2)之例列舉為氨、鹼金屬或鹼土類金屬之氫氧化物、碳酸鹽、碳酸氫鹽等;氨等。上述氫氧化物之具體例列舉為氫氧化鉀、氫氧化鈉等。上述碳酸鹽或碳酸氫鹽之具體例列舉為碳酸氫銨、碳酸銨、碳酸氫鉀、碳酸鉀、碳酸氫鈉、碳酸鈉等。 Examples of the inorganic basic compound (B2) include ammonia, alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, and the like; ammonia and the like. Specific examples of the hydroxide include potassium hydroxide and sodium hydroxide. Specific examples of the carbonate or bicarbonate include ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, and sodium carbonate.
除無機鹼性化合物(A)外使用有機鹼性化合物(B1)時,該有機鹼性化合物(B1)之使用量通常以每1kg研磨粒未達4莫耳較適當,基於表面品質等之觀點較好未達3莫耳,更好未達2莫耳。研磨用組成物中所含之有機鹼性化合物(B1)之莫耳數較好比無機鹼性化合物(A)之莫耳數少。或者,本文揭示之研磨用組成物亦可為實質上不含有機鹼性化合物(B1)之組成。其中,所謂研磨用組成物實質上不含有機鹼性化合物(B1)係指至少刻意不含有機鹼性化合物(B1)。因此,含無法避免之源自原料或製法之微量(例如每1kg研磨粒為0.01莫耳以 下,較好0.005莫耳以下)之有機鹼性化合物(B1)之研磨用組成物在本文中可包含於實質上不含有機鹼性化合物(B1)之研磨用組成物之概念。 When an organic basic compound (B1) is used in addition to the inorganic basic compound (A), the amount of the organic basic compound (B1) to be used is usually less than 4 mol per 1 kg of abrasive grains. From the viewpoint of surface quality and the like It is preferably less than 3 moles, more preferably less than 2 moles. The molar number of the organic basic compound (B1) contained in the polishing composition is preferably smaller than the molar number of the inorganic basic compound (A). Alternatively, the polishing composition disclosed herein may be a composition substantially free of an organic basic compound (B1). Here, the composition for polishing does not substantially contain an organic basic compound (B1) means that it does not contain at least the organic basic compound (B1) intentionally. Therefore, it contains unavoidable traces derived from raw materials or manufacturing methods (e.g. 0.01 mol per 1 kg of abrasive particles Hereinafter, the polishing composition of the organic basic compound (B1), which is preferably 0.005 mole or less, may be included herein as a concept of the polishing composition that does not substantially contain the organic basic compound (B1).
除無機鹼性化合物(A)外使用無機鹼性化合物(B2)時,該無機鹼性化合物(B2)之使用量通常以每1kg研磨粒未達1莫耳較適當,基於表面品質之觀點較好未達0.5莫耳,更好未達0.2莫耳。研磨用組成物中所含無機鹼性化合物(B2)之莫耳數較好比無機鹼性化合物(A)之莫耳數少。或者,本文揭示之研磨用組成物亦可為實質上不含無機鹼性化合物(B2)之組成。 When an inorganic basic compound (B2) is used in addition to the inorganic basic compound (A), the amount of the inorganic basic compound (B2) used is usually less than 1 mol per 1 kg of abrasive grains. It is less than 0.5 moles, more preferably less than 0.2 moles. The molar number of the inorganic basic compound (B2) contained in the polishing composition is preferably smaller than the molar number of the inorganic basic compound (A). Alternatively, the polishing composition disclosed herein may be a composition substantially free of an inorganic basic compound (B2).
除無機鹼性化合物(A)外使用鹼性化合物(B)時,研磨用組成物中所含之鹼性化合物(B)之莫耳數較好比無機鹼性化合物(A)之莫耳數少。或者,本文揭示之研磨用組成物亦可為實質上不含鹼性化合物(B)之組成。 When the basic compound (B) is used in addition to the inorganic basic compound (A), the molar number of the basic compound (B) contained in the polishing composition is preferably smaller than the molar number of the inorganic basic compound (A). . Alternatively, the polishing composition disclosed herein may be a composition substantially free of a basic compound (B).
本文揭示之研磨用組成物可含有螯合劑作為任意成分。螯合劑係與研磨組成物中可含之金屬雜質形成錯離子將其捕捉,藉此發揮抑制金屬雜質對研磨對象物污染之作用。 The polishing composition disclosed herein may contain a chelating agent as an arbitrary component. The chelating agent forms metal ions which may be contained in the polishing composition and traps them, thereby exerting the effect of suppressing the metal impurities from contaminating the object to be polished.
