TW201042019A

TW201042019A - Polishing agent for semiconductor substrate and method for polishing semiconductor substrate

Info

Publication number: TW201042019A
Application number: TW099112311A
Authority: TW
Inventors: Yutaka Nomura; Shigeru Nobe; Jin Amanokura; Naoyuki Koyama; Ayako Tobita
Original assignee: Hitachi Chemical Co Ltd
Priority date: 2009-04-20
Filing date: 2010-04-20
Publication date: 2010-12-01
Also published as: KR20120001766A; WO2010122985A1; JP5413456B2; JPWO2010122985A1; KR101277342B1

Abstract

This invention relates to a polishing agent for semiconductor substrate including abrasive particles, a 1,2,4-triazole, and a basic compound, wherein the basic compound is a basic compound containing nitrogen or is an inorganic basic compound, and a content of the basic compound is 0.1 mass% or more, and a pH is from 9 to 12.

Description

201042019 /p1Jt 六、發明說明： • 【發明所屬之技術領域】本發明是有關於一種適用於半導體基板之表面加工的半導體基板用研磨液、以及半導體基板的研磨方法。【先前技術】 / 以石夕為代表之半導體基板的研磨步驟通常有：用以進行由於切片（slicing)所產生之表面凹凸的平滑化及基板 Ο 面=厚度之均一化的磨削（lapping)步驟、用以精加工為目裇表面精度之拋光（Polishing)步驟（研磨步驟）。拋光步驟進一步分為被稱為粗研磨的1次拋光步驟、與被稱為精畨研磨的最終拋光（final polishing)步驟。1次拋光步，了以根據情況進一步分為被稱為1次拋光步驟及2次拋光步驟這兩個步驟。 • 拋光步驟不僅可用於通常之半導體基板之製造步驟中，而且還可以用於對使用後之半導體基板所進行的再生 ❹ ^理中。而且，近年來開始研究在具有被稱為矽貫通電極 (SiliconThrough_Via ’ TSV)之結構的半導體基板之製造中使用抛光步驟。 ,、被稱為TSV之結構是以貫穿半導體基板内部之形式形成如下所述之電極的結構，所述電極將形成於半導體基 ^表層之元件（device)與半導體基板之背面連接。於先 i於積層多枚半導體元件而形成一個半導體裝置（半導體封裝）之情形時，以打線接合（wireb〇nding)來進行上下之半導體元件彼此之間的連接。藉由採用所述之TSV結 3 201042019 34297pif 該打線接合之連接，可進-步縮小上下之半導體 :件彼此之間的連接所需之區域，因下之^ 術成為取代打線接合之新型技術。 ’ 作為形成TSV之步驟，—般而言是成有:r的背一 ^ 用研究了在對背面進行研叙步驟中使 mechanicaI ^ollsh^ ' ) 歹，照〇KI Techmcal Review 2007 年 l〇月 /第面l::0^ 7·0.3)。自製造效率之觀點考慮，對在該背面之拋光步财所使用之研磨液要求高速的研磨速度。導許^Ϊ先前提出了各種研磨液作為用以研磨形成半導體基板之代表性物質_㈤的研顧。例如 ?專”第3170273號說明書中揭示了：膠體二氧化矽[Technical Field] The present invention relates to a polishing liquid for a semiconductor substrate which is suitable for surface processing of a semiconductor substrate, and a polishing method for the semiconductor substrate. [Prior Art] The polishing step of a semiconductor substrate typified by Shi Xi usually includes: smoothing of surface unevenness due to slicing and uniformity of substrate surface = thickness uniformity The step is a finishing step (grinding step) for finishing the surface accuracy. The polishing step is further divided into a polishing step called coarse grinding, and a final polishing step called fine grinding. The polishing step is further divided into two steps, which are referred to as one polishing step and two polishing steps, depending on the case. • The polishing step can be used not only in the manufacturing steps of a typical semiconductor substrate, but also in the regeneration process performed on the used semiconductor substrate. Moreover, in recent years, research has been conducted on the use of a polishing step in the manufacture of a semiconductor substrate having a structure called a germanium through electrode (SiliconThrough_Via' TSV). The structure called TSV is a structure in which an electrode formed as described below is formed through the inside of the semiconductor substrate, and the electrode is connected to a device formed on the surface of the semiconductor substrate and the back surface of the semiconductor substrate. In the case where a plurality of semiconductor elements are stacked to form a semiconductor device (semiconductor package), the upper and lower semiconductor elements are connected to each other by wire bonding. By using the TSV junction 3 201042019 34297pif, the wire bonding connection, the upper and lower semiconductors can be further reduced in the area required for the connection between the components, and the next technique becomes a new technology to replace the wire bonding. As a step to form the TSV, it is generally: the back of the r is used to study the mechanicaI ^ollsh^ ' ) in the step of the study on the back side, according to the KI Techmcal Review 2007 /The first face l::0^ 7·0.3). From the viewpoint of manufacturing efficiency, a high-speed polishing rate is required for the polishing liquid used in the polishing step on the back surface. A variety of polishing liquids have been previously proposed as a representative substance for polishing a semiconductor substrate _(5). For example, "Special" No. 3170273 discloses: colloidal cerium oxide

