TW201412962A - Polishing composition, method for producing the polishing composition, and method for producing semiconductor substrate using the polishing composition - Google Patents
Polishing composition, method for producing the polishing composition, and method for producing semiconductor substrate using the polishing composition Download PDFInfo
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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Abstract
Description
本發明係關於研磨用組成物、該研磨用組成物之製造方法、及使用該研磨用組成物之半導體基板之製造方法。本說明書中之所謂半導體基板係包含經研磨之單結晶矽基板(以下亦簡稱為「矽基板」),或於該矽基板上形成積體電路而得之基板者。 The present invention relates to a polishing composition, a method for producing the polishing composition, and a method for producing a semiconductor substrate using the polishing composition. The semiconductor substrate in the present specification includes a polished single crystal germanium substrate (hereinafter also referred to simply as "germanium substrate"), or a substrate obtained by forming an integrated circuit on the germanium substrate.
矽基板之研磨方法一般已知係邊將研磨用組成物供給於矽基板表面邊進行研磨之方法。採用使用如此之研磨用組成物之研磨方法時,對於研磨後之矽基板表面會有研磨用組成物中之成分殘留而以此為原因而附著顆粒之情況。於對於矽基板之低缺陷且高平滑之要求增高中,抑制起因於此研磨用組成物之顆粒附著極為重要。例如,專利文獻1中揭示之研磨用組成物含有具有特定分子量及特定HLB 值之非離子活性劑等成分,藉此,抑制了顆粒對研磨後之矽基板表面之附著。 A method of polishing a tantalum substrate is generally known in which a polishing composition is supplied to a surface of a tantalum substrate for polishing. When the polishing method using such a polishing composition is used, the particles on the surface of the substrate after polishing may remain on the surface of the substrate, and the particles may adhere thereto. In the increase in the demand for low defects and high smoothness of the tantalum substrate, it is extremely important to suppress the adhesion of particles due to the polishing composition. For example, the polishing composition disclosed in Patent Document 1 contains a specific molecular weight and a specific HLB. A component such as a nonionic active agent, whereby the adhesion of the particles to the surface of the substrate after polishing is suppressed.
[專利文獻1]特開2011-181765號公報 [Patent Document 1] JP-A-2011-181765
本發明人經積極研究之結果,發現研磨用組成物含有固體原料的水溶性高分子、減少水溶性高分子之水溶解速度之溶解抑制劑、與水時,藉由使水溶性高分子之重量平均分子量、水溶性高分子之含量、與溶解抑制劑之含量滿足特定關係,而可抑制顆粒對研磨後之矽基板表面之附著。本發明係基於上述見解而完成者,其目的係提供一種可抑制顆粒對研磨對象物研磨後表面之附著的研磨用組成物、該研磨用組成物之製造方法、及使用該研磨用組成物之半導體基板之製造方法。 As a result of active research, the present inventors have found that the polishing composition contains a water-soluble polymer of a solid raw material, a dissolution inhibitor which reduces the water dissolution rate of the water-soluble polymer, and the weight of the water-soluble polymer by water. The average molecular weight, the content of the water-soluble polymer, and the content of the dissolution inhibitor satisfy a specific relationship, and the adhesion of the particles to the surface of the substrate after polishing can be suppressed. The present invention has been made in view of the above findings, and an object thereof is to provide a polishing composition capable of suppressing adhesion of particles to a surface after polishing of an object to be polished, a method for producing the polishing composition, and a composition for polishing the same. A method of manufacturing a semiconductor substrate.
為達成上述目的,本發明之一樣態係提供一種研磨用組成物,其係含有固體原料的水溶性高分子、發揮減少前述水溶性高分子之水溶解度之作用之溶解抑制劑、與水,且將前述水溶性高分子之重量平均分子量設為A、研磨用組成物中之前述水溶性高分子之含量[質量%]設為B、研磨 用組成物中之前述溶解抑制劑之含量[質量ppm]設為C時,C/(A×B)之值為70×10-3以下。 In order to achieve the above object, the present invention provides a polishing composition which is a water-soluble polymer containing a solid raw material, a dissolution inhibitor which functions to reduce the water solubility of the water-soluble polymer, and water, and The weight average molecular weight of the water-soluble polymer is A, the content of the water-soluble polymer in the polishing composition [% by mass] is B, and the content of the dissolution inhibitor in the polishing composition [ppm by mass] When C is set, the value of C/(A × B) is 70 × 10 -3 or less.
研磨用組成物中之溶解抑制劑之含量較好為80質量ppm以下。 The content of the dissolution inhibitor in the polishing composition is preferably 80 ppm by mass or less.
水溶性高分子之重量平均分子量較好為1000000以下。 The weight average molecular weight of the water-soluble polymer is preferably 1,000,000 or less.
研磨用組成物較好用於研磨矽基板之用途。 The polishing composition is preferably used for polishing a ruthenium substrate.
研磨用組成物較好係用於最終研磨矽基板之用途。 The polishing composition is preferably used for the final polishing of the ruthenium substrate.
另外,本發明之另一樣態係提供一種研磨用組成物之製造方法,其係具有將於前述水溶性高分子之表面有加成前述溶解抑制劑之表面處理水溶性高分子混合於水中並溶解之步驟。 Further, another aspect of the present invention provides a method for producing a polishing composition comprising a surface-treated water-soluble polymer having an addition of the dissolution inhibitor on a surface of the water-soluble polymer, mixed in water, and dissolved The steps.
本發明又另一樣態係提供一種半導體基板之製造方法,其包含使用前述樣態之研磨用組成物研磨矽基板之步驟。 Still another aspect of the present invention provides a method of producing a semiconductor substrate comprising the step of polishing a germanium substrate using the polishing composition of the above-described state.
依據本發明之研磨用組成物,可抑制顆粒對於研磨對象物之研磨後表面之附著。且,依據本發明之研磨用組成物之製造方法,可製造可抑制顆粒對於研磨對象物研磨後表面之附著之研磨用組成物。且,依據本發明之半導體基板之製造方法,可獲得高品質之半導體基板。 According to the polishing composition of the present invention, the adhesion of the particles to the polished surface of the object to be polished can be suppressed. Further, according to the method for producing a polishing composition of the present invention, it is possible to produce a polishing composition which can suppress adhesion of particles to the surface after polishing of the object to be polished. Further, according to the method for producing a semiconductor substrate of the present invention, a high-quality semiconductor substrate can be obtained.
以下,說明本發明之一實施形態。 Hereinafter, an embodiment of the present invention will be described.
本實施形態之研磨用組成物含有固體原料的水溶性高分子、可發揮減少水溶性高分之水溶解度之溶解抑制劑、與水。研磨用組成物較好進一步含有研磨粒、鹼性化合物、螯合劑及界面活性劑。研磨用組成物係將水溶性高分子等各種成分混合於水中而調製。 The polishing composition of the present embodiment contains a water-soluble polymer of a solid raw material, a dissolution inhibitor which exhibits water solubility which reduces water-soluble high score, and water. The polishing composition preferably further contains abrasive grains, a basic compound, a chelating agent, and a surfactant. The polishing composition is prepared by mixing various components such as a water-soluble polymer in water.
研磨用組成物係使用於研磨矽基板表面之用途。矽基板之研磨包含例如使自矽單晶錠塊切片而成之圓盤狀之矽基板表面平坦化之預研磨步驟(一次研磨及二次研磨),及去除預研磨後之矽基板表面上存在之微細凹凸並鏡面化之最終研磨步驟。研磨用組成物最好在最終研磨步驟中使用。使用研磨用組成物研磨表面之矽基板可較好地使用於半導體基板之製造。 The polishing composition is used for polishing the surface of the crucible substrate. The polishing of the ruthenium substrate includes, for example, a pre-polishing step (primary polishing and secondary polishing) for flattening the surface of the disk-shaped ruthenium substrate sliced from the ruthenium single crystal ingot, and removing the pre-polished ruthenium substrate surface The final grinding step of fine concavo-convex and mirroring. The polishing composition is preferably used in the final grinding step. The tantalum substrate on which the surface is polished using the polishing composition can be preferably used for the production of a semiconductor substrate.
水係成為研磨用組成物中之其他成分之分散介質或溶劑。水較好不阻礙研磨用組成物中含有之其他成分之作用。此種水之例列舉為例如過渡金屬離子之合計含量為100ppb以下之水。水之純度可藉由例如使用離子交換樹脂之雜質離子去除、利用過濾器之粒子去除、利用蒸餾等之操作而提高者。具體而言較好使用離子交換水、純水、超純水、蒸餾水等。 The water system is a dispersion medium or a solvent of other components in the polishing composition. The water preferably does not hinder the action of other components contained in the polishing composition. Examples of such water are, for example, water having a total content of transition metal ions of 100 ppb or less. The purity of water can be improved by, for example, removal of impurity ions using an ion exchange resin, removal of particles by a filter, and operation by distillation or the like. Specifically, ion-exchanged water, pure water, ultrapure water, distilled water or the like is preferably used.
水溶性高分子係在研磨或洗滌等之矽基板表面處理時,發揮提高矽基板表面之濡濕性之作用。水溶性高分子在研磨用組成物調製時,係以固體狀態混合於水中。所謂固體原料的水溶性高分子意指在溶於水中前之原料狀態,在溫度23℃、相對濕度50%、及1大氣壓之環境下以目視為固體狀態之水溶性高分子。又,以下將「固體原料的水溶性高分子」僅記載為「水溶性高分子」。 The water-soluble polymer functions to improve the wettability of the surface of the ruthenium substrate when it is subjected to surface treatment of the substrate such as polishing or washing. When the water-soluble polymer is prepared in the polishing composition, it is mixed in water in a solid state. The water-soluble polymer of the solid raw material means a water-soluble polymer which is regarded as a solid state in an environment of a temperature of 23 ° C, a relative humidity of 50%, and a pressure of 1 atm before being dissolved in water. In addition, the "water-soluble polymer of a solid raw material" is only described as "water-soluble polymer".