螯合劑之例列舉為胺基羧酸系螯合劑及有機膦酸系螯合劑。胺基羧酸系螯合劑之例包含乙二胺四乙酸、乙二胺四乙酸鈉、氮基三乙酸、氮基三乙酸鈉、氮基三乙酸銨、 羥基乙基乙二胺三乙酸、羥基乙基乙二胺三乙酸鈉、二伸乙基三胺五乙酸、二伸乙基三胺五乙酸鈉、三伸乙基四胺六乙酸及三伸乙基四胺六乙酸鈉。有機膦酸系螯合劑之例包含2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、胺基三(亞甲基膦酸)、乙二胺肆(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)、乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、乙烷-1-羥基-1,1-二膦酸、乙烷-1-羥基-1,1,2-三膦酸、乙烷-1,2-二羧基-1,2-二膦酸、甲烷羥基膦酸、2-膦醯基丁烷-1,2-二羧酸、1-膦醯基丁烷-2,3,4-三羧酸及α-甲基膦醯基琥珀酸。該等中以有機膦酸系螯合劑較佳,其中較佳者列舉為乙二胺肆(亞甲基膦酸)及二伸乙基三胺五六乙酸。最佳之螯合劑列舉為乙二胺肆(亞甲基膦酸)。 Examples of the chelating agent include an aminocarboxylic acid-based chelating agent and an organic phosphonic acid-based chelating agent. Examples of the amino carboxylic acid-based chelating agent include ethylenediamine tetraacetic acid, sodium ethylenediamine tetraacetate, nitrogen triacetic acid, sodium nitrogen triacetate, ammonium nitrogen triacetate, Hydroxyethyl ethylenediamine triacetic acid, sodium hydroxyethyl ethylenediamine triacetate, diethylene triamine pentaacetic acid, sodium diethylene triamine pentaacetate, triethylene tetraamine hexaacetic acid, and triethylene glycol Sodium tetraamine hexaacetate. Examples of the organic phosphonic acid-based chelating agent include 2-aminoethylphosphonic acid, 1-hydroxyethylene-1,1-diphosphonic acid, aminotris (methylenephosphonic acid), and ethylenediamine Methylphosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1- Hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxyl-1,2-diphosphonic acid, methane hydroxyphosphonic acid, 2-phosphinofluorenylbutane-1,2-dicarboxylic acid, 1-phosphinofluorenylbutane-2,3,4-tricarboxylic acid and α-methylphosphinofluorenylsuccinic acid. Among these, an organic phosphonic acid-based chelating agent is preferable, and among them, ethylenediamine (methylenephosphonic acid) and diethylene triamine pentahexaacetic acid are preferred. The most preferred chelating agent is ethylenediamine (methylenephosphonic acid).
本文揭示之研磨用組成物中可含界面活性劑(典型為分子量未達1×104之水溶性有機化合物)作為任意成分。藉由使用界面活性劑,可提高研磨用組成物之分散安定性。界面活性劑可單獨使用1種或組合2種以上使用。 The polishing composition disclosed herein may contain a surfactant (typically a water-soluble organic compound having a molecular weight of less than 1 × 10 4 ) as an arbitrary component. By using a surfactant, the dispersion stability of the polishing composition can be improved. The surfactant can be used singly or in combination of two or more kinds.
至於界面活性劑,較好採用陰離子性或非離子性者。基於低起泡性或pH調整之容易性之觀點,更好為非離子性之界面活性劑。列舉為例如聚乙二醇、聚丙二醇、聚四亞甲基二醇等之氧伸烷基聚合物;聚氧伸乙基烷基醚、聚氧伸乙基烷基苯基醚、聚氧伸乙基烷基胺、聚氧伸乙基脂肪酸酯、聚氧伸乙基甘油醚脂肪酸酯、聚氧伸乙基山梨糖 醇酐脂肪酸酯等之聚氧伸烷基加成物;複數種之氧伸烷基之共聚物(二嵌段型、三嵌段型、無規型、交互型)等之非離子性界面活性劑。 As the surfactant, an anionic or nonionic one is preferably used. From the viewpoint of low foamability or ease of pH adjustment, a nonionic surfactant is more preferred. Examples are oxyalkylene polymers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like; polyoxyethylene ethyl ether, polyoxyethyl alkyl phenyl ether, and polyoxyethylene Ethylalkylamine, polyoxyethylene fatty acid ester, polyoxyethylene ethyl glyceryl ether fatty acid ester, polyoxyethylene sorbose Polyoxyalkylene adducts of alcohol anhydride fatty acid esters, etc .; nonionic interfaces of plural types of oxyalkylene copolymers (diblock, triblock, random, interactive), etc. Active agent.
界面活性劑之使用量以每1kg研磨粒為5g以下較佳,較好為2g以下,更好為1g以下。本文揭示之研磨用組成物可較好以實質上不含界面活性劑之樣態實施。 The amount of the surfactant used is preferably 5 g or less per 1 kg of abrasive particles, more preferably 2 g or less, and even more preferably 1 g or less. The polishing composition disclosed herein can be preferably implemented in a state substantially free of a surfactant.
本文揭示之研磨用組成物在不顯著妨礙本發明效果之範圍內,亦可視需要進一步含有有機酸、有機酸鹽、無機酸、無機酸鹽、防腐劑、防黴劑等之可使用於研磨用組成物(典型為矽晶圓之拋光步驟所用之研磨用組成物)之習知添加劑。 The polishing composition disclosed herein may further contain organic acids, organic acid salts, inorganic acids, inorganic acid salts, preservatives, and antifungal agents as long as they do not significantly impede the effects of the present invention. A conventional additive for a composition, typically a polishing composition used in the polishing step of a silicon wafer.
有機酸之例列舉為甲酸、乙酸、丙酸等脂肪酸,苯甲酸、鄰苯二甲酸等芳香族羧酸,檸檬酸、草酸、酒石酸、蘋果酸、馬來酸、富馬酸、琥珀酸、有機磺酸、有機膦酸等。有機酸鹽之例列舉為有機酸之鹼金屬鹽(鈉鹽、鉀鹽等)或銨鹽等。無機酸之例列舉為硫酸、硝酸、鹽酸、碳酸等。無機酸鹽之例列舉為無機酸之鹼金屬鹽(鈉鹽、鉀鹽等)或銨鹽。有機酸及其鹽、及無機酸及其鹽可單獨使用1種或組合2種以上使用。 Examples of organic acids include fatty acids such as formic acid, acetic acid, and propionic acid; aromatic carboxylic acids such as benzoic acid and phthalic acid; citric acid, oxalic acid, tartaric acid, malic acid, maleic acid, fumaric acid, succinic acid, organic Sulfonic acid, organic phosphonic acid, etc. Examples of the organic acid salt include alkali metal salts (such as sodium salts and potassium salts) and ammonium salts of organic acids. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, and carbonic acid. Examples of the inorganic acid salt include alkali metal salts (such as sodium salts and potassium salts) or ammonium salts of inorganic acids. The organic acid and its salt, and the inorganic acid and its salt can be used singly or in combination of two or more kinds.