Uolkrnl silica)及矽膠（silicagd)可用作在半導體元件 (semiconductor device)之製造中最頻繁使用的半導體姓晶表面之研磨劑。而且，在美國專利第317〇273號說明中記載了：所使用之溶膠（S()1)之膠體二氧化石夕及石夕膠: 一次粒子的粒徑為 4 nm〜200 nm。在美國專利第4169337號說明書中揭示了：藉由使用將一次粒子之粒徑為 4 nm〜200 nm、較佳的是4 nm〜1〇〇 nm的膠體形態的二氧化矽或矽膠之任意者與水溶性胺組合而成者作為研磨劑，可有效地對半導體基板、特別是石夕之半導體基板表面進行研磨。與存在於矽溶膠或凝膠中之二氧化矽相關的胺之量為〇·5質量％〜5·〇質量％、較佳的 201042019 是1.0質量％〜5.〇質量％、最佳的是2 〇質量％〜4量 %。 .、在美國專利第4462188號說明書中揭示了：藉由使用〇.1質量％〜5.0質量％ (最佳的是2.G f量％〜4 ()質量％) 的水溶性四級銨鹽或者添加有四級銨鹽基的水性二氧化矽組成物，可改良矽基板的研磨速度。 ΟUolkrnl silica and silicagd can be used as abrasives for semiconductor surface sites which are most frequently used in the manufacture of semiconductor devices. Further, in the description of U.S. Patent No. 317,273, the colloidal silica (S()1) used is a colloidal silica dioxide and a cerium: the primary particles have a particle diameter of 4 nm to 200 nm. In the specification of U.S. Patent No. 4,169,337, it is disclosed that any of the colloidal forms of cerium oxide or tantalum having a primary particle diameter of 4 nm to 200 nm, preferably 4 nm to 1 〇〇 nm, is used. When combined with a water-soluble amine, it can be used as an abrasive to effectively polish the surface of a semiconductor substrate, particularly a semiconductor substrate. The amount of the amine associated with the cerium oxide present in the cerium sol or the gel is 5·5 mass% to 5·〇 mass%, preferably 201042019 is 1.0 mass% to 5. 〇 mass%, and most preferably 2 〇 mass% ~ 4% by volume. In the specification of U.S. Patent No. 4,462,188, it is disclosed that the water-soluble quaternary ammonium salt is used by using 11% by mass to 5.0% by mass (optimally, 2. G f amount % to 4 ()% by mass). Alternatively, an aqueous cerium oxide composition having a quaternary ammonium salt group may be added to improve the polishing rate of the ruthenium substrate. Ο

G 在日本專利特公昭似㈣號公報中揭示了：將石夕或鍺半導體材料研磨為高度之表面精加卫狀態的方法。在日本專利特公昭57·5,號公報巾記.技射，研磨液是 =用具有經改該理之賴狀卿，二氧切濃度為約2 約50質量％，且pH為11〜12·5的研磨液。而且，於膠體狀鄉找質處射，祕學轉狀姆子包覆比=積為約2W/g〜_ m2/g之二氧切粒子的表面 :使:_個未包覆粒子表面上的㈣子表面包覆有約i 個〜約50個紹原子。通常情況下，在pH為u以上之範為研磨粒子之"氧切解聚合成秘魏鹽而使 P中並不^相/懷此’在日本專利特公昭57_58775號公報中並不產生解聚合，可以在阳為進行研磨。 #阳為11以上之範圍内迅速地在二轉利制眧62侧33號公報中揭*了一 =嗪1研磨液含㈣嗪或魏上附有低魏基取代基性膠體石夕溶膠或凝膠，且相對 ΐ::?1質量%〜5質量%之派嗪。而且，在曰本專利特_ 62-則3號公報中揭示了以圓 5 201042019 34297pif 藉由日本專利特開昭必勒號公報，料磨液巾含有㈣之情形時，與使用魏乙基乙醇胺 (ammo ethyl ethanolamine)之情形相比氧化石夕即可獲得同等之研磨速度。而且，在昭62-30333號公報中記載了：在強驗性的旅嘻的系^中$ 調整ΡΗ所必需的苛性驗（eaustie alM) 在日本專利特開2_·_2號公報中揭示了一磨用組成物，其特徵在於含有：研磨材料、唾類及 ^ ^ B 2006-80302 物^ 了藉由將销及其衍生物添加至研磨用組成物中’可“研磨驗成物之研磨能力 =:氮原子的未共用電子對(二=二 :接作用於研磨對象物上’並且具趙揭示了應用味峻的i 導體糊制平G2指684號公報巾，作為減低半石t S表面凹凸之研磨液’揭示了含有水、膠體二氧化二胺之類的水溶性高分子、及如氯化舞之類 /生现類的研磨液。然而，於使用日本專利特門单號公報中記載之研磨液之情形時產生了如下之二時間變長添加了水溶性高分子而造成研磨速度降低，加作為專r寺開2008-53414號公報中，至於用以減低之—種的亮點缺陷(_ point defect)的研磨液， I不了研磨用組成物中之納離子及乙酸離子之任一者的濃 201042019 ^為=町、或者研磨馳成財之麟子及乙酸離 ^ 為1〇Ppb以下’研磨用組成物較佳地含有如羥二基纖維素之_水雜高分子、如氨之軸鹼、及如朦 Ο ❹ 類的研磨粒的研磨液。在曰本專利特開 Μ 7 Z號公報巾記載之研聽巾，含有紅基纖維素、料為水紐s分子，_子及乙馨子之濃度〈—貝，顯不出改善咖的結果。然而，在實例中所示 ^水溶性高分子的添加量為_2質量％以下，因此在使 ^本1 利特開娜_號公報$記载之研磨液之情 ^果iM^^PD &外之缺陷（例如基板表面之凹凸）等的半=體基板的抛光步驟藉由分為多個步驟而達成加工曰縮短化效率化及南品質化，在各個拋光步驟中之的並不相同’在各個抛光步驟中所使用之研磨液之特性亦不相同。在粗研磨之階段，為了齡在磨削步騄等中產生的比 ^大的凹^者除去受到損傷（damage)的半導體基板部刀，而要求高速之研磨速度。另一方面，在精加工研磨中，主要目的在於實能達成的表蚊高度平滑似及半導職板之缺為滿足上述特性，雖然發明了如先前技術中所示種研磨液及研磨方法，但並不能充分滿足性，、進—步改良研綠騎磨找。要求 7 201042019 34297pif 為了板之材料進行研磨之情形時， :磨速度间逮化，有效的是提高研磨液之阳。然的研磨液在多數情訂於其研磨触方面存在偏平拉性ρ，即使是同—組成之研舰，但研磨速度、傷痕、〜性等研磨特性並不穩n且，在使用量的研舰之情_，存在如下問題： ;研磨粒而造成產生傷痕、廢棄處理【發明内容】 θ 之第—目的在於提供—種可藉由高速穩定之拋 '_、導體基板之加工時間、使步驟管理變容易、以穩定之半導縣㈣半導縣板研磨液以及使用該半導體基板研磨_半導體基板的研磨方法。本發明之第二目的在於提供-種可將半導體基板之表為凹凸少且平滑、缺陷少之表面的半導體基ί 用研磨液以及半導體基板用研磨液的研磨方法。，本發明之第二目的在於提供一種可以實用之研磨速度且較^之研磨量而將半導體基板之表面研磨加王為凹凸少之平滑表面的半導體基板用研磨液以及半導體基板用研磨液的研磨方法。主本發明者等人發現於研磨粒子中使用二氧化矽（Si〇2) 之h形時，可降低時間及研磨液之pH，降低研磨速度。另外，本發明者等人發現藉由將規定之添加劑與二氧化矽併用，可控制pH及研磨速度，且可減低研磨後之基板表面之粗輪度，從而完成本發明。 201042019 <第—半導體基板用研磨液（第一發明）> 1 2 4^1明之第一半導體基板用研磨液含有研磨粒子、榀二坐、鹼性化合物，所述鹼性化合物是含氮鹼性化合，或…機驗性化合物，所述驗性化合物的含量為0.1質量 0以上’ pH為9以上且12以下。 Ο Ο ㈣ί由第Γ發明，可高速地進行由以轉為代表之材料之半導體基板的研磨。而且，藉由所述第一發明，磨===;:磨液之。Η降低，因此可使研於第發明中，鹼性化合物起到用以獲得研磨速产作用。而且，存在半導體基板用研磨液中之ί性斑二添加量越多，則研磨速度會變得越高之傾向。自 a較咼之研磨速度之觀點考慮，驗性化合物之含量較佳 =0.15質量％以上，更佳的是G2質量％以上。而且，雜2於則之增㈣造狀表面祕度,€、化或二氧化〇夕解聚0之觀點考慮，鹼性化合物之含量較佳的是5.質量〇/〇以下，更佳的是2質量％以下。銨或ΓίΓ是於第—發財，含氮驗性化合物含有氫氧化 ’ 5虱乳化四甲基銨。而且，較佳的是於第一發明益 =驗性化合物含錢氧化_氫氧钱。這麵性化合^ 於低臭味之方面較為優異。 <第二半導體基板用研磨液（第二發明）> 本發明H導縣㈣研磨液含有表面經銘酸鹽貿之改質二氧化石夕、無機驗性化合物，所述改質二氧化 9 201042019 34297pif 矽之含量為0.01質量％以上且u 上且12以下。置/°以下’pH為9以藉由第二發明，可高速地進行所形成之半導體基板的研磨。因此^等為代表之材料導體基板之加工時間。错由本發明可減低半較佳的是於第二發明中， 7 nm〜50 nm。虱化矽之一次粒徑為藉由使改質一氧化石夕之—次粒容易獲得實用之研磨速度。而且，藉^ 7:以上’變得 =粒經為一下’變得容易抑制傷痕钟或於第二發财，錢驗性化合物含有氣氧化如上所述，於第二發明中，無機鹼性化合物亦㈣丨用以獲得研磨速度之溶解劑的作用。而且，存 ==驗性化合物之添加量越多，則研磨“ ==越同之傾向。而且，於第二發明中，藉由改質二氧 f與無機雜化合物之組合錢改質二氧切（研磨粒之表面電位變得最大，因此可使研磨速度高速化。於化合物中’於低臭味之方面而言，氫氧化鉀或氫氧化鈉較為優異。較佳的是第二發明更含有12,4·三唑。藉此可抑制保存時或使用時研磨液之ρΗ降低，研磨液之品質穩定，因此可使研磨速度之降低及變動極其小。 201042019 其結果可進行穩定之拋光，使步驟管理變容易，以及加工品質穩定之半導體基板。 