水溶性高分子可使用分子中具有選自陽離子基、陰離子基及非離子基之至少一種官能基者,具體而言可使用分子中含羥基、羧基、醯氧基、磺基、四級氮構造、雜環構造、乙烯基構造、聚氧伸烷基構造等者之任一者。具體例列舉為纖維素衍生物、聚(N-醯基伸烷基亞胺)等亞胺衍生物、聚乙烯醇之羥基部分之一部分經取代為4級氮構造之聚乙烯醇衍生物,聚乙烯醇、聚乙烯吡咯烷酮、構造之一部分含聚乙烯吡咯烷酮之聚合物、聚乙烯己內醯胺、構造之一部分含聚乙烯己內醯胺之共聚物、聚氧乙烯、具有聚氧伸烷基構造之聚合物、具有該等之二嵌段型或三嵌段型、無規型、交互型之複數種構造之聚合物等。 The water-soluble polymer may be one having at least one functional group selected from the group consisting of a cationic group, an anionic group and a nonionic group in the molecule, and specifically, a hydroxyl group, a carboxyl group, a decyloxy group, a sulfo group or a quaternary nitrogen structure in the molecule may be used. Any one of a heterocyclic structure, a vinyl structure, and a polyoxyalkylene structure. Specific examples thereof include an imine derivative such as a cellulose derivative or a poly(N-fluorenylalkyleneimine), a polyvinyl alcohol derivative in which one of the hydroxyl groups of the polyvinyl alcohol is partially substituted with a 4-stage nitrogen structure, and polyethylene. Alcohol, polyvinylpyrrolidone, a polymer containing polyvinylpyrrolidone in one part of the structure, polyethylene caprolactam, a copolymer containing polyethylene caprolactam in one part of the structure, polyoxyethylene, having a polyoxyalkylene structure A polymer, a polymer having such a diblock type or a triblock type, a random type, an interactive type, and the like.
上述水溶性高分子中,就提高矽基板表面之濡濕性、抑制顆粒附著及降低表面粗糙度等之觀點而言,以纖維素衍生物、聚乙烯吡咯烷酮、或具有聚氧伸烷基構造之聚合物較佳。纖維素衍生物之具體例列舉為羥基乙基纖維素、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。纖維素衍生物中,就提高對矽基板表面賦予濡濕性之能力,且具有良好之洗淨去除性之方面而言,最好為羥基乙基纖維素。且,水溶性高分子可單獨使用一種,亦可組合兩種以上使用。 In the above water-soluble polymer, a cellulose derivative, polyvinylpyrrolidone, or a polymerization having a polyoxyalkylene group structure is used from the viewpoint of improving the wettability of the surface of the tantalum substrate, suppressing adhesion of particles, and lowering surface roughness. The material is preferred. Specific examples of the cellulose derivative are hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, ethylhydroxyl Ethyl cellulose, Carboxymethyl cellulose and the like. Among the cellulose derivatives, hydroxyethyl cellulose is preferred in terms of improving the ability to impart moisture repellency to the surface of the ruthenium substrate and having good washability. Further, the water-soluble polymer may be used singly or in combination of two or more.
水溶性高分子之重量平均分子量以聚環氧乙烷換算,較好為1000以上,更好為10000以上,又更好為100000以上,最好為200000以上。隨著水溶性高分子之重量平均分子量增大,矽基板表面之濡濕性提高。水溶性高分子之重量平均分子量較好為2000000以下,更好為1000000以下,又更好為800000以下,再更好為500000以下,最好為300000以下。隨著水溶性高分子之重量平均分子量減少,研磨用組成物之安定性獲得提高。且,將水溶性高分子之重量平均分子量設為1000000以下時,可減低研磨後之矽基板之研磨表面之霧濁程度。 The weight average molecular weight of the water-soluble polymer is preferably 1,000 or more, more preferably 10,000 or more, still more preferably 100,000 or more, and most preferably 200,000 or more in terms of polyethylene oxide. As the weight average molecular weight of the water-soluble polymer increases, the wettability of the surface of the ruthenium substrate increases. The weight average molecular weight of the water-soluble polymer is preferably 2,000,000 or less, more preferably 1,000,000 or less, still more preferably 800,000 or less, still more preferably 500,000 or less, and most preferably 300,000 or less. As the weight average molecular weight of the water-soluble polymer decreases, the stability of the polishing composition is improved. Further, when the weight average molecular weight of the water-soluble polymer is 1,000,000 or less, the degree of haze of the polished surface of the substrate after polishing can be reduced.
研磨用組成物中之水溶性高分子之含量較好為0.002質量%以上,更好為0.004質量%以上,又更好為0.006質量%以上,再更好為0.008質量%以上,最好為0.01質量%以上。隨著研磨用組成物中之水溶性高分子之含量增大,更提高矽基板表面之濡濕性。研磨用組成物中之水溶性高分子之含量較好為0.5質量%以下,更好為0.2質量%以下,又更好為0.1質量%以下,再更好為0.05質量%以下,最好為0.03質量%以下。隨著研磨用組成物中之水溶性高分子之含量減少,研磨用組成物之安定性獲得提高。 The content of the water-soluble polymer in the polishing composition is preferably 0.002% by mass or more, more preferably 0.004% by mass or more, still more preferably 0.006% by mass or more, still more preferably 0.008% by mass or more, and most preferably 0.01% by weight. More than % by mass. As the content of the water-soluble polymer in the polishing composition increases, the wettability of the surface of the ruthenium substrate is further improved. The content of the water-soluble polymer in the polishing composition is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, and most preferably 0.03% by mass. Below mass%. As the content of the water-soluble polymer in the polishing composition is reduced, the stability of the polishing composition is improved.
溶解抑制劑係藉由加成於水溶性高分子之表面,具體而言係藉由結合於水溶性高分子之官能基,例如羥基等之水溶性部位(親水性部位)上,而暫時降低水溶性高分子之親水性,而減低水溶性高分子之水溶解速度者。溶解抑制劑在研磨用組成物之調製中,係以加成於水溶性高分子表面之狀態混合於水中。以下,將表面已加成溶解抑制劑之水溶性高分子稱為表面處理水溶性高分子。表面處理水溶性高分子在溶解於水之過程中,分離為水溶性高分子與溶解抑制劑。結果,研磨用組成物成為含有水溶性高分子與溶解抑制劑。 The dissolution inhibitor is added to the surface of the water-soluble polymer, specifically by binding to a functional group of the water-soluble polymer, for example, a water-soluble portion (hydrophilic portion) such as a hydroxyl group, thereby temporarily reducing water solubility. The hydrophilicity of the polymer, and the water dissolution rate of the water-soluble polymer is reduced. The dissolution inhibitor is mixed in water in a state of being added to the surface of the water-soluble polymer in the preparation of the polishing composition. Hereinafter, a water-soluble polymer having a dissolution inhibitor added to the surface is referred to as a surface-treated water-soluble polymer. The surface-treated water-soluble polymer is separated into a water-soluble polymer and a dissolution inhibitor in the process of being dissolved in water. As a result, the polishing composition contains a water-soluble polymer and a dissolution inhibitor.
表面處理水溶性高分子混合於水中時,在溶解於水中前先均一分散於水中,形成水分散體。隨後,因表面處理水溶性高分子之水解產生水溶性高分子與溶解抑制劑而溶解於水中。因此,使用表面處理水溶性高分子時,與使用溶解抑制劑未加成於表面之水溶性高分子之情況相比,可更顯著地抑制水溶性高分子引起溶解不良,例如顯著抑制產生粒狀之塊體等之虞。其結果,可抑制顆粒對於研磨後矽基板表面之附著。 When the surface-treated water-soluble polymer is mixed in water, it is uniformly dispersed in water before being dissolved in water to form an aqueous dispersion. Subsequently, the water-soluble polymer and the dissolution inhibitor are produced by hydrolysis of the surface-treated water-soluble polymer to be dissolved in water. Therefore, when the water-soluble polymer is surface-treated, the solubility of the water-soluble polymer can be more significantly inhibited than in the case of using the water-soluble polymer which is not added to the surface of the dissolution inhibitor, for example, the granularity is remarkably suppressed. The block is equal to the block. As a result, adhesion of the particles to the surface of the ruthenium substrate after polishing can be suppressed.
溶解抑制劑之例列舉為例如醛類,具體舉例為例如甲醛、丁醛、甘油醛等單醛,或草酸二醛(乙二醛)、丙二酸二醛(丙二醛)、琥珀酸二醛(丁二醛)等二醛。其中,就可更佳地抑制顆粒附著之觀點而言,以草酸二醛最佳。溶解抑制劑可單獨使用一種,亦可組合兩種以上使 用。又,使溶解抑制劑加成於水溶性高分子表面上之表面處理可藉例如特開昭49-71077號公報或特開2000-63565號公報等中揭示之方法進行。 Examples of the dissolution inhibitor are exemplified by, for example, aldehydes, and specific examples thereof include monoaldehydes such as formaldehyde, butyraldehyde, and glyceraldehyde, or oxalic acid dialdehyde (glyoxal), malonic acid dialdehyde (malondialdehyde), and succinic acid II. Dialdehyde such as aldehyde (succinaldehyde). Among them, oxalic acid dialdehyde is most preferable from the viewpoint of more preferably suppressing the adhesion of particles. The dissolution inhibitor may be used singly or in combination of two or more. use. Further, the surface treatment for adding the dissolution inhibitor to the surface of the water-soluble polymer can be carried out by a method disclosed in, for example, JP-A-49-71077 or JP-A-2000-63565.