防腐劑及防黴劑之例列舉為異噻唑啉系化合物、對羥基苯甲酸酯類、苯氧基乙醇等。 Examples of the antiseptic and antifungal agent are isothiazoline compounds, parabens, phenoxyethanol, and the like.
本文揭示之研磨用組成物較好實質上不含氧 化劑。係因為研磨用組成物中含氧化劑時,藉由將該組成物供給於矽晶圓,使該矽晶圓之表面氧化而產生氧化膜,藉此可降低研磨速率。此處氧化劑之具體例列舉為過氧化氫(H2O2)、二氯異氰尿酸鈉等。又,所謂研磨用組成物實質上不含氧化劑係指至少刻意不含氧化劑。 The polishing composition disclosed herein is preferably substantially free of an oxidizing agent. This is because when the polishing composition contains an oxidant, the composition is supplied to a silicon wafer, and the surface of the silicon wafer is oxidized to generate an oxide film, thereby reducing the polishing rate. Specific examples of the oxidant herein include hydrogen peroxide (H 2 O 2 ), sodium dichloroisocyanurate, and the like. It should be noted that the composition for polishing does not substantially contain an oxidant means that it does not contain at least an oxidant intentionally.
本文揭示之研磨用組成物典型上係以含該研磨用組成物之研磨液之形態供給於研磨對象物,使用於該研磨對象物之研磨。上述研磨液可為例如將本文揭示之任一研磨用組成物稀釋(典型上係以水稀釋)而調製者。或者,亦可直接使用該研磨用組成物作為研磨液。亦即,本文揭示之技術中之研磨用組成物之概念包含供給於研磨對象物的該研磨對象物之研磨所用之研磨液(作用漿液)與經稀釋作為研磨液使用之濃縮液(研磨液之原液)兩者。至於含本文揭示之研磨用組成物的研磨液之其他例列舉為調整該組成物之pH而成之研磨液。 The polishing composition disclosed herein is typically supplied to a polishing object in the form of a polishing liquid containing the polishing composition, and is used for polishing the polishing object. The polishing liquid may be prepared by diluting any of the polishing compositions disclosed herein (typically, dilution with water). Alternatively, the polishing composition may be directly used as a polishing liquid. That is, the concept of the polishing composition in the technology disclosed herein includes a polishing liquid (acting slurry) used for polishing the polishing object supplied to the polishing object, and a concentrated liquid (a polishing liquid) Stock solution) both. As another example of the polishing liquid containing the polishing composition disclosed herein, a polishing liquid obtained by adjusting the pH of the composition is mentioned.
本文揭示之研磨液中之研磨粒含量並未特別限制,典型上為0.05重量%以上,較好為0.1重量%以上,更好為0.2重量%以上,又更好為0.3重量%以上(例如,0.4重量%以上)。藉由增加研磨粒之含量,可實現更高的研磨速率。且,基於研磨用組成物之分散安定性等之觀點,通常上述含量以10重量%以下為適當,較好為7重量%以下,更好為5重量%以下,又更好為3重量%以 下。基於獲得更高表面品質之觀點,可將研磨粒之含量設為2重量%以下,亦可設為1重量%以下,亦可設為0.8重量%以下(例如0.5重量%以下)。 The content of the abrasive particles in the polishing liquid disclosed herein is not particularly limited, but is typically 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and more preferably 0.3% by weight or more (for example, 0.4% by weight or more). By increasing the content of abrasive particles, a higher polishing rate can be achieved. In addition, from the viewpoint of dispersion stability and the like of the polishing composition, the content is usually 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, and still more preferably 3% by weight or less. under. From the viewpoint of obtaining higher surface quality, the content of the abrasive grains may be set to 2% by weight or less, or 1% by weight or less, or 0.8% by weight or less (for example, 0.5% by weight or less).
研磨液之pH較好為8.0以上,更好為9.0以上,又更好為9.5以上。研磨液之pH變高時,有矽晶圓之研磨速率提高之傾向。研磨液之pH上限值並無特別限制,較好為12.0以下,更好為11.5以下,又更好為11.0以下。藉此,可防止研磨液中所含之研磨粒(尤其是附突起之二氧化矽粒子)因鹼性化合物而溶解,可抑制研磨粒之機械研磨作用之下降。上述pH對於矽晶圓之研磨所用之研磨液可較為適用。研磨液之pH可藉由使用pH計(例如,堀場製作所製之玻璃電極式氫離子濃度指示計(型號F-23)),且使用標準緩衝液(苯二甲酸鹽pH緩衝液pH:4.01(25℃)、中性磷酸鹽pH緩衝液pH:6.86(25℃)、碳酸鹽pH緩衝液pH:10.01(25℃))經3點校正後,將玻璃電極放入研磨液中,測定經過2分鐘以上且安定之值予以掌握。 The pH of the polishing liquid is preferably 8.0 or more, more preferably 9.0 or more, and still more preferably 9.5 or more. As the pH of the polishing liquid becomes higher, the polishing rate of the silicon wafer tends to increase. The upper limit of the pH of the polishing liquid is not particularly limited, but is preferably 12.0 or less, more preferably 11.5 or less, and even more preferably 11.0 or less. Thereby, the abrasive particles (especially the silicon dioxide particles with protrusions) contained in the polishing liquid can be prevented from being dissolved by the basic compound, and the reduction of the mechanical polishing effect of the abrasive particles can be suppressed. The above-mentioned pH may be more suitable for a polishing liquid used for polishing silicon wafers. The pH of the polishing liquid can be determined by using a pH meter (for example, a glass electrode hydrogen ion concentration indicator (model F-23) manufactured by Horiba), and using a standard buffer (phthalate pH buffer pH: 4.01). (25 ° C), neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C)) After 3 points correction, the glass electrode was placed in the polishing solution and the measurement process was completed. Master the stable value for more than 2 minutes.