ΟG. In Japanese Patent Publication No. (4), a method of grinding a stone or a semiconductor material into a highly polished surface is disclosed. In Japanese Patent Publication No. Sho 57.5, No. 5, the technical solution, the polishing liquid is used, and the dioxin concentration is about 2 to about 50% by mass, and the pH is 11 to 12. · 5 grinding fluid. Moreover, in the colloidal township to find the quality of the surface, the secret transformation of the merging ratio = the product of about 2W / g ~ _ m2 / g of the surface of the dioxoid particles: so that: _ uncoated particles on the surface The (iv) sub-surface is coated with about i to about 50 Shao atoms. In general, in the case where the pH is u or more, the particle of the abrasive particle is "oxygen-cleaved and polymerized into a secret salt, and the P is not in the phase." In Japanese Patent Publication No. Sho 57_58775, no solution is produced. Polymerization can be carried out in the yang. #阳为11范围内, rapidly disclosed in the No. 33 of the second transfer system, No. 33, a = azine 1 slurry containing (tetrazine) or Wei with a low-weilk-substituted colloidal sol or sol Gel, and relative to:: 1% by mass to 5% by mass of pyrazine. Further, in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 3, No. 3, 2010, the disclosure of the Japanese Patent Publication No. 3, No. 3, pp. In the case of ethyl ethanolamine, the same grinding speed can be obtained compared to the case of oxidized stone. Further, Japanese Patent Publication No. Sho 62-30333 discloses that the caustic test (eaustie alM) necessary for the adjustment of the 嘻 in the 嘻嘻在在在在在在 eau eau eau eau eau eau eau eau eau eau eau eau eau eau eau eau eau eau eau A grinding composition characterized by comprising: an abrasive material, a saliva, and a grinding material capable of "grinding a test article" by adding a pin and a derivative thereof to the polishing composition. =: the unshared electron pair of the nitrogen atom (two = two: acting on the object to be polished) and Zhao revealed that the application of the i-conductor paste flat G2 refers to the No. 684 publication towel as a reduction of the half stone t S surface The uneven polishing liquid 'discloses a water-soluble polymer containing water, colloidal diamine, and a polishing liquid such as a chlorinated dance or the like. However, in the Japanese Patent Application No. In the case of the described polishing liquid, the following two times have become longer, and the water-soluble polymer is added to cause a decrease in the polishing rate, and it is added as a highlight defect in the publication of the Japanese Patent Publication No. 2008-53414. (_ point defect) of the slurry, I can not use the grinding The concentration of either the nano-ion and the acetic acid ion in the product is 201042019 ^ is = machi, or the kiln and the acetic acid are less than 1 〇 Ppb or less. The polishing composition preferably contains, for example, hydroxy A polishing liquid of a cellulose-based water-based polymer, such as a shaft of ammonia, and an abrasive particle such as an anthraquinone. The earphones described in the Japanese Patent Laid-Open Publication No. 7 Z-A. The cellulose and the material are water s molecules, and the concentration of _ and EB seeds is not the result of improving the coffee. However, the addition amount of the water-soluble polymer shown in the examples is _2 mass% or less. Therefore, the polishing step of the half-substrate substrate such as the defect of the polishing liquid described in the Japanese Patent Publication No. 1 (the surface roughness of the substrate) The process is divided into a plurality of steps to achieve processing, shortening efficiency and south quality, which are different in each polishing step. 'The characteristics of the polishing liquid used in each polishing step are also different. In the stage, the damage generated by the grinding in the grinding step or the like is removed. In the case of finishing polishing, the main purpose of the finishing is to achieve a high degree of smoothness of the mosquitoes and the lack of a semi-finished board to satisfy the above characteristics. Although a polishing liquid and a grinding method as shown in the prior art have been invented, it is not sufficiently satisfactory, and the green grinding and grinding are further improved. Requirements 7 201042019 34297pif For the grinding of the material of the board, : grinding When the speed is caught, it is effective to increase the yang of the slurry. However, most of the slurry has a flat pull ρ in terms of its abrasive contact, even if it is the same composition, but the grinding speed, scar, and sex The grinding characteristics are not stable, and in the case of the use of the ship, there are the following problems:; grinding particles to cause scratches, waste disposal [invention] θ of the first - the purpose is to provide - a high speed Stable throwing '_, processing time of the conductor substrate, making the step management easy, stabilizing the semi-conducting county (4) semi-lead plate grinding liquid and grinding