研磨用組成物中之溶解抑制劑之含量(研磨用組成物調製時基於加成於水溶性高分子表面之溶解抑制劑的加成量之含量)較好為1質量ppm以上,更好為5質量ppm以上。隨著研磨用組成物中之溶解抑制劑含量增大,亦即隨著研磨用組成物調製時之水溶性高分子之親水性降低程度增大,起因於水溶性高分子之顆粒附著減少。研磨用組成物中之溶解抑制劑含量較好為80質量ppm以下,更好為50質量ppm以下,又更好為30質量ppm以下,最好為15質量ppm以下。隨著研磨用組成物中之溶解抑制劑含量減少,起因於溶解抑制劑之顆粒附著減少。 The content of the dissolution inhibitor in the polishing composition (the content of the addition amount of the dissolution inhibitor added to the surface of the water-soluble polymer at the time of preparation of the polishing composition) is preferably 1 ppm by mass or more, more preferably 5 Above mass ppm. As the content of the dissolution inhibitor in the polishing composition increases, that is, the degree of decrease in the hydrophilicity of the water-soluble polymer when the polishing composition is prepared increases, the adhesion of the particles due to the water-soluble polymer decreases. The content of the dissolution inhibitor in the polishing composition is preferably 80 ppm by mass or less, more preferably 50 ppm by mass or less, still more preferably 30 ppm by mass or less, and most preferably 15 ppm by mass or less. As the content of the dissolution inhibitor in the polishing composition is decreased, the particle adhesion due to the dissolution inhibitor is reduced.
研磨用組成物中之溶解抑制劑含量係設定為對於水溶性高分子之重量平均分子量及研磨用組成物中之水溶性高分子含量滿足特定關係。亦即,將水溶性高分子之重量平均分子量設為A、研磨用組成物中之水溶性高分子之含量[質量%]設為B、研磨用組成物中之溶解抑制劑之含量[質量ppm]設為C時,C/(A×B)之值處於特定範圍內。 The content of the dissolution inhibitor in the polishing composition is set to satisfy a specific relationship with respect to the weight average molecular weight of the water-soluble polymer and the water-soluble polymer content in the polishing composition. In other words, the weight average molecular weight of the water-soluble polymer is A, the content of the water-soluble polymer in the polishing composition [% by mass] is B, and the content of the dissolution inhibitor in the polishing composition [ppm by mass] When C is set to C, the value of C/(A × B) is within a specific range.
水溶性高分子之重量平均分子量A、水溶性高分子之含量B、及溶解抑制劑之含量C分別與使水溶性高分子均一溶解於水中之難易度有關。 The weight average molecular weight A of the water-soluble polymer, the content B of the water-soluble polymer, and the content C of the dissolution inhibitor are respectively related to the ease with which the water-soluble polymer is uniformly dissolved in water.
隨著重量平均分子量A變大,水溶性高分子1分子中所含之羥基等之水合點之數量變多。結果,用以溶解水溶性 高分子所需之水量變多,而難以使水溶性高分子均一溶解於水中。因此,水溶性高分子之重量平均分子量A可說是表示使水溶性高分子之各分子均一溶解於水中之困難性之參數。 As the weight average molecular weight A becomes larger, the number of hydration points of the hydroxyl group or the like contained in one molecule of the water-soluble polymer increases. As a result, to dissolve water solubility The amount of water required for the polymer is increased, and it is difficult to uniformly dissolve the water-soluble polymer in water. Therefore, the weight average molecular weight A of the water-soluble polymer can be said to be a parameter indicating difficulty in uniformly dissolving each molecule of the water-soluble polymer in water.
水溶性高分子之含量B較大時,研磨用組成物中之水溶性高分子之分子數變多。因此,含量B愈大,研磨用組成物中之水溶性高分子之分子彼此之接觸頻率愈增大。結果,水溶性高分子之分子彼此容易絡合,而難以使水溶性高分子均一溶解於水中。因此,水溶性高分子之含量B可說是表示研磨用組成物中之水溶性高分子全體均一溶解於水中之困難性之參數。 When the content B of the water-soluble polymer is large, the number of molecules of the water-soluble polymer in the polishing composition increases. Therefore, the larger the content B, the more the frequency of contact of the molecules of the water-soluble polymer in the polishing composition with each other. As a result, the molecules of the water-soluble polymer are easily complexed with each other, and it is difficult to uniformly dissolve the water-soluble polymer in water. Therefore, the content B of the water-soluble polymer can be said to be a parameter indicating the difficulty in uniformly dissolving the entire water-soluble polymer in the polishing composition in water.
因此,水溶性高分子之重量平均分子量A與水溶性高分子之含量B之乘積(亦即A×B)係表示研磨用組成物中之水溶性高分子均一溶解於水中之困難性之綜合參數,該數值愈大,愈難以使水溶性高分子均一溶解於水中。 Therefore, the product of the weight average molecular weight A of the water-soluble polymer and the content B of the water-soluble polymer (that is, A × B) is a comprehensive parameter indicating the difficulty in uniformly dissolving the water-soluble polymer in the polishing composition in water. The larger the value, the more difficult it is to dissolve the water-soluble polymer uniformly in water.
另一方面,溶解抑制劑之含量C較大時,研磨用組成物中之溶解抑制劑之分子數變多。因此,含量C愈大,則溶解抑制劑越能對於水溶性高分子中之較多水合點產生作用。結果,抑制了水溶性高分子之水合點之作用,而使水溶性高分子均一溶解於水中變得容易。因此,C/(A×B)可說是表示研磨用組成物中之水溶性高分子均一地溶解於水中之困難性與溶解抑制劑減低該困難性之作用大小之間之比率的參數。該數值愈大,則水溶性高分子愈容易均一溶解於水中。 On the other hand, when the content C of the dissolution inhibitor is large, the number of molecules of the dissolution inhibitor in the polishing composition increases. Therefore, the larger the content C, the more the dissolution inhibitor acts on the more hydration points in the water-soluble polymer. As a result, the action of the hydration point of the water-soluble polymer is suppressed, and it becomes easy to uniformly dissolve the water-soluble polymer in water. Therefore, C/(A × B) can be said to be a parameter indicating the ratio between the difficulty in uniformly dissolving the water-soluble polymer in the polishing composition in water and the magnitude of the effect of the dissolution inhibitor on reducing the difficulty. The larger the value, the easier the water-soluble polymer is uniformly dissolved in water.
C/(A×B)之值較好為2.5×10-3以上,更好為3.0×10-3以上,又更好為3.5×10-3以上,最好為4.0×10-3以上。隨著C/(A×B)之值增大,水溶性高分子均一溶解於水中變容易,結果減少了附著於研磨後之矽基板表面之顆粒數。 The value of C/(A × B) is preferably 2.5 × 10 -3 or more, more preferably 3.0 × 10 -3 or more, still more preferably 3.5 × 10 -3 or more, and most preferably 4.0 × 10 -3 or more. As the value of C/(A×B) increases, it becomes easy to dissolve the water-soluble polymer uniformly in water, and as a result, the number of particles adhering to the surface of the polished ruthenium substrate is reduced.
然而,另一方面,於C/(A×B)之數值過大時,亦會發生附著於研磨後之矽基板表面上之顆粒數增大之問題。此認為原因係相對於水溶性高分子過量存在之溶解抑制劑附著於矽基板表面上。因此,C/(A×B)之值較好為70×10-3以下,更好為30×10-3以下,又更好為20×10-3以下,再更好為10×10-3以下,最好為6.0×10-3以下。隨著C/(A×B)之值減少,起因於溶解抑制劑之附著於研磨後之矽基板表面上之顆粒數隨之減少。 On the other hand, however, when the value of C/(A × B) is too large, the problem of an increase in the number of particles adhering to the surface of the ruthenium substrate after polishing also occurs. This is considered to be because the dissolution inhibitor present in excess with respect to the water-soluble polymer adheres to the surface of the ruthenium substrate. Therefore, the value of C/(A × B) is preferably 70 × 10 -3 or less, more preferably 30 × 10 -3 or less, still more preferably 20 × 10 -3 or less, and even more preferably 10 × 10 - 3 or less, preferably 6.0 × 10 -3 or less. As the value of C/(A×B) decreases, the number of particles due to adhesion of the dissolution inhibitor to the surface of the polished ruthenium substrate decreases.
又,溶解抑制劑之含量C及C/(A×B)之值可藉由改變研磨用組成物調製時所用之表面處理水溶性高分子中之溶解抑制劑加成量而調整。研磨用組成物中之溶解抑制劑之含量C可作為研磨用組成物中所含之表面處理水溶性高分子之水解物的溶解抑制劑及其類似物之量進行測定。加成於水溶性高分子表面之溶解抑制劑與上述水解物具有不同化學構造時,可藉由將上述水解物之量之測定值換算成溶解抑制劑而算出溶解抑制劑之含量C。研磨組成物中所含之上述水解物之量可藉由例如使用高速液體層析儀或虹吸電泳裝置而測定。 Further, the content of the dissolution inhibitor C and the value of C/(A × B) can be adjusted by changing the amount of the dissolution inhibitor added to the surface-treated water-soluble polymer used for preparation of the polishing composition. The content C of the dissolution inhibitor in the polishing composition can be measured as the amount of the dissolution inhibitor of the hydrolyzate of the surface-treated water-soluble polymer contained in the polishing composition and the like. When the dissolution inhibitor added to the surface of the water-soluble polymer has a different chemical structure from the hydrolyzate, the content C of the dissolution inhibitor can be calculated by converting the measured value of the amount of the hydrolyzate into a dissolution inhibitor. The amount of the above hydrolyzate contained in the polishing composition can be determined, for example, by using a high speed liquid chromatograph or a siphon electrophoresis apparatus.
研磨用組成物可含有研磨粒。研磨粒係發揮物理性研磨矽基板表面之作用。 The polishing composition may contain abrasive grains. The abrasive grain system functions to physically polish the surface of the substrate.
作為研磨粒之例列舉為無機粒子、有機粒子及有機無機複合粒子。無機粒子之具體例列舉為例如由二氧化矽、氧化鋁、氧化鈰、氧化鈦等金屬氧化物所成之粒子,以及氮化矽粒子、碳化矽粒子及氮化硼粒子。有機粒子之具體例列舉為例如聚甲基丙烯酸甲酯(PMMA)粒子。 Examples of the abrasive grains include inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include, for example, particles made of a metal oxide such as cerium oxide, aluminum oxide, cerium oxide, or titanium oxide, and cerium nitride particles, cerium carbide particles, and boron nitride particles. Specific examples of the organic particles are, for example, polymethyl methacrylate (PMMA) particles.