本文揭示之研磨用組成物在供給於研磨對象物之前亦可為經濃縮之形態(亦即,研磨液之濃縮液形態)。該經濃縮之形態的研磨用組成物基於製造、流通、保存等時之便利性或降低成本等之觀點而言較有利。濃縮倍率例如以體積換算可為2倍~100倍左右,通常宜為5倍~50倍左 右。較佳之一樣態之研磨用組成物之濃縮倍率為10倍~40倍。 The polishing composition disclosed herein may be in a concentrated form (that is, a concentrated liquid form of a polishing liquid) before being supplied to the object to be polished. This concentrated polishing composition is advantageous from the viewpoints of convenience, cost reduction, and the like during production, distribution, and storage. The concentration ratio can be about 2 to 100 times in volume conversion, and usually about 5 to 50 times. right. Preferably, the concentration ratio of the polishing composition in the same state is 10 to 40 times.
處於該濃縮液形態之研磨用組成物可以在期望之時點經稀釋而調製研磨液,並將該研磨液供給於研磨對象物之樣態使用。上述稀釋典型上可藉由將前述水系溶劑添加於上述濃縮液中並混合而進行。此外,上述水系溶劑為混合溶劑時,可僅添加該水系溶劑之構成成分中之一部分成分並經稀釋,亦可添加以與上述水系溶劑不同之量比含有該等構成成分之混合溶劑進行稀釋。此外,如後述之多劑型研磨用組成物中,可使該等中之一部分藥劑稀釋後與其他藥劑混合而調製研磨液,亦可混合複數種藥劑後稀釋其混合物而調製研磨液。 The polishing composition in the form of the concentrated liquid can be diluted at a desired point to prepare a polishing liquid, and the polishing liquid can be used by supplying it to the object to be polished. The dilution is typically performed by adding the aqueous solvent to the concentrated solution and mixing them. In addition, when the water-based solvent is a mixed solvent, only a part of the constituents of the water-based solvent may be added and diluted, or a mixed solvent containing the constituents at a different ratio from the water-based solvent may be added and diluted. In addition, in a multi-dose type polishing composition described later, one part of these agents may be diluted and mixed with other agents to prepare a polishing liquid, or a plurality of agents may be mixed to dilute the mixture to prepare a polishing liquid.
上述濃縮液之NV可為例如50重量%以下。基於研磨用組成物之安定性(例如研磨粒之分散安定性)或過濾性等之觀點,通常,濃縮液之NV宜設為40重量%以下,較好為30重量%以下,更好為20重量%以下,例如15重量%以下。且,基於製造、流通、保存等時之便利性或成本降低等之觀點,濃縮液之NV宜設為0.5重量%以上,較好為1重量%以上,更好為3重量%以上,例如為5重量%以上。 The NV of the concentrated liquid may be, for example, 50% by weight or less. From the viewpoints of the stability of the polishing composition (such as the dispersion stability of the abrasive particles) or the filterability, the NV of the concentrated liquid is generally preferably 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight. Less than or equal to 15% by weight. In addition, from the standpoint of convenience, cost reduction, etc. during manufacturing, distribution, storage, etc., the NV of the concentrated liquid should preferably be 0.5% by weight or more, preferably 1% by weight or more, and more preferably 3% by weight or more. 5% by weight or more.
上述濃縮液中之研磨粒含量可設為例如50重量%以下。基於研磨用組成物之安定性(例如,研磨粒之分散安定性)或過濾性等之觀點,通常,上述含量較好為45重量%以下,更好為40重量%以下。較佳之一樣態 中,可將研磨粒之含量設為30重量%以下,亦可設為20重量%以下(例如15重量%以下)。此外,基於製造、流通、保存等時之便利性或成本降低等之觀點,研磨粒之含量可設為例如0.5重量%以上,較好為1重量%以上,更好為3重量%以上(例如4重量%以上)。 The content of the abrasive particles in the concentrated liquid may be, for example, 50% by weight or less. From the viewpoints of the stability of the polishing composition (for example, the dispersion stability of the abrasive particles) and the filterability, the content is usually preferably 45% by weight or less, more preferably 40% by weight or less. Better state The content of the abrasive grains may be 30% by weight or less, or 20% by weight or less (for example, 15% by weight or less). In addition, from the viewpoints of convenience, cost reduction, and the like during manufacturing, distribution, and storage, the content of the abrasive particles can be set to, for example, 0.5% by weight or more, preferably 1% by weight or more, and more preferably 3% by weight or more (for example, 4% by weight or more).
本文揭示之研磨用組成物可為一劑型、亦可為以二劑型為代表之多劑型。例如,構成為使含有該研磨用組成物之構成成分(典型上為水系溶劑以外之成分)中之一部分成分的A液,與含剩餘成分之B液混合並使用於研磨對象物之研磨。 The polishing composition disclosed herein may be a one-dose form or a multi-dose form represented by a two-dose form. For example, the A liquid containing a part of the constituents (typically, components other than the water-based solvent) of the polishing composition is mixed with the B liquid containing the remaining components and is used for polishing the object to be polished.
本文揭示之研磨用組成物之製造方法並未特別限制。例如可使用翼式攪拌機、超音波分散機、均質混合機等之習知混合裝置,混合研磨用組成物中所含之各成分。混合該等成分之樣態並未特別限制,例如可一次混合全部成分,亦可依適當設定之順序混合。 The manufacturing method of the polishing composition disclosed herein is not particularly limited. For example, a conventional mixing device such as a wing mixer, an ultrasonic disperser, and a homomixer can be used to mix each component contained in the polishing composition. The form of mixing these components is not particularly limited, and for example, all the components may be mixed at a time, or they may be mixed in an appropriately set order.