using the semiconductor substrate_semiconductor base Grinding method. A second object of the present invention is to provide a polishing method for a semiconductor-based polishing liquid and a polishing liquid for a semiconductor substrate which can exhibit a surface having a small unevenness, a small amount of irregularities, and a small number of defects. A second object of the present invention is to provide a polishing liquid for a semiconductor substrate and a polishing liquid for a semiconductor substrate, which are capable of polishing a surface of a semiconductor substrate at a polishing rate and a polishing amount which is less than a polishing amount. method. The inventors of the present invention have found that when the h-shape of cerium oxide (Si〇2) is used in the abrasive particles, the time and the pH of the polishing liquid can be lowered, and the polishing rate can be lowered. Further, the inventors of the present invention have found that by using a predetermined additive in combination with cerium oxide, the pH and the polishing rate can be controlled, and the coarse rotation of the surface of the substrate after polishing can be reduced, thereby completing the present invention. 201042019 <The first polishing liquid for semiconductor substrate (first invention)> The first polishing liquid for semiconductor substrate of the first semiconductor substrate contains abrasive particles, a ruthenium, a basic compound, and the basic compound is nitrogen. A basic compound, or a functional compound, wherein the content of the test compound is 0.1 mass% or more, and the pH is 9 or more and 12 or less. Ο Ο (4) ί Invented by the third invention, the polishing of the semiconductor substrate of the material represented by the conversion can be performed at high speed. Moreover, with the first invention, grinding ===;: grinding liquid. The ruthenium is lowered, so that it can be studied in the first invention, and the basic compound is used to obtain a quick-moving effect. Further, in the polishing liquid for a semiconductor substrate, the larger the amount of the plaque added, the higher the polishing rate tends to be. The content of the test compound is preferably 0.15% by mass or more, and more preferably G2% by mass or more, from the viewpoint of the polishing rate of 咼. Moreover, the addition of the impurity to the fourth is increased (4) the surface topography of the shape, and the content of the basic compound is preferably 5. mass 〇 / 〇 or less, more preferably It is 2% by mass or less. Ammonium or ΓίΓ is the first to be rich, and the nitrogen-containing test compound contains hydroxide 虱 5 虱 emulsified tetramethylammonium. Moreover, it is preferred in the first invention that the test compound contains money oxidized hydroxyhydrogen. This surface combination is superior to low odor. <Second Semiconductor Substrate Polishing Liquid (Second Invention)> The present invention has a surface-modified salt dioxide, an inorganic test compound, and an improved inorganic dioxide. 9 201042019 34297pif The content of bismuth is 0.01% by mass or more and u is above 12 or less. The pH is set to be lower than or equal to or lower than 9 by the second invention, whereby the formed semiconductor substrate can be polished at a high speed. Therefore, ^ and so on represent the processing time of the material conductor substrate. The error can be reduced by the present invention in the second invention, 7 nm to 50 nm. The primary particle size of the bismuth telluride is easy to obtain a practical polishing speed by modifying the primary oxidized stone. Moreover, by ^7: the above 'becomes = the grain is a little bit' becomes easy to suppress the scar clock or the second fortune, the money test compound contains gas oxidation as described above, in the second invention, the inorganic basic compound Also (4) use the solvent to obtain the grinding speed. Moreover, the more the addition amount of the test compound is, the more the same is applied, and the second invention is modified by the combination of the modified dioxine f and the inorganic hetero compound. Since the surface potential of the abrasive grains is maximized, the polishing rate can be increased. In the case of the compound, potassium hydroxide or sodium hydroxide is excellent in terms of low odor. It contains 12,4·triazole. This can suppress the decrease of the pH of the polishing liquid during storage or use, and the quality of the polishing liquid is stable. Therefore, the polishing rate can be reduced and the variation is extremely small. 201042019 The result is stable polishing. It is easy to manage the steps and process the semiconductor substrate with stable quality.