該等具體例中以二氧化矽較佳。二氧化矽之具體例列舉為膠體二氧化矽、發煙二氧化矽及溶凝膠法二氧化矽。該等中,就減少研磨後之矽基板表面產生之刮痕之觀點而言,以膠體二氧化矽及發煙二氧化矽較佳,最好為膠體二氧化矽。該等二氧化矽可單獨使用一種,亦可組合兩種以上使用。 Among these specific examples, cerium oxide is preferred. Specific examples of the cerium oxide are colloidal cerium oxide, fumed cerium oxide, and sol-gel cerium oxide. Among these, colloidal cerium oxide and fumed cerium oxide are preferred, and colloidal cerium oxide is preferred from the viewpoint of reducing scratches on the surface of the substrate after polishing. These cerium oxides may be used alone or in combination of two or more.
使用之二氧化矽之真比重較好為1.5以上,更好為1.6以上,又更好為1.7以上。隨著二氧化矽之真比重增加,獲得了研磨矽基板時之高的研磨速度。二氧化矽之真比重較好為2.2以下,更好為2.0以下,又更好為1.9以下。隨著二氧化矽之真比重減少,提高了研磨後之矽基板表面品質,具體改善了霧濁程度。二氧化矽之真比重係由乾燥之二氧化矽粒子之重量、將該二氧化矽粒子浸漬於已知體積之乙醇時之總重量而算出。 The true specific gravity of the cerium oxide used is preferably 1.5 or more, more preferably 1.6 or more, and still more preferably 1.7 or more. As the true specific gravity of the cerium oxide increases, a high polishing rate when the ruthenium substrate is polished is obtained. The true specific gravity of cerium oxide is preferably 2.2 or less, more preferably 2.0 or less, and still more preferably 1.9 or less. As the true specific gravity of the cerium oxide is reduced, the surface quality of the ruthenium substrate after polishing is improved, and the degree of haze is specifically improved. The true specific gravity of cerium oxide is calculated from the weight of the dried cerium oxide particles and the total weight of the cerium oxide particles immersed in a known volume of ethanol.
研磨粒之平均一次粒徑較好為5nm以上,更好為10nm以上,又更好為20nm以上。隨著研磨粒之平均一次粒徑增大,獲得了研磨矽基板時之高的研磨速度。研磨粒之平 均一次粒徑較好為100nm以下,更好為70nm以下,又更好為50nm以下。隨著研磨粒之平均一次粒徑減小,提高了研磨用組成物之安定性。 The average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 20 nm or more. As the average primary particle size of the abrasive particles increases, a high polishing rate when the ruthenium substrate is polished is obtained. Abrasive grain The primary primary particle diameter is preferably 100 nm or less, more preferably 70 nm or less, and still more preferably 50 nm or less. As the average primary particle size of the abrasive particles decreases, the stability of the polishing composition is improved.
研磨粒之平均一次粒徑之值係由例如以BET法測定之比表面積算出。研磨粒之比表面積測定可使用例如Micromeritics公司製之”Flow SorbII 2300”進行。 The value of the average primary particle diameter of the abrasive grains is calculated, for example, from the specific surface area measured by the BET method. The specific surface area measurement of the abrasive grains can be carried out using, for example, "Flow Sorb II 2300" manufactured by Micromeritics.
研磨粒之平均二次粒徑較好為10nm以上,更好為20nm以上,又更好為30nm以上。隨著研磨粒之平均二次粒徑增大,獲得了研磨矽基板時之高的研磨速度。研磨粒之平均二次粒徑較好為200nm以下,更好為150nm以下,又更好為100nm以下。隨著研磨粒之平均二次粒徑減小,提高了研磨用組成物之安定性。研磨粒之平均二次粒徑可使用例如大塚電子公司製之FPAR-1000,利用動態光散射法測定。 The average secondary particle diameter of the abrasive grains is preferably 10 nm or more, more preferably 20 nm or more, and still more preferably 30 nm or more. As the average secondary particle diameter of the abrasive grains increases, a high polishing speed at the time of polishing the ruthenium substrate is obtained. The average secondary particle diameter of the abrasive grains is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less. As the average secondary particle size of the abrasive particles decreases, the stability of the polishing composition is improved. The average secondary particle diameter of the abrasive grains can be measured by a dynamic light scattering method using, for example, FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
研磨粒之長徑/短徑比之平均值較好為1.0以上,更好為1.05以上,又更好為1.1以上。隨著上述長徑/短徑比之平均值增大,獲得了研磨矽基板時之高的研磨速度。研磨粒之長徑/短徑比之平均值較好為3.0以下,更好為2.0以下,又更好為1.5以下。隨著上述長徑/短徑比之平均值減小,而減少於研磨後之矽基板表面產生之刮痕。 The average value of the long diameter/short diameter ratio of the abrasive grains is preferably 1.0 or more, more preferably 1.05 or more, still more preferably 1.1 or more. As the average value of the above-described long diameter/short diameter ratio increases, a high polishing rate at the time of polishing the ruthenium substrate is obtained. The average value of the long diameter/short diameter ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less. As the average value of the long diameter/short diameter ratio decreases, the scratch generated on the surface of the substrate after polishing is reduced.
上述長徑/短徑比係與研磨粒之形狀有關之值,可使用例如研磨粒之電子顯微鏡影像求出。具體而言,畫出特定個數(例如200個)研磨粒之掃描型電子顯微鏡影像中之與各研磨粒切線之最小長方形。接著,算出將各長方形 之長邊長度(長徑之值)除以同一長方形之短邊長度(短徑之值)之值,藉由算出該等之平均值,可求出長徑/短徑比之平均值。 The value of the long diameter/short diameter ratio and the shape of the abrasive grains can be determined by, for example, an electron microscope image of the abrasive grains. Specifically, a minimum rectangle of the tangential line of each abrasive grain in a scanning electron microscope image of a specific number (for example, 200) of abrasive grains is drawn. Next, calculate each rectangle The length of the long side (the value of the long diameter) is divided by the value of the short side length (the value of the short diameter) of the same rectangle, and the average value of the long diameter/short diameter ratio can be obtained by calculating the average value of the same.
研磨用組成物中之研磨粒含量較好為0.1質量%以上,更好為0.2質量%以上,又更好為0.3質量%以上。隨著研磨粒含量增大,獲得了研磨矽基板時之高的研磨速度。研磨用組成物中之研磨粒含量較好為10質量%以下,更好為5質量%以下,又更好為3質量%以下,最好為1質量%以下。隨著研磨粒之含量減少,而提高了研磨用組成物之安定性。 The content of the abrasive grains in the polishing composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more. As the abrasive grain content increases, a high polishing speed at the time of polishing the ruthenium substrate is obtained. The content of the abrasive grains in the polishing composition is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and most preferably 1% by mass or less. As the content of the abrasive particles is reduced, the stability of the polishing composition is improved.
研磨用組成物可含有鹼性化合物。鹼性化合物係發揮化學性研磨矽基板表面之作用(化學蝕刻)。藉此,容易提高利用研磨用組成物對矽基板之研磨速度。 The polishing composition may contain a basic compound. The basic compound functions to chemically polish the surface of the substrate (chemical etching). Thereby, it is easy to improve the polishing rate of the substrate by the polishing composition.
至於鹼性化合物之具體例列舉為鹼金屬之氫氧化物或鹽、氫氧化四級銨或其鹽、氨、胺等。鹼金屬之具體例列舉為鉀、鈉等。鹽之具體例列舉為碳酸鹽、碳酸氫鹽、硫酸鹽、乙酸鹽等。四級銨之具體例列舉為四甲基銨、四乙基銨、四丁基銨等。鹼金屬之氫氧化物或鹽之具體例列舉為氫氧化鉀、碳酸鉀、碳酸氫鉀、硫酸鉀、乙酸鉀、氯化鉀等。氫氧化四級銨或其鹽之具體例列舉為氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丁基銨等。胺之具體例列舉為甲胺、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、無水哌啶、哌啶六水合物、1-(2-胺基乙基)哌啶、N-甲基哌啶、胍等。該等鹼性化合物可單獨使用一種,亦可組合兩種以上使用。 Specific examples of the basic compound are exemplified by hydroxides or salts of alkali metals, quaternary ammonium hydroxide or salts thereof, ammonia, amines and the like. Specific examples of the alkali metal are exemplified by potassium, sodium, and the like. Specific examples of the salt are exemplified by carbonate, hydrogencarbonate, sulfate, acetate, and the like. Specific examples of the quaternary ammonium are exemplified by tetramethylammonium, tetraethylammonium, tetrabutylammonium and the like. Specific examples of the hydroxide or salt of the alkali metal include potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, potassium sulfate, potassium acetate, potassium chloride and the like. Specific examples of the quaternary ammonium hydroxide or a salt thereof are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like. Specific examples of the amine are exemplified by methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, and B. Diamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, di-ethyltriamine, tri-ethyltetramine, anhydrous piperidine, piperidine hexahydrate, 1 -(2-Aminoethyl)piperidine, N-methylpiperidine, hydrazine, and the like. These basic compounds may be used alone or in combination of two or more.
鹼性化合物中,以選自氨、銨鹽、鹼金屬氫氧化物、鹼金屬鹽及四級銨氫氧化物之至少一種較佳。鹼性化合物中,更好為選自氨、氫氧化鉀、氫氧化鈉、氫氧化四甲基銨、氫氧化四乙基銨、碳酸氫鈉、碳酸銨、碳酸氫鉀、碳酸鉀、碳酸氫鈉及碳酸鈉之至少一種,更好為選自氨、氫氧化鉀、氫氧化鈉、氫氧化四甲基銨及氫氧化四乙基銨之至少一種,更好為氨及氫氧化四甲基銨之少一種,最好為氨。 Among the basic compounds, at least one selected from the group consisting of ammonia, an ammonium salt, an alkali metal hydroxide, an alkali metal salt, and a quaternary ammonium hydroxide is preferred. More preferably, the basic compound is selected from the group consisting of ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, sodium hydrogencarbonate, ammonium carbonate, potassium hydrogencarbonate, potassium carbonate, and hydrogencarbonate. At least one of sodium and sodium carbonate is more preferably at least one selected from the group consisting of ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and tetraethylammonium hydroxide, more preferably ammonia and tetramethylammonium hydroxide. One of the less ammonium, preferably ammonia.