本文揭示之研磨用組成物較好使用作為用於研磨矽晶圓(典型上為單結晶矽晶圓)之研磨用組成物。以下,針對使用本文揭示之研磨用組成物對研磨對象物進行研磨之方法的較佳樣態加以說明。 The polishing composition disclosed herein is preferably used as a polishing composition for polishing a silicon wafer (typically a single crystal silicon wafer). Hereinafter, a preferable aspect of a method for polishing an object to be polished using the polishing composition disclosed herein will be described.
亦即,準備含本文揭示之任一研磨用組成物之研磨液 (典型上為漿液狀之研磨液,有時亦稱為研磨漿液)。準備上述研磨液時,可包含對研磨用組成物施加濃度調整(例如稀釋)、pH調整等之操作而調製研磨液。或者,上述研磨用組成物可直接使用作為研磨液。此外,多劑型之研磨用組成物之情況下,準備上述研磨液時,可包含混合該等之藥劑、於該混合前稀釋1或複數種藥劑、於該混合後稀釋該混合物等。 That is, preparing a polishing liquid containing any of the polishing compositions disclosed herein (Typically a slurry-like polishing liquid, sometimes referred to as a polishing slurry). When the polishing liquid is prepared, the polishing liquid may be prepared by applying operations such as concentration adjustment (for example, dilution) and pH adjustment to the polishing composition. Alternatively, the polishing composition can be directly used as a polishing liquid. In addition, in the case of a multi-dose type polishing composition, when preparing the above-mentioned polishing liquid, it may include mixing such pharmaceuticals, diluting one or more pharmaceuticals before mixing, diluting the mixture after mixing, and the like.
接著,將該研磨液供給於研磨對象物,以常用方法進行研磨。例如,進行矽晶圓之最初單面研磨步驟時,係將經過摩擦步驟及兩面研磨步驟(1次研磨步驟)之矽晶圓固定在一般之單面研磨裝置上,通過該研磨裝置之研磨墊將研磨液供給於上述矽晶圓之表面(研磨對象面)。典型上,係邊連續供給上述研磨液,邊將研磨墊抵壓於矽晶圓表面並使二者相對移動(例如旋轉移動)。隨後,視需要再經過2次研磨步驟,進行最後之最終拋光而完成研磨對象物之研磨。 Next, this polishing liquid is supplied to an object to be polished, and is polished by a usual method. For example, when performing the first single-side polishing step of a silicon wafer, the silicon wafer that has undergone the rubbing step and the double-side polishing step (one polishing step) is fixed to a general single-side polishing device, and the polishing pad of the polishing device A polishing liquid is supplied to the surface (surface to be polished) of the silicon wafer. Typically, the polishing liquid is continuously supplied, and the polishing pad is pressed against the surface of the silicon wafer and the two are moved relative to each other (for example, rotational movement). Subsequently, if necessary, go through two more grinding steps to perform the final final polishing to complete the polishing of the object to be polished.
又,使用本文揭示之研磨用組成物之研磨步驟中所使用之研磨墊並無特別限制。例如可使用不織布類型、毛氈類型、聚胺基甲酸酯類型、含研磨粒者、不含研磨粒者等之任一種。 The polishing pad used in the polishing step using the polishing composition disclosed herein is not particularly limited. For example, any of a non-woven fabric type, a felt type, a polyurethane type, an abrasive particle-containing material, and an abrasive particle-free material can be used.
依據本說明書,提供包含使用本文揭示之研磨用組成物研磨矽晶圓之步驟之矽晶圓製造方法。本文揭示之矽晶圓之製造方法亦可進一步包含在使用上述研磨用組成物之研磨步驟之前,進行上述矽晶圓之兩面研磨之步 驟。且,亦可進一步包含對經過使用上述研磨用組成物之研磨步驟之矽晶圓施以最終拋光之步驟。此處所謂最終拋光係指目標物之製造製程中之最後拋光步驟(亦即,該步驟之後不再進行拋光之步驟)。上述兩面研磨步驟或最終拋光步驟可使用本文揭示之研磨用組成物進行,亦可使用其他研磨用組成物進行。 According to this specification, a method for manufacturing a silicon wafer including a step of polishing a silicon wafer using the polishing composition disclosed herein is provided. The manufacturing method of the silicon wafer disclosed herein may further include a step of polishing both sides of the silicon wafer before using the polishing step of the polishing composition. Step. In addition, the method may further include a step of subjecting the silicon wafer subjected to the polishing step using the polishing composition to a final polishing step. The so-called final polishing here refers to the last polishing step in the manufacturing process of the target (that is, the step in which polishing is not performed after this step). The above-mentioned two-side polishing step or final polishing step may be performed using the polishing composition disclosed herein, or may be performed using other polishing compositions.
較佳之一樣態中,使用上述研磨用組成物之矽晶圓研磨步驟為比最終拋光更上游之拋光步驟。其中,對經過兩面研磨步驟之矽晶圓進行之最初單面研磨步驟(最初之2次研磨步驟)中,較好使用上述研磨用組成物。本文揭示之研磨用組成物可較好地使用作為上述最初2次研磨步驟中之矽晶圓研磨所用之研磨用組成物。 In a preferred aspect, the polishing step of the silicon wafer using the polishing composition described above is a polishing step upstream of the final polishing. Among these, in the first single-side polishing step (the first two polishing steps) performed on the silicon wafer that has undergone the double-side polishing step, the above-mentioned polishing composition is preferably used. The polishing composition disclosed herein can be preferably used as a polishing composition for polishing a silicon wafer in the first two polishing steps.