另外，作為半導體基板的研磨方法之發明，本發明提供-種半導縣㈣研財法，其是用㈣射貫通電極的半導體基板的研磨方法，其包括：切基板之其中一個面上形成凹凸部之步驟；使金屬埋入至所述凹凸部之步驟；對絲板之另-個面進行背面研磨之步驟；使用第一半導體基板用研磨液或第二半導體基㈣研磨液，對另一個面進行研磨以使金屬露出之研磨步驟。 =可以-崎符良好之研磨速度，—面將在形成石夕 ΐ坦化^之過程中所產生的背面研磨後之销傷層充分地導導體基板的研磨方法之發明，本發明提 ί 夕晶圓磨削或研磨後’對石夕晶圓進行餘第-步驟；使用第—半導體基板用研磨液或研磨液，對粗晶圓進行研磨之粗研磨步另外’在本發明中，將心對成域品之㈣圓加:稱為「精加工研磨」，將作為精加工 —、隱奴而進仃的研磨加工稱為「粗研磨右為此種半導體基板的研磨， ^ 體基板之表面進行研磨加1方法貝速地對半導 t為半導體基板的研磨方法之發明供-種半導體基板的研磨方法，其是用於再二2 11 201042019 34Zy/pif 基板的研磨方法，其包括：對附著濕式蝕刻之步驟；使用第〜半導、者物之矽晶圓進行導體基板用研磨液’對經濕式飿磨液或第二半研磨步驟。日日圓進行研磨之粗若為此種半導體基板的研磨方而回收的半導體基板（測試晶圓等之了再利用附著物，且高速研磨加4凹凸較少之不需要之Further, as an invention of a polishing method for a semiconductor substrate, the present invention provides a method for polishing a semiconductor substrate using a (four) through-electrode, which comprises: forming a bump on one surface of a substrate a step of embedding the metal into the concave and convex portion; a step of back grinding the other surface of the silk plate; using the first semiconductor substrate polishing liquid or the second semiconductor substrate (four) polishing liquid to the other A grinding step of grinding the surface to expose the metal. = can be - a good grinding speed of the Kasumi, - the invention of the grinding method of the conductive substrate after the back grinding of the pin-shaped wound layer produced in the process of forming the stone ΐ ΐ ^ ^ ^ ^ ^ After the wafer is ground or polished, 'the remaining step-step is performed on the Shi Xi wafer; the coarse grinding step of grinding the coarse wafer using the polishing liquid or the polishing liquid for the first semiconductor substrate is additionally 'in the present invention, the heart For the four-dimensional product (four) round addition: it is called "finishing grinding", and it is called "finishing grinding", which is called "finishing grinding". This is the surface of the substrate. A method for polishing a semiconductor substrate by a method of polishing by a method of polishing a semiconductor semiconductor substrate with a semi-conducting t, which is a polishing method for a second 2 11 201042019 34Zy/pif substrate, comprising: a step of adhering to the wet etching; using the first to semi-conductive material, the polishing liquid for the conductor substrate is used for the wet honing liquid or the second half-grinding step. Research on semiconductor substrates Semiconductor substrate (wafer testing peer and the reuse of the recovered deposit, it does not require the high-speed and less grinding irregularities plus 4

〈第三半導體基板用研磨液（第三發明月）:面。本發明之$二半導縣細研雜含有 1，2,4-三唑、水溶性高分子、广子、 12以下。祕化口物，PH為9以上且半導==:::: ===形成之另外，較佳的是水溶性高分子之含量_ 板用研磨液之總質量為〇._質量％以上且ig質^%二<The third semiconductor substrate polishing liquid (third invention month): surface. In the present invention, the second semi-conducting county contains 1,2,4-triazole, a water-soluble polymer, and a broad range of 12 or less. The secret substance has a pH of 9 or more and a semiconducting ==:::: === is formed. Further, the content of the water-soluble polymer is preferably _. The total mass of the polishing liquid for the plate is 〇.% by mass or more. And ig quality ^% two

且’憾的是1,2,4·三奴含量相對於半導體基板用研磨液之總質量為〇.〇1質量％以上且1〇質量％以下。藉由使水溶性高分子及U4·三嗤之含量為上述範固，可更確實地將半導體基板之表面研磨加工之平滑表面。〈第四半導體基板用研磨液（第四發明）> 本發明之第四半導體基板用研磨液含有研磨粒子、 ’2’4 一唾、水溶性咼分子、驗性化合物，所述ι，2,4_三唾之含量相對於半導體基板用研磨液之總質量為〇〇5質量％ 12 201042019 =且0·5質f%以下’所述水溶性高分子之含量相對於 =V體基板用研磨液之總質量為0施f量％以上且0 量％以下，pH為9以上且12以下。 . 之矣Ϊ此!將由以料為代表之材料所形狀半導體基板之表面研磨加工為凹凸纽平滑、缺陷少之表面。另外’作為半導體基板的研磨方法之發明供一種半導體基板的研磨方法，i 月托 Ο Ο 刻，準備粗晶圓之步驟；對叙曰圆，隹—二由液，研磨液或第四半導體基板用研磨 :步:粗研磨步驟後的彻進一步進行研磨的精加工研由^充分消除於Μ圓上所存在磨加工為缺陷少之表面。 j且研而且’作為半導體基板的研磨方法 2半導體基板的研磨方法，其是用於再利用二體基板的研磨方法，其包括：之牛導體濕式餘刻之步驟；，W =者有附者物之⑪晶圓進行磨步驟，·使日圓進行研磨之粗研用研磨液’對粗研磨步驟後的⑦晶土板加工研磨步驟。步進仃研磨的精右為此種半導體基板的研磨方法，而回收的半導體基板（夺=了再利用附著物，且提供於石夕晶圓上戶;表面除去不需要之圓上所存在之微小凹凸被消除且缺 13 201042019 34297pif 陷較少之可再利用的半導體基板。 <第五半導體基板用研磨液（第五發明）〉本發明之第五半導體基板用研磨液含有研磨粒子、 1，2,4-二唑、水溶性高分子、鹼性化合物，所述三唑之含量相對於半導體基板用研磨液之總質量為〇2質量％以上且3.0質量％以下，所述水溶性高分子之含量相對於半導體基板用研磨液之總f量為讀f量％以上且〇2質量％以下，pH為9以上且12以下。、由此可維持對於半導體基板的規定的研磨速度，且在基板表面存在凹凸之情形時優先研磨凸部。另外，作為半導體基板的研磨方法之發明，本發明提供-種半導縣板的研磨方法，其是驗再湘之半導體基板的研磨方法，其包括：對附著有附著物之石夕晶圓進行濕，姓刻後’財晶11]進行研磨而準備粗晶圓之步驟；使用第三半導縣板料磨液或第五半導體基板用研磨液，對所述粗晶圓進行研磨之粗研磨步驟。