研磨用組成物中之鹼性化合物之含量較好為0.001質量%以上,更好為0.002質量%以上,又更好為0.003質量%以上。隨著研磨用組成物中之鹼性化合物之含量增大,獲得了研磨矽基板時之高的研磨速度。研磨用組成物中之鹼性化合物含量較好為1.0質量%以下,更好為0.5質量%以下,又更好為0.2質量%以下,最好為0.1質量%以下。隨著研磨用組成物中之鹼性化合物含量減少,而容易地維持矽基板之形狀。 The content of the basic compound in the polishing composition is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and still more preferably 0.003% by mass or more. As the content of the basic compound in the polishing composition is increased, a high polishing rate at the time of polishing the ruthenium substrate is obtained. The content of the basic compound in the polishing composition is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and most preferably 0.1% by mass or less. As the content of the basic compound in the polishing composition is reduced, the shape of the ruthenium substrate is easily maintained.
研磨用組成物之pH較好為8.0以上,更好為8.5以上,又更好為9.0以上。隨著研磨用組成物之pH增大,獲得了研磨矽基板時之高的研磨速度。研磨用組成物之pH較好為12.5以下,更好為12.0以下,又更好為11.5以下。隨著研 磨用組成物之pH減少,而容易地維持矽基板之形狀。 The pH of the polishing composition is preferably 8.0 or more, more preferably 8.5 or more, still more preferably 9.0 or more. As the pH of the polishing composition increases, a high polishing rate at the time of polishing the ruthenium substrate is obtained. The pH of the polishing composition is preferably 12.5 or less, more preferably 12.0 or less, still more preferably 11.5 or less. With research The pH of the grinding composition is reduced, and the shape of the crucible substrate is easily maintained.
研磨用組成物可含有螯合劑。螯合劑係藉由捕捉研磨系中之金屬雜質並形成錯合物,而發揮抑制矽基板之金屬污染的作用。 The polishing composition may contain a chelating agent. The chelating agent functions to suppress metal contamination of the ruthenium substrate by capturing metal impurities in the polishing system and forming a complex.
螯合劑之具體例列舉為例如胺基羧酸系螯合劑、及有機膦酸系螯合劑。胺基羧酸系螯合劑之具體例舉例有乙二胺四乙酸、乙二胺四乙酸鈉、氮基(nitrilo)三乙酸、氮基三乙酸鈉、氮基三乙酸銨、羥基乙基伸乙二胺三乙酸、羥基乙基伸乙二胺三乙酸鈉、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、三伸乙基四胺六乙酸鈉等。有機膦酸系螯合劑之具體例列舉為2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、胺基三(伸乙基膦酸)、伸乙二胺肆(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、α-甲基膦醯基琥珀酸等。該等中以有機膦酸系螯合劑較佳,最好為伸乙二胺肆(亞甲基膦酸)。該等螯合劑可單獨使用一種,亦可組合兩種以上使用。 Specific examples of the chelating agent include, for example, an aminocarboxylic acid-based chelating agent and an organic phosphonic acid-based chelating agent. Specific examples of the aminocarboxylic acid-based chelating agent include ethylenediaminetetraacetic acid, sodium edetate, nitrilo triacetic acid, sodium nitrotriacetate, ammonium oxytriacetate, and hydroxyethyl acetonitrile. Amine triacetic acid, sodium hydroxyethyl ethylenediamine triacetate, diethylidene triamine pentaacetic acid, sodium diethylammonium pentaacetate, triethylammonium hexaacetate, triethylammonium hexaacetate Sodium and so on. Specific examples of the organic phosphonic acid-based chelating agent are 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotris(ethylphosphonic acid), and ethylenediamine.肆 (methylene phosphonic acid), di-ethyltriamine penta (methylene phosphonic 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-dicarboxy-1,2-diphosphonic acid, methane hydroxyl Phosphonic acid, 2-phosphonium butane-1,2-dicarboxylic acid, 1-phosphonium butane-2,3,4-tricarboxylic acid, α-methylphosphonium succinic acid and the like. Among these, an organic phosphonic acid-based chelating agent is preferred, and ethylenediamine oxime (methylene phosphonic acid) is preferred. These chelating agents may be used alone or in combination of two or more.
研磨用組成物可含有界面活性劑。界面活性劑係發揮抑制矽基板之研磨面粗糙之作用。藉此,可容易地減低研磨後之矽基板面之霧濁程度。尤其,研磨用組成物含鹼性化合物時,容易因鹼性化合物進行之化學蝕刻而於研磨後之矽基板表面產生粗糙。因此,鹼性化合物與界面活性劑併用尤其有效。 The polishing composition may contain a surfactant. The surfactant acts to suppress the roughness of the polished surface of the ruthenium substrate. Thereby, the degree of haze of the substrate surface after polishing can be easily reduced. In particular, when the polishing composition contains a basic compound, it is likely to be roughened on the surface of the substrate after polishing by chemical etching by the alkaline compound. Therefore, the use of a basic compound in combination with a surfactant is particularly effective.
界面活性劑之重量平均分子量較好未達1000。界面活性劑可為陰離子性或非離子性。其中以非離子性界面活性劑較佳。非離性界面活性劑由於起泡性低,故研磨用組成物之調製時或使用時之操作性變得容易。且,使用非離子性界面活性劑時,研磨用組成物之pH調整變得容易。 The weight average molecular weight of the surfactant is preferably less than 1,000. The surfactant can be anionic or nonionic. Among them, a nonionic surfactant is preferred. Since the non-separating surfactant has low foaming property, workability at the time of preparation of the polishing composition or at the time of use becomes easy. Further, when a nonionic surfactant is used, pH adjustment of the polishing composition is facilitated.
非離子性界面活性劑之具體例列舉為氧基伸烷基之均聚物、複數種類之氧基伸烷基之共聚物、聚氧伸烷基加成物。氧基伸烷基之均聚物之具體例列舉為聚氧伸乙基、聚乙二醇、聚氧伸丙基及聚氧伸丁基。複數種之氧基伸烷基之共聚物之具體例列舉為聚氧伸乙基聚氧丙二醇及聚氧伸乙基聚氧丁二醇。 Specific examples of the nonionic surfactant are exemplified by a homopolymer of an oxyalkylene group, a copolymer of a plurality of kinds of oxyalkylene groups, and a polyoxyalkylene alkyl adduct. Specific examples of the homopolymer of the oxyalkylene group are polyoxyethylene ethyl, polyethylene glycol, polyoxypropylidene and polyoxybutylene. Specific examples of the copolymer of a plurality of oxyalkylene groups are polyoxyethylene ethyl oxypropylene glycol and polyoxyethylene polyoxybutylene glycol.
聚氧伸烷基加成物之具體例列舉為聚氧伸乙基烷基醚、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、聚氧乙二醇醚脂肪酸酯、聚氧伸乙基山梨糖醇酐脂肪酸酯等。更具體列舉為聚氧伸乙基聚氧伸丙基共聚物、聚氧乙二醇、聚氧伸乙基丙基醚、聚氧伸乙基丁基醚、聚氧伸乙基戊基醚、聚氧伸乙基己基醚、聚氧伸乙基辛基醚、聚氧伸乙基-2-乙基己基醚、聚氧伸乙基壬基 醚、聚氧伸乙基癸基醚、聚氧伸乙基異癸基醚、聚氧伸乙基十三烷基醚、聚氧伸乙基月桂基醚、聚氧伸乙基鯨蠟基醚、聚氧伸乙基硬脂基醚、聚氧伸乙基異硬脂基醚、聚氧伸乙基油基醚、聚氧伸乙基苯基醚、聚氧伸乙基辛基苯基醚、聚氧伸乙基壬基苯基醚、聚氧伸乙基十二烷基苯基醚、聚氧伸乙基苯乙烯化苯基醚、聚氧伸乙基月桂基胺、聚氧伸乙基硬脂基胺、聚氧伸乙基油基胺、聚氧伸乙基硬脂基醯胺、聚氧伸乙基油基醯胺、聚氧伸乙基單月桂酸酯、聚氧伸乙基單硬脂酸酯、聚氧伸乙基二硬脂酸酯、聚氧伸乙基單油酸酯、聚氧伸乙基二油酸酯、單月桂酸聚氧伸乙基山梨糖醇酐、單棕櫚酸聚氧伸乙基山梨糖醇酐、單硬脂酸聚氧伸乙基山梨糖醇酐、單油酸聚氧伸乙基山梨糖醇酐、三油酸聚氧伸乙基山梨糖醇酐、四油酸聚氧伸乙基山梨糖醇、聚氧伸乙基蓖麻油、聚氧伸乙基硬蓖麻油等。 Specific examples of the polyoxyalkylene alkyl adduct are polyoxyethylene ethyl ether, polyoxyethylidene ether, polyoxyethylene alkylamine, polyoxyethyl alcohol ester , polyoxyethylene glycol ether fatty acid ester, polyoxyethylene ethyl sorbitan fatty acid ester and the like. More specifically, polyoxyethylene ethyl polyoxypropyl propylene copolymer, polyoxyethylene glycol, polyoxyethylene ethyl propyl ether, polyoxyethylene ethyl butyl ether, polyoxyethylene ethyl pentyl ether, Polyoxyethylene ethylhexyl ether, polyoxyethylene ethyl octyl ether, polyoxyethylene ethyl-2-ethylhexyl ether, polyoxyethyl ether Ether, polyoxyethylene ethyl decyl ether, polyoxyethylene ethyl isodecyl ether, polyoxyethylene ethyl tridecyl ether, polyoxyethylene ethyl lauryl ether, polyoxyethyl ether cetyl ether , polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl isostearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl phenyl ether, polyoxyethyl octyl phenyl ether , polyoxyethylidene phenyl ether, polyoxyethylene ethyl dodecyl phenyl ether, polyoxyethyl styrene ether, polyoxyethylene ethyl laurylamine, polyoxyethylene Stearylamine, polyoxyethylene ethyl oleylamine, polyoxyethylidene stearylamine, polyoxyethylene ethyl decylamine, polyoxyethylene ethyl laurate, polyoxyethylene Monostearate, polyoxyethylene ethyl distearate, polyoxyethylidene monooleate, polyoxyethylene ethyl oleate, polylaurate monoethyl sorbitan , monopalmitic acid polyoxyethylene ethyl sorbitan, monostearic acid polyoxyethylene ethyl sorbitan, monooleic acid polyoxyethylene ethyl sorbitan, trioleic acid polyoxyethylene ethyl sorbitol Sugar alcohol anhydride, tetraoleic acid polyoxyethylene ethyl sorbitol, polyoxyethylene Sesame oil, polyoxyethylene castor oil extending ethyl hard.