以下,說明本發明有關之數個實施例,但並非意圖將本發明限制於該實施例所示者。又,以下說明中「份」及「%」只要未特別指明則為重量基準。 Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in the embodiments. In addition, "part" and "%" in the following description are based on weight unless otherwise specified.
混合表面具有複數個突起之二氧化矽粒子(研磨粒A)、氨水(濃度29%)、水溶性聚合物及純水,調製本例之研磨用組成物。 A plurality of protruding silicon dioxide particles (abrasive particles A), ammonia water (29% concentration), a water-soluble polymer, and pure water were mixed on the surface to prepare the polishing composition of this example.
表面具有粒徑比使用之研磨粒A中之體積平均粒徑大之二氧化矽粒子之突起高度之平均為5.5nm,平均突起度為0.27。該研磨粒A之平均一次粒徑DP1為30nm,平均 二次粒徑DP2為58nm。上述平均粒徑DP1係使用Micromeritics公司製之表面積測定裝置,商品名「Flow Sorb II 2300」測定者。此外,上述二次平均粒徑DP2係使用日機裝股份有限公司製之型號「UPA-UT151」測定之體積平均二次粒徑。 The average height of the protrusions of the silicon dioxide particles having a surface diameter larger than the volume average particle diameter in the used abrasive grain A was 5.5 nm, and the average protrusion degree was 0.27. The average primary particle diameter D P1 of this abrasive grain A was 30 nm, and the average secondary particle diameter D P2 was 58 nm. The average particle diameter D P1 is measured using a surface area measuring device manufactured by Micromeritics, trade name "Flow Sorb II 2300". In addition, the above-mentioned secondary average particle diameter D P2 is a volume average secondary particle diameter measured using a model "UPA-UT151" manufactured by Nikkiso Co., Ltd.
水溶性聚合物係使用Mw為約120×104之羥基乙基纖維素(HEC)。 As the water-soluble polymer, hydroxyethyl cellulose (HEC) having a Mw of about 120 × 10 4 was used.
研磨粒A、氨水及水溶性聚合物之使用量為使研磨用組成物中之研磨粒A之含量成為0.46%,氨(NH3)之含量成為0.041%,水溶性聚合物之含量成為0.009%(相對於研磨粒1kg為19.6g)之量。所得研磨用組成物之pH為10.4。 The amount of abrasive grain A, ammonia water and water-soluble polymer is used so that the content of abrasive grain A in the polishing composition becomes 0.46%, the content of ammonia (NH 3 ) becomes 0.041%, and the content of water-soluble polymer becomes 0.009%. (19.6 g with respect to 1 kg of abrasive particles). The pH of the obtained polishing composition was 10.4.
實施例1中,使用表面具有複數個突起之二氧化矽粒子(研磨粒B)取代研磨粒A。表面具有粒徑比所使用之研磨粒B中之體積平均粒徑大之二氧化矽粒子之突起高度之平均為5.5nm,平均突起度為0.25。該研磨粒B之平均一次粒徑DP1為30nm,平均二次粒徑DP2為58nm。其他方面與實施例1相同,調製本例之研磨用組成物。該研磨用組成物之pH為10.4。 In Example 1, the abrasive grains A were replaced with silica particles (abrasive grains B) having a plurality of protrusions on the surface. The average height of the protrusions of the silicon dioxide particles having a larger surface diameter than the volume average particle diameter of the abrasive grains B used was 5.5 nm, and the average protrusion degree was 0.25. The average primary particle diameter D P1 of the abrasive particles B was 30 nm, and the average secondary particle diameter D P2 was 58 nm. Otherwise, it was the same as Example 1, and the polishing composition of this example was prepared. The polishing composition had a pH of 10.4.
混合研磨粒A、氨水(濃度29%)、氫氧化四甲基銨 (TMAH)、水溶性聚合物及純水,調製本例之研磨用組成物。水溶性聚合物係使用與實施例1相同之HEC。研磨粒A、氨水、TMAH及水溶性聚合物之使用量為使研磨用組成物中之研磨粒A之含量成為0.46%、氨(NH3)之含量成為0.03%,TMAH之含量成為0.06%,水溶性聚合物之含量成為0.009%之量。所得研磨用組成物之pH為10.8。 The abrasive grain A, ammonia water (concentration: 29%), tetramethylammonium hydroxide (TMAH), water-soluble polymer, and pure water were mixed to prepare the polishing composition of this example. As the water-soluble polymer, the same HEC as in Example 1 was used. The amount of abrasive particles A, ammonia, TMAH, and water-soluble polymer is used so that the content of abrasive particles A in the polishing composition is 0.46%, the content of ammonia (NH 3 ) is 0.03%, and the content of TMAH is 0.06%. The content of the water-soluble polymer becomes an amount of 0.009%. The pH of the obtained polishing composition was 10.8.
實施例1中,使用平均一次粒徑DP1為35nm,平均二次粒徑DP2為64nm之花生形狀之膠體二氧化矽(研磨粒C)取代研磨粒A。其他方面與實施例1相同,調製本例之研磨用組成物。pH為10.4, In Example 1, peanut-shaped colloidal silicon dioxide (abrasive particles C) having an average primary particle diameter D P1 of 35 nm and an average secondary particle diameter D P2 of 64 nm were used instead of the abrasive particles A. Otherwise, it was the same as Example 1, and the polishing composition of this example was prepared. pH is 10.4,
實施例1中,使用平均一次粒徑DP1為80nm,平均二次粒徑DP2為97nm之球狀膠體二氧化矽(研磨粒D)取代研磨粒A。其他方面與實施例1相同,調製本例之研磨用組成物。pH為10.6, In Example 1, spherical colloidal silica (abrasive particles D) having an average primary particle diameter D P1 of 80 nm and an average secondary particle diameter D P2 of 97 nm were used instead of the abrasive particles A. Otherwise, it was the same as Example 1, and the polishing composition of this example was prepared. pH is 10.6,
實施例1中,以在研磨用組成物中之含量成為1.365%之量使用TMAH取代氨水。其他方面與實施例1相同,調製本例之研磨用組成物。pH為11.0。 In Example 1, TMAH was used in place of ammonia water so that the content in the polishing composition became 1.365%. Otherwise, it was the same as Example 1, and the polishing composition of this example was prepared. The pH was 11.0.