若為此種半導體基板的研磨方法，則可以將數個步驟進行的粗研磨以—個步料特，目此可在粗研磨中產生的半導縣板的研賴耗。由此亦可獲得= 使石夕晶圓的再利用次數變多的效果。又、另外，作為半導體基板的研磨方法之發明，供一種半導體基板的研磨方法，其是用以形二叔的半導體基板的研磨方法，其包括：在矽基板之二=電極面上形成凹部之步驟；使金屬埋入至所述二二了個 I ;對 14 201042019 ~ —-产— 矽基板之另一個面進行背面研磨之步驟；使用第三半導體基板用研磨液或第五半導體基板用研磨液，對另—個面進行研磨以使金屬露出之研磨步驟。由此可以較少之研磨量而將在形成矽貫通電極之過程中產生的背面研磨後之研削痕充分地平坦化。Further, the content of the 1, 2, 4, and three slaves is 〇1% by mass or more and 1% by mass or less based on the total mass of the polishing liquid for the semiconductor substrate. By setting the content of the water-soluble polymer and U4·tripocene to the above range, the smooth surface of the surface of the semiconductor substrate can be more reliably polished. <The fourth semiconductor substrate polishing liquid (fourth invention)> The fourth semiconductor substrate polishing liquid of the present invention contains abrasive particles, '2'4 saliva, water-soluble cerium molecules, and an inspective compound, the ι, 2 The content of 4_three saliva is 〇〇5 mass% with respect to the total mass of the polishing liquid for a semiconductor substrate. 12 201042019 = and 0·5 mass f% or less 'the content of the water-soluble polymer is relative to the body of the V-body substrate The total mass of the polishing liquid is 0% by volume or more and 0% by volume or less, and the pH is 9 or more and 12 or less. Then, the surface of the semiconductor substrate shaped by the material represented by the material is polished to have a smooth surface with few irregularities and few defects. In addition, the invention as a method of polishing a semiconductor substrate is provided for a method of polishing a semiconductor substrate, a step of preparing a rough wafer, and a step of preparing a rough wafer, and a liquid crystal, a polishing liquid or a fourth semiconductor substrate. Grinding: Step: The finishing of the grinding after the rough grinding step is completely eliminated by the surface which is sufficiently removed from the grinding process to have few defects. And a grinding method for a semiconductor substrate as a method of polishing a semiconductor substrate, which is a polishing method for recycling a two-body substrate, comprising: a step of wet-remaining of a bovine conductor; The 11th wafer of the object is subjected to a grinding step, and the grinding liquid for grinding the Japanese yen is subjected to a grinding process for the 7-soil plate after the rough grinding step. The fine electrode of the step 仃 grinding is the polishing method of the semiconductor substrate, and the recovered semiconductor substrate (received the reused attachment, and is provided on the Shixi wafer; the surface is removed on the unnecessary circle) The micro-concave-convex is eliminated and is missing. 13 201042019 34297pif A semiconductor substrate that can be reused in a small amount. <The fifth semiconductor substrate polishing liquid (Fifth invention)> The fifth semiconductor substrate polishing liquid of the present invention contains abrasive particles, 1 a 2,4-diazole, a water-soluble polymer, and a basic compound, wherein the content of the triazole is 〇2% by mass or more and 3.0% by mass or less based on the total mass of the polishing liquid for a semiconductor substrate, and the water solubility is high. The content of the molecule is a reading f amount % or more and 〇 2 mass % or less, and a pH of 9 or more and 12 or less with respect to the total f amount of the polishing liquid for a semiconductor substrate. Thus, a predetermined polishing rate for the semiconductor substrate can be maintained, and When the surface of the substrate has irregularities, the convex portion is preferentially polished. Further, as a method of polishing the semiconductor substrate, the present invention provides a method for polishing a semi-conducting plate, which is an inspection method. The polishing method of the semiconductor substrate of Xiang includes the steps of: wetting the Shi Xi wafer to which the attached matter is attached, and grinding the surface to prepare the rough wafer after the last name; using the third semi-conducting county sheet a coarse