該等非離子性界面活性劑中,以氧基伸烷基之均聚物或複數種之氧基伸烷基之共聚物較佳。該情況下,容易將研磨後之矽基板表面之霧濁降低至實用上特別適合之程度。其理由認為是稍具有親水性之醚鍵與稍具有疏水性之伸烷基於該等聚合物之分子鏈中交互存在所致。 Among these nonionic surfactants, a copolymer of an alkyloxy group or a plurality of alkyloxy groups is preferred. In this case, it is easy to reduce the haze on the surface of the substrate after polishing to a level that is particularly suitable for practical use. The reason for this is considered to be that the slightly hydrophilic ether bond and the slightly hydrophobic alkyl group interact in the molecular chain of the polymers.
氧基伸烷基之均聚物或複數種之氧基伸烷基之共聚物中之氧基伸乙基單位之比率較好為85質量%以上,更好為90質量%以上。隨著聚合物中之氧基伸乙基單位之比率增大,抑制了顆粒對研磨後之矽基板表面之附著。 The ratio of the oxy-ethyl group in the homopolymer of the oxyalkylene group or the oxyalkylene group of the plurality of alkylene groups is preferably 85% by mass or more, more preferably 90% by mass or more. As the ratio of the oxygen-extended ethyl units in the polymer increases, the adhesion of the particles to the surface of the substrate after grinding is inhibited.
非離子性界面活性劑之HLB(hydrophile-lipophile balance,親脂-親油平衡)值較好為17以上,更好為18以上。隨著非離子性界面活性劑之HLB值增大,抑制了顆粒對研磨後之矽基板表面之附著。 Non-ionic surfactant HLB (hydrophile-lipophile The balance, lipophilic-lipophilic balance value is preferably 17 or more, more preferably 18 or more. As the HLB value of the nonionic surfactant increases, the adhesion of the particles to the surface of the substrate after grinding is inhibited.
界面活性劑可單獨使用一種,亦可組合兩種以上使用。 The surfactants may be used alone or in combination of two or more.
研磨用組成物中之界面活性劑含量較好為0.0001質量%以上,更好為0.001質量%以上。隨著界面活性劑含量增大,更減少了研磨後之矽基板表面之霧濁程度。研磨用組成物中之界面活性劑含量較好為0.05質量%以下,更好為0.02質量%以下。隨著界面活性劑之含量減少,抑制了顆粒對研磨後之矽基板表面之附著。 The content of the surfactant in the polishing composition is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more. As the surfactant content increases, the degree of haze on the surface of the substrate after grinding is further reduced. The content of the surfactant in the polishing composition is preferably 0.05% by mass or less, more preferably 0.02% by mass or less. As the amount of surfactant is reduced, the adhesion of the particles to the surface of the substrate after grinding is inhibited.
研磨用組成物亦可視需要進一步含有研磨用組成物一般含有之習知添加劑,例如有機酸、有機酸鹽、無機酸、無機酸鹽、防腐劑、防黴劑等。例如於添加有機酸、有機酸鹽、無機酸及無機酸鹽之任一種時,可藉由與水溶性高分子之相互作用,提高研磨後之矽基板表面之親水性。 The polishing composition may further contain a conventional additive generally contained in the polishing composition, such as an organic acid, an organic acid salt, an inorganic acid, a mineral acid salt, a preservative, an antifungal agent, or the like. For example, when any of an organic acid, an organic acid salt, an inorganic acid, and a mineral acid salt is added, the hydrophilicity of the surface of the ruthenium substrate after polishing can be improved by interaction with the water-soluble polymer.
有機酸之具體例列舉為甲酸、乙酸、丙酸等脂肪酸,苯甲酸、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。有機酸鹽之具體例列舉為該等有機酸之鈉鹽及鉀鹽等鹼金屬鹽,或銨鹽。 Specific examples of the organic acid 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, and organic compounds. Sulfonic acid, organic phosphonic acid, and the like. Specific examples of the organic acid salt are exemplified by alkali metal salts such as sodium salts and potassium salts of the organic acids, or ammonium salts.
無機酸之具體例列舉為硫酸、硝酸、鹽酸、碳酸等。 無機酸鹽之具體例列舉為該等無機酸之鈉鹽及鉀鹽等鹼金屬鹽、或銨鹽。 Specific examples of the inorganic acid are sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, and the like. Specific examples of the inorganic acid salt are exemplified by an alkali metal salt such as a sodium salt or a potassium salt of the inorganic acid or an ammonium salt.
有機酸鹽及無機酸鹽中,就抑制矽基板之金屬污染之觀點而言,較好為銨鹽。 Among the organic acid salts and inorganic acid salts, an ammonium salt is preferred from the viewpoint of suppressing metal contamination of the tantalum substrate.
有機酸及其鹽、以及無機酸及其鹽可單獨使用一種,亦可組合兩種以上使用。 The organic acid and the salt thereof, and the inorganic acid and the salt thereof may be used alone or in combination of two or more.
防腐劑及防黴劑之具體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。 Specific examples of the preservative and the antifungal agent include an isothiazoline compound, a paraben, a phenoxyethanol, and the like.
接著,針對本實施形態之研磨用組成物之製造方法加以敘述。 Next, a method of producing the polishing composition of the present embodiment will be described.
研磨用組成物係藉由經過將表面處理水溶性高分子(表面已加成溶解抑制劑之水溶性高分子)混合於水中使之溶解之步驟而調製。且,可視需要進一步於研磨用組成物中混合研磨粒等其他成分。 The polishing composition is prepared by a step of mixing a surface-treated water-soluble polymer (a water-soluble polymer having a surface-added dissolution inhibitor) in water to dissolve it. Further, other components such as abrasive grains may be further mixed in the polishing composition as needed.
於水中混合之表面處理水溶性高分子先分散於水中。隨後,藉由進行攪拌操作,使分散之表面處理水溶性高分子水解而產生水溶性高分子與溶解抑制劑,使該等溶解於水中。結果,獲得水溶性高分子及溶解抑制劑溶解於水中之研磨用組成物。表面處理水溶性高分子之使用量及表面處理水溶性高分子中之水溶性高分子之重量平均分子量及溶解抑制劑之加成量係以使最終獲得之研磨用組成物具有上述特定範圍之C/(A×B)之值之方式予以選定。 The surface-treated water-soluble polymer mixed in water is first dispersed in water. Subsequently, the dispersed surface-treated water-soluble polymer is hydrolyzed by a stirring operation to produce a water-soluble polymer and a dissolution inhibitor, and these are dissolved in water. As a result, a polishing composition in which a water-soluble polymer and a dissolution inhibitor are dissolved in water is obtained. The amount of the water-soluble polymer to be surface-treated and the weight average molecular weight of the water-soluble polymer in the surface-treated water-soluble polymer and the addition amount of the dissolution inhibitor are such that the finally obtained polishing composition has the above specific range C The value of /(A×B) is selected.
表面處理水溶性高分子就均一分散於水中之觀點而言較好使用粒度細者。具體而言,表面處理水溶性高分子之 粒度較好為1000μm以下,更好為500μm以下,最好為200μm以下。使用具有上述範圍之粒度的表面處理水溶性高分子時,因表面處理水溶性高分子容易均一地分散於水中,故獲得了微細分散體。 The surface-treated water-soluble polymer is preferably finely divided from the viewpoint of uniform dispersion in water. Specifically, the surface treatment of the water-soluble polymer The particle size is preferably 1000 μm or less, more preferably 500 μm or less, and most preferably 200 μm or less. When the water-soluble polymer is surface-treated with a particle size within the above range, the surface-treated water-soluble polymer is easily and uniformly dispersed in water, so that a fine dispersion is obtained.
另一方面,表面處理水溶性高分子之粒度較好為10μm以上,更好為20μm以上,又更好為50μm以上,再更好為90μm以上,最好為120μm以上。使用上述粒度範圍之表面處理水溶性高分子時,進一步抑制了顆粒對研磨後之矽基板表面之附著。 On the other hand, the particle size of the surface-treated water-soluble polymer is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 50 μm or more, still more preferably 90 μm or more, and most preferably 120 μm or more. When the water-soluble polymer is treated with the surface of the above particle size range, the adhesion of the particles to the surface of the substrate after polishing is further suppressed.
表面處理水溶性高分子於水中混合後之攪拌操作較好在將鹼性化合物添加於於水中分散有表面處理水溶性高分子之分散體中等,使分散體作成鹼性(例如pH8以上12以下)後進行。該情況下,可促進自表面處理水溶性高分子水解成水溶性高分子及溶解抑制劑,使水溶性高分子更適當地溶解。 It is preferred to add a basic compound to a dispersion in which a surface-treated water-soluble polymer is dispersed in water, and to make the dispersion alkaline (for example, pH 8 or more and 12 or less). Afterwards. In this case, hydrolysis of the water-soluble polymer from the surface treatment into a water-soluble polymer and a dissolution inhibitor can be promoted, and the water-soluble polymer can be more appropriately dissolved.