實施例1中,以在研磨用組成物中之含量成為0.84%之量使用氫氧化鉀(KOH)取代氨水。其他方面與實施例1相同,調製本例之研磨用組成物。pH為11.0。 In Example 1, potassium hydroxide (KOH) was used in place of ammonia water in such an amount that the content in the polishing composition became 0.84%. Otherwise, it was the same as Example 1, and the polishing composition of this example was prepared. The pH was 11.0.
實施例1中,以在研磨用組成物中之含量成為2.235%之量使用三乙醇胺取代氨水。其他方面與實施例1相同,調製本例之研磨用組成物。pH為11.0。 In Example 1, triethanolamine was used in place of ammonia water so that the content in the polishing composition became 2.235%. Otherwise, it was the same as Example 1, and the polishing composition of this example was prepared. The pH was 11.0.
各例之研磨用組成物直接使用作為研磨液,進行以下之評價試驗,其結果示於表1。試驗片係使用藉由兩面研磨裝置將直徑6英吋(約150mm)之矽晶圓(傳導型:P型,結晶方位:〈100〉,電阻率:0.1Ω.cm以上未達100Ω.cm)調整成表面粗糙度0.5nm~1.5nm後,藉以下條件洗淨(SC-1洗淨)者。 The polishing composition of each example was directly used as a polishing liquid, and the following evaluation tests were performed. The results are shown in Table 1. The test piece was a silicon wafer with a diameter of 6 inches (approximately 150 mm) (conduction type: P type, crystal orientation: <100>, resistivity: 0.1 Ω.cm or more and less than 100 Ω.cm) using a double-sided grinding device. After adjusting to a surface roughness of 0.5 nm to 1.5 nm, wash under the following conditions (SC-1 cleaning).
將NH4OH(29%):H2O2(31%):去離子水(DIW)=1:1:15(體積比)之洗淨液收容於第1洗淨槽及第2洗淨槽各槽中且保持在80℃。洗淨係藉由將洗淨對象物浸漬於第1洗淨槽中5分鐘,隨後經過利用超純水之洗滌槽,於第2洗淨槽中浸漬5分鐘而進行。 NH 4 OH (29%): H 2 O 2 (31%): deionized water (DIW) = 1: 1: 15 (volume ratio) was stored in the first washing tank and the second washing Each tank was kept at 80 ° C. The washing is performed by immersing the object to be cleaned in the first washing tank for 5 minutes, and then passing through the washing tank using ultrapure water, and immersing in the second washing tank for 5 minutes.
測定上述試驗片之重量(W1[g])。使之浸漬於2.5%濃度之氫氟酸中10秒後,以流量7升/分鐘之水流洗淨10秒。藉以下條件研磨該試驗片。 The weight (W1 [g]) of the test piece was measured. It was immersed in hydrofluoric acid having a concentration of 2.5% for 10 seconds, and then washed with a flow of water at a flow rate of 7 liters / minute for 10 seconds. This test piece was ground under the following conditions.
研磨裝置:不二越機械工業股份有限公司製之單面研磨裝置,型號「SPM-15」 Grinding device: Single-sided grinding device manufactured by Fujitsu Machinery Industry Co., Ltd., model "SPM-15"
研磨墊:FUJIMI INCORPORATED股份有限公司製,毛氈研磨墊「Surfin 000FM」 Polishing pad: felt polishing pad "Surfin 000FM" made by FUJIMI INCORPORATED Co., Ltd.
研磨壓力:94g/cm2 Grinding pressure: 94g / cm 2
壓盤轉數:30轉/分鐘 Platen revolutions: 30 rpm
研磨頭轉數:30轉/分鐘 Grinding head revolutions: 30 rpm
研磨時間:30分鐘 Grinding time: 30 minutes
研磨液之供給速率:500mL/分鐘(源源流出而使用) Supply rate of polishing liquid: 500mL / min
研磨液之溫度:25℃ Temperature of grinding liquid: 25 ℃
以上述SC-1洗淨條件洗淨研磨後之試驗片後,測定其重量(W2[g])。由其結果,根據以下之計算式,算出因研磨而減少之厚度(研磨量)。 After the polished test piece was washed under the above SC-1 washing conditions, the weight (W2 [g]) was measured. From the results, the thickness (polishing amount) reduced by polishing was calculated from the following calculation formula.
(W1-W2)[g]/矽密度[g/cm3](=2.33g/cm3)/被研磨面積[cm2](=363cm2)=研磨量[cm] (W1-W2) [g] / Density of silicon [g / cm 3 ] (= 2.33g / cm 3 ) / Area to be polished [cm 2 ] (= 363cm 2 ) = Grinding amount [cm]
該研磨量除以研磨時間(=30分鐘)算出研磨速率。又,藉以下5階段使該研磨速率點數化。 This polishing amount was divided by the polishing time (= 30 minutes) to calculate the polishing rate. The polishing rate was counted in the following five steps.