polishing step of polishing the coarse wafer by a polishing liquid or a polishing liquid for a fifth semiconductor substrate. If the semiconductor substrate is polished, the coarse polishing performed in several steps may be performed as a step. In this way, it is possible to obtain the effect of increasing the number of reuses of the Shixi wafer by the research and development of the semi-conducting plate produced by the rough grinding. Further, as a method of polishing the semiconductor substrate, The invention provides a polishing method for a semiconductor substrate, which is a polishing method for forming a semiconductor substrate having a second shape, comprising: a step of forming a concave portion on a second electrode surface of the germanium substrate; and embedding the metal to the second two a step of back-grinding the other surface of the substrate of 14 201042019 to the substrate, and polishing the other surface by using the polishing liquid for the third semiconductor substrate or the polishing liquid for the fifth semiconductor substrate The polishing step of exposing the metal is performed, whereby the grinding marks after the back surface polishing which are generated in the process of forming the tantalum through electrode can be sufficiently flattened with a small amount of polishing.

OO

另外，於所述粗研磨步驟中，於將粗晶圓之研磨量定義為L (nm)、將粗晶圓之初始階差定義為（则）及將 „之粗晶圓之階差定義為Ru (nm)之情形時，較佳的是在滿足Rt0SL$Rt0xL3且研磨粗晶圓僅L (nm)時 (即’僅以初赠差的13倍以下的研磨量進行研磨），同夺滿足 L/ ( Rt0-Rtl ) $ 1 3 及 Rti $ 1 〇q ( nm )。另外，最終的研磨量當然也可以為上述之⑻紅⑻⑴）二上。向且 --較佳的是於上述之半導體基板的研磨方法中，亦可更包含使用研磨液對粗研磨步驟後之粗晶圓進行之精加工研磨步驟，所述研磨液含有研磨粒子、1，2,本二唑、水溶性高分子、鹼性化合物，pH為9以上且12以’下: 由此可將半導體基;^之表面研磨力口工為日凸少且平滑、缺陷少之表面。、另外’較佳的是於上述之半導體基板的研磨方法更包含使料磨㈣粗研磨步之粗晶圓進行研牿加工研磨步驟’所述研磨液含有研餘子、1，2,4_三唾、^ 溶性高分子、驗性化合物，所述之含^目對半導體基板用研磨液之總f量為GG5 f量％以上且^ 15 201042019 34297pit =°ί:二下:二巧水溶性高分子之含量相對於半導體基板用 1、文之'么質置為〇.〇01質量％以上且〇J質量％以下，ρΗ 為9以上幻2以下。由此可將半導體基板之表面更確實地精加工研磨加卫為凹凸少且平滑、缺陷少之表面。、，另外’較佳的是於上述第三半導體基板用研磨液、第四半導體基板㈣魏及第五半導縣板料磨液中，水溶性高分子為非離子性高分子。藉由使用非離子性高分子，可使減低半導體基板表面之凹凸的效果變得更顯著。車乂佳的疋非離子性高分子是選自聚乙烯咕洛細及聚乙稀 °比洛炫_之共聚物的至少—種。而且，水溶性高分子亦可為包含選自聚乙烯吡咯烷酮及聚乙烯吡咯烷酮之共聚物的至少一種的混合物。於上述本發明之半導體基板用研磨液中，作為研磨對象之半導體基板較佳的是矽或者於基板構成中包含矽的基板。即’本發明對矽或者於基板構成中包含矽的基板的研磨速度特別優異。於本發明之半導體基板的研磨方法中，使用上述本發明之半導體基板用研磨液而研磨半導體基板之表面。藉由此種研磨方法’可將半導體基板之表面高速研磨加工為平滑且缺陷少之表面。 [發明之效果] 於本發明中’可提供一種可藉由高速穩定之拋光而減低半導體基板之加工時間、使步驟管理變容易、以及加工品質穩定之半導體基板的半導體基板研磨液以及使用該半 16 201042019 • A. 導體基板研磨液的半導體基板的研磨方法。而且，藉由本發明可提供一種可將半導體基板之表面研磨加工為凹凸少且平滑、缺陷少之表面的半導體基板用 • 研磨液以及半導體基板用研磨液的研磨方法。土而且，藉由本發明可提供一種可以實用之研磨速度且較少之研磨量而將半導體基板之表面研磨加卫為凹凸少之平滑表面的半導體基板用研磨液以及半導體基板用研磨液 0 的研磨方法。 ▲為讓本發明之上述和其他目的、特徵和優點能更明顯易懂’下文特舉較佳實施例，並配合所附圖式，作詳細說明如下。，w 【實施方式】以下，視需要參照圖式對本發明之一實施形態之半導體基板用研磨液及使用該研磨液之半導體基板的研磨方法加以詳細說明。 <第一半導體基板用研磨液> D 作為第一發明之實施形態，對含有研磨粒子、丨,2,4_ 三唑、鹼性化合物，所述鹼性化合物是含氮鹼性化合物或無機鹼性化合物，所述鹼性化合物的含量為〇1質量％以上，pH為9以上且12以下的半導體基板用研磨液加以說明。於第一實施形態中，即使在研磨液之pH為9以上且 12以下之較高的鹼性區域中亦可控制pH之降低，因此可使隨時間經過所造成之研磨速度降低以及變動極其小，且 17 201042019 34297pif 可進行高速之半導體基板抛光。 (pH) Ο 於第一實施形態_，為獲得對於半導體基板之充分之研磨速度，使半導體基板用研磨液之pH之下限為9〇以 ^。於獲得更優異之研磨速度之方面而言，較佳的是pH 馮9.5 Μ上。另外，為了充分抑制在保存時或使用時研磨液之PH降低，ρΗ之上限為12 〇，較佳的是115以佳的是11.0以下。 PH例如可藉由12,4_三唑及/或鹼性化合物之添加量而調整。另外，半導體基板用研磨液之pH可藉由pH計（例如橫河電機股份有限公司製造、Model pH81)而進行測定。 (1，2,4-三唾及鹼性化合物）In addition, in the rough grinding step, the amount of grinding of the rough wafer is defined as L (nm), the initial step of the rough wafer is defined as (then), and the step of the thick wafer is defined as In the case of Ru (nm), it is preferable to satisfy Rt0SL$Rt0xL3 and polish the rough wafer only L (nm) (that is, 'grinding only by the polishing amount of 13 times or less of the initial weight difference) L / ( Rt0-Rtl ) $ 1 3 and Rti $ 1 〇q ( nm ). In addition, the final amount of polishing may of course be the above (8) red (8) (1)). In the polishing method of the semiconductor substrate, the finishing polishing step of the coarse wafer after the rough polishing step using the polishing liquid containing the abrasive particles, 1, 2, the present diazole, and the water-soluble polymer may be further included. Basic compound, pH is 9 or more and 12 is 'under: Thus, the surface of the semiconductor can be used as a surface with less convexity and smoothness and less defects. Further, it is preferable to The polishing method of the semiconductor substrate further comprises: grinding the coarse wafer of the coarse grinding step of the material grinding step to carry out the grinding processing step of the grinding process' The polishing liquid contains the researcher, the 1,2,4_tris, the soluble polymer, and the test compound, and the total amount of the polishing liquid of the semiconductor substrate is GG5 f or more and ^ 15 201042019 34297pit =°ί:Two: The content of the water-soluble polymer of Diqi is relative to the semiconductor substrate, and the quality of the material is 〇.