且,為使表面處理水溶性高分子均一分散於水中,並且使水溶性高分子均一地溶解於水中,較好儘可能使表面處理水溶性高分子之固體粒子與水多接觸。可藉由適當地設定表面處理水溶性高分子之混合速度或溶解時間(亦即攪拌時間)等條件使其為可能。 Further, in order to uniformly disperse the surface-treated water-soluble polymer in water and uniformly dissolve the water-soluble polymer in water, it is preferred to contact the surface-treated water-soluble polymer solid particles with water as much as possible. It is possible to appropriately set the mixing speed or the dissolution time (that is, the stirring time) of the surface-treated water-soluble polymer.
表面處理水溶性高分子之混合速度,就水1L而言,於1分鐘內較好為0.01g以上,更好為0.1g以上,又更好為1g以上,再更好為5g以上,最好為10g以上。且,表面處理水溶性高分子之混合速度,就水1L而言,於1分鐘內較好 為100g以下,更好為70g以下,又更好為50g以下,最好為30g以下。 The mixing speed of the surface-treated water-soluble polymer is preferably 0.01 g or more in 1 minute, more preferably 0.1 g or more, more preferably 1 g or more, and still more preferably 5 g or more. It is 10g or more. Moreover, the mixing speed of the surface-treated water-soluble polymer is better in 1 minute in terms of water 1L. It is 100 g or less, more preferably 70 g or less, still more preferably 50 g or less, and most preferably 30 g or less.
溶解時間較好為1小時以上,更好為3小時以上,最好為6小時以上。且,溶解時間較好為48小時以下,更好為36小時以下,最好為24小時以下。 The dissolution time is preferably 1 hour or longer, more preferably 3 hours or longer, and most preferably 6 hours or longer. Further, the dissolution time is preferably 48 hours or shorter, more preferably 36 hours or shorter, and most preferably 24 hours or shorter.
作為用於使表面處理水溶性高分子與水混合之攪拌機,可使用例如葉片式攪拌機、均質混練機、均質機。使用葉片式攪拌機時,轉速較好為100rpm以上2000rpm以下。使用均質混練機或均質機時,轉速較好為1000rpm以上10000rpm以下。 As the agitator for mixing the surface-treated water-soluble polymer and water, for example, a vane type agitator, a homomixer, and a homogenizer can be used. When a vane type agitator is used, the rotation speed is preferably 100 rpm or more and 2000 rpm or less. When a homomixer or a homogenizer is used, the rotation speed is preferably from 1000 rpm to 10,000 rpm.
接著,針對半導體基板之製造方法加以敘述。 Next, a method of manufacturing a semiconductor substrate will be described.
半導體基板之製造方法具有使用本實施形態之研磨用組成物研磨矽基板表面之步驟。矽基板之研磨係藉由一邊將研磨用組成物供給於矽基板表面,一邊將研磨墊抵壓向同一表面使矽基板及研磨墊旋轉而進行。此時,藉由研磨墊與矽基板表面間之摩擦產生之物理作用研磨矽基板表面。研磨用組成物含有研磨粒時,藉由研磨粒與矽基板表面間之摩擦產生之物理作用研磨矽基板表面。研磨用組成物含有鹼性化合物時,除上述物理作用以外,亦藉由鹼性化合物之化學作用研磨矽基板之表面。 The method for producing a semiconductor substrate has a step of polishing the surface of the ruthenium substrate using the polishing composition of the present embodiment. The polishing of the ruthenium substrate is performed by applying the polishing composition to the surface of the ruthenium substrate while pressing the polishing pad against the same surface to rotate the ruthenium substrate and the polishing pad. At this time, the surface of the crucible substrate is polished by the physical action generated by the friction between the polishing pad and the surface of the crucible substrate. When the polishing composition contains abrasive grains, the surface of the ruthenium substrate is polished by the physical action of friction between the abrasive grains and the surface of the ruthenium substrate. When the polishing composition contains a basic compound, in addition to the above physical effects, the surface of the ruthenium substrate is also polished by the chemical action of the basic compound.
依據以上詳述之本實施形態可發揮如下之效果。 According to the embodiment described above in detail, the following effects can be exhibited.
(1)研磨用組成物含有固體原料的水溶性高分子、與發揮減少水溶性高分子之水溶解速度之作用之溶解抑制劑、與水。將水溶性高分子之重量平均分子量設為A、研 磨用組成物中之水溶性高分子之含量[質量%]設為B、研磨用組成物中之溶解抑制劑之含量[質量ppm]設為C時,C/(A×B)之值為70×10-3以下。藉此,可抑制顆粒對研磨後之矽基板表面之附著。 (1) A water-soluble polymer containing a solid raw material and a dissolution inhibitor and water which function to reduce the water dissolution rate of the water-soluble polymer. The weight average molecular weight of the water-soluble polymer is A, the content of the water-soluble polymer in the polishing composition [% by mass] is B, and the content of the dissolution inhibitor in the polishing composition [ppm] is set to In the case of C, the value of C/(A × B) is 70 × 10 -3 or less. Thereby, adhesion of the particles to the surface of the substrate after polishing can be suppressed.
(2)研磨用組成物中之溶解抑制劑含量為80ppm以下時,抑制了起因於溶解抑制劑之顆粒附著。因此,可進一步抑制顆粒對研磨後之矽基板表面之附著。 (2) When the content of the dissolution inhibitor in the polishing composition is 80 ppm or less, the adhesion of particles due to the dissolution inhibitor is suppressed. Therefore, the adhesion of the particles to the surface of the substrate after polishing can be further suppressed.
(3)水溶性高分子之重量平均分子量為1000000以下時,可減低研磨後之矽基板表面之霧濁程度。 (3) When the weight average molecular weight of the water-soluble polymer is 1,000,000 or less, the degree of haze on the surface of the substrate after polishing can be reduced.
(4)於研磨矽基板之用途,尤其是最終研磨矽基板之用途中藉由使用研磨用組成物,而容易地獲得品質安定之矽基板。 (4) A substrate having a stable quality can be easily obtained by using the polishing composition in the use of polishing the ruthenium substrate, particularly in the final use of the ruthenium substrate.
(5)半導體基板之製造方法包含使用上述研磨用組成物研磨矽基板之步驟。藉此,形成品質安定之矽基板,且可由同一矽基板製造高品質之半導體基板。 (5) A method of manufacturing a semiconductor substrate, comprising the step of polishing a germanium substrate using the polishing composition described above. Thereby, a substrate of stable quality is formed, and a high-quality semiconductor substrate can be manufactured from the same substrate.
又,前述實施形態亦可變更如下。 Further, the above embodiment may be modified as follows.
.前述實施形態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。 . The polishing composition of the above embodiment may be in one dosage form or in a multi-dosage form represented by two dosage forms.
.前述實施形態之研磨用組成物在製造時及銷售時亦可為濃縮之狀態。亦即,前述實施形態之研磨用組成物可以研磨用組成物之原液形態製造及銷售。 . The polishing composition of the above embodiment may be in a concentrated state at the time of production and at the time of sale. That is, the polishing composition of the above embodiment can be produced and sold in the form of a stock solution of the polishing composition.
.前述實施形態之研磨用組成物亦可藉由以水稀釋研磨用組成物之原液而調製。該情況之稀釋倍率較好為2倍以上,更好為5倍以上,又更好為10倍以上。隨著上述稀 釋倍率增大,研磨用組成物之原液輸送成本變得較便宜,並且可節省保存場所。上述稀釋倍率較好為100倍以下,更好為50倍以下,又更好為40倍以下。隨著上述稀釋倍率減少,可提高研磨用組成物原液之安定性。 . The polishing composition of the above embodiment can also be prepared by diluting a stock solution of the polishing composition with water. The dilution ratio in this case is preferably 2 times or more, more preferably 5 times or more, and still more preferably 10 times or more. With the above thin The release ratio is increased, the raw liquid transportation cost of the polishing composition becomes cheaper, and the storage place can be saved. The above dilution ratio is preferably 100 times or less, more preferably 50 times or less, and still more preferably 40 times or less. As the above dilution ratio decreases, the stability of the polishing composition stock solution can be improved.
.前述實施形態之研磨用組成物中含有之各成分可在研磨用組成物之正要製造前以過濾器過濾。前述實施形態之研磨用組成物亦可在正要使用前以過濾器過濾。藉由施以過濾處理,而去除研磨用組成物中之粗大異物,提高研磨用組成物之品質。 . Each component contained in the polishing composition of the above embodiment can be filtered by a filter before the polishing composition is manufactured. The polishing composition of the above embodiment may be filtered by a filter just before use. By applying a filtration treatment, coarse foreign matter in the polishing composition is removed, and the quality of the polishing composition is improved.
上述過濾處理中所用之過濾器材質及構造並無特別限制。過濾器之材質列舉為例如纖維素、尼龍、聚碸、聚醚碸、聚丙烯、聚四氟乙烯(PTFE)、聚碳酸酯、玻璃等。過濾器之構造列舉為例如深層過濾器(depth filters)、褶型過濾器(pleats filters)、薄膜過濾器等。 The material and structure of the filter used in the above filtration treatment are not particularly limited. The material of the filter is exemplified by, for example, cellulose, nylon, polyfluorene, polyether oxime, polypropylene, polytetrafluoroethylene (PTFE), polycarbonate, glass, and the like. The configuration of the filter is exemplified by, for example, depth filters, pleats filters, membrane filters, and the like.
.使用前述實施形態之研磨用組成物研磨矽基板時使用之研磨墊並無特別限制。可使用例如不織布類、麂皮類、含研磨粒之類型、不含研磨粒之類型之任一種研磨墊。 . The polishing pad used in polishing the ruthenium substrate using the polishing composition of the above embodiment is not particularly limited. Any of the types of polishing pads, such as non-woven fabrics, suede, abrasive-containing types, and abrasive-free particles, can be used.