5點:23nm/分鐘以上 5 o'clock: 23nm / min or more
4點:21nm/分鐘以上未達23nm/分鐘 4 o'clock: 21nm / min or more but less than 23nm / min
3點:19nm/分鐘以上未達21nm/分鐘 3 o'clock: 19nm / min or more but less than 21nm / min
2點:17nm/分鐘以上未達19nm/分鐘 2 o'clock: 17nm / min or more but less than 19nm / min
1點:1nm/分鐘以上未達17nm/分鐘 1 point: 1nm / min or more but less than 17nm / min
藉由使用研磨漿液(FUJIMI INCORPORATED股份有限公司製,商品名「GLANZOX 2100」)對上述試驗片進行預研磨,調整成表面粗糙度0.1nm~10nm後,藉以下條件進行研磨。 The above test piece was pre-polished by using a polishing slurry (manufactured by FUJIMI INCORPORATED Co., Ltd., trade name "GLANZOX 2100"), adjusted to a surface roughness of 0.1 nm to 10 nm, and polished under the following conditions.
研磨裝置:不二越機械工業股份有限公司製之單面研磨裝置,型號「SPM-15」 Grinding device: Single-sided grinding device manufactured by Fujitsu Machinery Industry Co., Ltd., model "SPM-15"
研磨墊:FUJIMI INCORPORATED股份有限公司製,毛氈研磨墊「Surfin 000FM」 Polishing pad: felt polishing pad "Surfin 000FM" made by FUJIMI INCORPORATED Co., Ltd.
研磨壓力:94g/cm2 Grinding pressure: 94g / cm 2
壓盤轉數:30轉/分鐘 Platen revolutions: 30 rpm
研磨頭轉數:30轉/分鐘 Grinding head revolutions: 30 rpm
研磨時間:5分鐘 Grinding time: 5 minutes
研磨液之供給速率:500mL/分鐘(源源流出而使用) Supply rate of polishing liquid: 500mL / min
研磨液之溫度:25℃ Temperature of grinding liquid: 25 ℃
以上述SC-1洗淨條件洗淨研磨後之試驗片後,使用KLM Tencol公司製之晶圓檢查裝置,商品名「AWIS3110」測定濁度。且,藉以下5階段將其結果點數化。 After the polished test piece was cleaned under the above SC-1 cleaning conditions, the turbidity was measured using a wafer inspection apparatus manufactured by KLM Tencol Corporation under the trade name "AWIS3110". The results are counted in the following five stages.
5點:0.035ppm以上未達0.040ppm 5 points: 0.035ppm or more and less than 0.040ppm
4點:0.040ppm以上未達0.045ppm 4 points: 0.040ppm or more and less than 0.045ppm
3點:0.045ppm以上未達0.050ppm 3 points: 0.045ppm or more and less than 0.050ppm
2點:0.050ppm以上未達0.060ppm 2 points: 0.050ppm or more and less than 0.060ppm
1點:0.060ppm以上 1 point: 0.060ppm or more
使用KLM Tencol公司製之晶圓檢查裝置,商品名「AWIS3110」,計算洗淨後之直徑6英吋矽晶圓表面存在之80nm以上大小之缺陷(顆粒)個數。且其結果藉以下之5階段點數化。 A wafer inspection device made by KLM Tencol Corporation, trade name "AWIS3110" was used to calculate the number of defects (particles) above 80 nm in size on the surface of a 6-inch diameter silicon wafer after cleaning. And the result is converted into 5 points by the following points.
5點:計數未達600 5 points: Count is less than 600
4點:計數600以上未達700 4 points: counting from 600 to 700
3點:計數700以上未達800 3 points: counting from 700 to 800
2點:計數800以上未達900 2 points: counting from 800 to 900
14點:計數900以上 14 points: counting over 900
如表1所示,依據使用組合含有附突起之二氧化矽粒子與氨之研磨用組成物之實施例1、2,相較於使用表面不具有複數個突起之形狀之二氧化矽粒子,具體而言為花生形狀或球狀之膠體二氧化矽作為研磨粒之比較例1、2,可使研磨速率提高10%~20%。此外,依據實施例1、2,濁度及缺陷數任一方面均可維持與比較例1相同程度之高的表面品質。使用氨以外亦使用TMAH作為研磨促進劑之實施例3相較於單獨使用氨之實施例1、2,有獲得更高研磨速率提升效果,且缺陷數亦相等,但濁度值稍上升之傾向。 As shown in Table 1, according to Examples 1 and 2 in which a polishing composition containing silicon dioxide particles with protrusions and ammonia was used, compared with the use of silicon dioxide particles having a shape without a plurality of protrusions on the surface, specifically, In terms of Comparative Examples 1 and 2 in which peanut-shaped or spherical colloidal silica is used as abrasive particles, the grinding rate can be increased by 10% to 20%. In addition, according to Examples 1 and 2, both the turbidity and the number of defects can maintain the same high surface quality as that of Comparative Example 1. Compared with Examples 1 and 2 using ammonia alone, Example 3, which uses TMAH as a polishing accelerator in addition to ammonia, has a higher polishing rate improvement effect, and the number of defects is also equal, but the turbidity value tends to increase slightly. .
另一方面,使用不含無機鹼性化合物(A)之研磨用組成物之比較例3~5儘管使用附突起之二氧化矽粒子,但研磨速率仍較比較例1低。單獨使用KOH作為研磨促進劑之比較例3與比較例1相比較濁度值大為上升,且表面品質降低。 On the other hand, Comparative Examples 3 to 5 in which a polishing composition containing no inorganic basic compound (A) was used. Although the silicon dioxide particles with protrusions were used, the polishing rate was lower than that in Comparative Example 1. In Comparative Example 3 in which KOH was used alone as a polishing accelerator, the turbidity value increased significantly compared to Comparative Example 1, and the surface quality decreased.
以上,已詳細說明本發明之具體例,但該等僅為例示,並非限制申請專利範圍。申請專利範圍中記載之技術包含以上例示之具體例之各種變形、變更者。 In the foregoing, specific examples of the present invention have been described in detail, but these are merely examples and do not limit the scope of patent application. The technology described in the scope of the patent application includes various modifications and changes to the specific examples illustrated above.
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