.使用前述實施形態之研磨用組成物研磨矽基板時,亦可回收已使用過之研磨用組成物,再使用於矽基板之研磨中。再使用研磨用組成物之方法列舉為例如將自研磨裝置排出之使用過之研磨用組成物回收於桶槽中,自桶槽內再循環至研磨裝置內使用之方法。藉由再使用研磨用組成物,可減少作為廢液被處理之研磨用組成物之量,並且減 少研磨用組成物之使用量。此就可降低環境負荷方面,及可抑制矽基板之研磨成本方面為有用。 . When the ruthenium substrate is polished by using the polishing composition of the above embodiment, the used polishing composition can be recovered and used for polishing the ruthenium substrate. Further, the method of using the polishing composition is, for example, a method in which the used polishing composition discharged from the polishing apparatus is collected in a tank and recycled from the tank to the polishing apparatus. By using the polishing composition again, the amount of the polishing composition treated as the waste liquid can be reduced and reduced The amount of the composition used for grinding is small. This makes it possible to reduce the environmental load and to suppress the polishing cost of the substrate.
再使用研磨用組成物時,水溶性高分子等各成分因研磨而消耗且損失。因此,較好將水溶性高分子等各成分之減少量補充於研磨用組成物中。所補充之成分可各別添加於研磨用組成物中,亦可依據桶槽之大小或研磨條件等,以任意濃度含兩種以上成分之混合物添加於研磨用組成物中。藉由對再使用之研磨用組成物補充各成分之減少量,可維持研磨用組成物之組成,可使研磨用組成物之功能持續地發揮。 When the polishing composition is used again, each component such as a water-soluble polymer is consumed and lost by polishing. Therefore, it is preferred to supplement the amount of reduction of each component such as a water-soluble polymer to the polishing composition. The components to be added may be separately added to the polishing composition, or may be added to the polishing composition at a concentration of a mixture containing two or more components depending on the size of the tank or the polishing conditions. By supplementing the amount of reduction of each component with the polishing composition to be used, the composition of the polishing composition can be maintained, and the function of the polishing composition can be continuously exhibited.
.前述實施形態之研磨用組成物亦可在研磨矽基板以外之用途中使用。例如,亦可用以獲得由不銹鋼等之金屬、塑膠、玻璃、及藍寶石等所成之研磨製品。 . The polishing composition of the above embodiment can also be used for applications other than polishing a ruthenium substrate. For example, it is also possible to obtain an abrasive article made of metal such as stainless steel, plastic, glass, and sapphire.
接著,針對由前述實施形態可掌握之技術思想加以描述。 Next, the technical idea that can be grasped by the above embodiment will be described.
(A)一種研磨用組成物,其係將溶解抑制劑加成於固體原料的水溶性高分子表面,並調配水溶解速度已被減低之表面處理水溶性高分子與水而成,且含有前述水溶性高分子與前述溶解抑制劑。 (A) a polishing composition obtained by adding a dissolution inhibitor to a surface of a water-soluble polymer of a solid raw material, and preparing a surface-treated water-soluble polymer and water having a reduced water dissolution rate, and containing the foregoing A water soluble polymer and the aforementioned dissolution inhibitor.
藉由將草酸二醛(溶解抑制劑)加成於羥基乙基纖維素(水溶性高分子)之表面而成之表面處理水溶性高分子,以表1所示之條件混合於離子交換水中,調製含羥基 乙基纖維素及草酸二醛之實施例1~45及比較例1之混合液。使用之表面處理水溶性高分子之羥基乙基纖維素之重量平均分子量、及草酸二醛之加成量為多樣。且,藉由以表1所示之條件將羥基乙基纖維素直接混合於離子交換水中,調製含有羥基乙基纖維素之比較例2之混合液。 The surface-treated water-soluble polymer obtained by adding oxalic acid dialdehyde (dissolution inhibitor) to the surface of hydroxyethyl cellulose (water-soluble polymer) was mixed in ion-exchanged water under the conditions shown in Table 1, Modulation of hydroxyl groups A mixture of Examples 1 to 45 and Comparative Example 1 of ethyl cellulose and oxalic acid dialdehyde. The weight average molecular weight of the hydroxyethyl cellulose of the surface-treated water-soluble polymer and the amount of addition of oxalic acid dialdehyde are various. Further, a mixture of Comparative Example 2 containing hydroxyethylcellulose was prepared by directly mixing hydroxyethylcellulose in ion-exchanged water under the conditions shown in Table 1.
接著,將平均一次粒徑35nm之膠體二氧化矽(研磨粒)與氨(鹼性化合物)及離子交換水混合於上述各混合液中,調製實施例1~45及比較例1~2之研磨用組成物。各研磨用組成物之共通組成示於表2。另外,各研磨用組成物中之羥基乙基纖維素及草酸二醛之含量、以及各研磨用組成物中之羥基乙基纖維素之重量平均分子量示於表4。研磨用組成物中之草酸二醛之含量係使用高速液體層析儀測定。研磨用組成物中之羥基乙基纖維素之含量係基於表面處理水溶性高分子之使用量與研磨用組成物中之草酸二醛之含量算出。 Next, colloidal cerium oxide (abrasive grains) having an average primary particle diameter of 35 nm and ammonia (basic compound) and ion-exchanged water were mixed in each of the above mixed liquids to prepare polishing of Examples 1 to 45 and Comparative Examples 1 and 2. Use the composition. The common composition of each polishing composition is shown in Table 2. The content of hydroxyethylcellulose and oxalic acid dialdehyde in each polishing composition and the weight average molecular weight of hydroxyethylcellulose in each polishing composition are shown in Table 4. The content of oxalic acid dialdehyde in the polishing composition was measured using a high speed liquid chromatograph. The content of the hydroxyethylcellulose in the polishing composition was calculated based on the amount of the surface-treated water-soluble polymer used and the content of oxalic acid dialdehyde in the polishing composition.
接著,使用各研磨用組成物,以表3所記載之條件最終研磨預研磨後之矽基板表面。使用之矽基板直徑為300mm,傳導型為P型,結晶方位為<100>,電阻率為0.1Ω.cm以上且100Ω.cm以下,且使用FUJIMI Incorperated股份有限公司製之研磨漿液(商品名GLANZOX 1103)進行預研磨者。接著,針對使用各研磨用組成物進行最終研磨後之矽基板,進行顆粒及霧濁程度之評價。 Next, using the respective polishing compositions, the surface of the pre-polished ruthenium substrate was finally polished under the conditions described in Table 3. After use, the substrate diameter is 300mm, the conductivity type is P type, the crystal orientation is <100>, and the resistivity is 0.1Ω. Above cm and 100Ω. The pre-grinding was carried out using a polishing slurry (trade name: GLANZOX 1103) manufactured by FUJIMI Incorperated Co., Ltd.. Next, the ruthenium substrate after final polishing using each polishing composition was evaluated for the degree of granules and haze.
使用KLA Tencor公司製之晶圓檢查裝置“Surfscan SP2”,測量研磨後之矽基板表面上存在之37nm以上大小之顆粒個數。結果示於表4之“顆粒”欄中。表4之“顆粒”欄中所示之“A”表示顆粒個數未達100個,“B”表示100個以上且未達120個,“C”表示120個以上且未達140個,“D”表示140個以上且未達160個,“E”表示160個以上且未達200個,“F”表示200個以上且未達300個,“G”表示300個以上。 The wafer inspection apparatus "Surfscan SP2" manufactured by KLA Tencor Co., Ltd. was used to measure the number of particles having a size of 37 nm or more present on the surface of the substrate after polishing. The results are shown in the "Particles" column of Table 4. The "A" shown in the "Particles" column of Table 4 indicates that the number of particles is less than 100, "B" indicates 100 or more and less than 120, and "C" indicates 120 or more and less than 140, " D" indicates 140 or more and less than 160, "E" indicates 160 or more and less than 200, "F" indicates 200 or more and less than 300, and "G" indicates 300 or more.
使用KLA Tencor公司製之晶圓檢查裝置“Surfscan SP2”,基於以相同裝置之DWO模式測量研磨後之矽基板表面時所得之測定值評價相同表面之霧濁程度。結果示於表4之“霧濁程度”欄中。表4之“霧濁程度”欄中所示之“A”表示測定值未達0.11ppm,“B”表示0.11ppm以上且未達0.12ppm,“C”表示0.12ppm以上且未達0.13ppm。 The wafer inspection apparatus "Surfscan SP2" manufactured by KLA Tencor Co., Ltd. was used to evaluate the degree of haze on the same surface based on the measured value obtained by measuring the surface of the polished tantalum substrate in the DWO mode of the same apparatus. The results are shown in the column of "degree of haze" in Table 4. "A" shown in the column of "degree of haze" in Table 4 indicates that the measured value is less than 0.11 ppm, "B" indicates 0.11 ppm or more and less than 0.12 ppm, and "C" indicates 0.12 ppm or more and less than 0.13 ppm.
如表4所示,使用含有水溶性高分子及溶解抑制劑之實施例1~45及比較例1之研磨用組成物時,相較於不含溶解抑制劑之比較例2之研磨用組成物時,所測得之顆粒數 較少。且,使用C/(A×B)之值為70×10-3以下之實施例1~45之研磨用組成物時,相較於使用C/(A×B)之值超過70×10-3之比較例1之研磨用組成物時,所測得之顆粒數更少。由該結果顯示藉由使水溶性高分子之重量平均分子量(A)、水溶性高分子之含量(B)、及溶解抑制劑之含量(C)以滿足特定之關係之方式調製研磨用組成物,可有效抑制顆粒對於研磨後之矽基板表面之附著。 As shown in Table 4, when the polishing compositions of Examples 1 to 45 and Comparative Example 1 containing a water-soluble polymer and a dissolution inhibitor were used, the polishing composition of Comparative Example 2 containing no dissolution inhibitor was used. At the time, the number of particles measured was small. Further, when the polishing composition of Examples 1 to 45 having a C/(A × B) value of 70 × 10 -3 or less was used, the value exceeding C × (A × B) was more than 70 × 10 - In the case of the polishing composition of Comparative Example 1, the number of particles measured was smaller. The results show that the polishing composition is prepared such that the weight average molecular weight (A) of the water-soluble polymer, the content (B) of the water-soluble polymer, and the content (C) of the dissolution inhibitor satisfy a specific relationship. It can effectively inhibit the adhesion of the particles to the surface of the substrate after grinding.
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