〇01% by mass or more and 〇J% by mass or less, and ρΗ is 9 or more. The surface of the semiconductor substrate can be more precisely finished and polished to a surface having less unevenness and smoothness and less defects. Further, it is preferably a polishing liquid for the third semiconductor substrate, and a fourth In the semiconductor substrate (4) Wei and the fifth semi-conductor plate mill liquid, the water-soluble polymer is a non-ionic polymer. By using a non-ionic polymer, the effect of reducing the unevenness on the surface of the semiconductor substrate can be made more remarkable.乂乂疋疋疋疋疋疋是是是是是是疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋Copolymer of pyrrolidone and polyvinylpyrrolidone In the polishing liquid for a semiconductor substrate of the present invention, it is preferable that the semiconductor substrate to be polished is a substrate including ruthenium or a ruthenium in the substrate structure. That is, the present invention includes or includes a substrate. In the polishing method of the semiconductor substrate of the present invention, the surface of the semiconductor substrate is polished using the polishing liquid for a semiconductor substrate of the present invention. The surface of the semiconductor substrate can be polished by such a polishing method. High-speed polishing is a surface that is smooth and has few defects. [Effect of the Invention] In the present invention, it is possible to provide a high-speed stable polishing to reduce the processing time of a semiconductor substrate, facilitate step management, and stabilize processing quality. A semiconductor substrate polishing liquid for a semiconductor substrate and a polishing method for a semiconductor substrate using the semiconductor wafer polishing liquid using the semiconductor wafer 16 201042019. Further, according to the present invention, it is possible to provide a polishing method for polishing a semiconductor substrate and a polishing liquid for a semiconductor substrate, which are capable of polishing a surface of a semiconductor substrate into a surface having few irregularities, smoothness, and few defects. Further, according to the present invention, it is possible to provide a polishing liquid for a semiconductor substrate and a polishing liquid for a semiconductor substrate 0 in which a surface of a semiconductor substrate can be polished and a smooth surface having a small number of irregularities can be provided at a practical polishing rate and a small amount of polishing. method. The above and other objects, features, and advantages of the present invention will become more apparent and understood < [Embodiment] Hereinafter, a polishing liquid for a semiconductor substrate according to an embodiment of the present invention and a polishing method of a semiconductor substrate using the polishing liquid will be described in detail with reference to the drawings. <First polishing liquid for semiconductor substrate> D As an embodiment of the first invention, it contains abrasive particles, ruthenium, 2,4-triazole, a basic compound which is a nitrogen-containing basic compound or inorganic The basic compound, the content of the basic compound is 〇1% by mass or more, and the polishing liquid for a semiconductor substrate having a pH of 9 or more and 12 or less is described. In the first embodiment, the pH can be controlled to be lowered even in a relatively high alkaline region where the pH of the polishing liquid is 9 or more and 12 or less, so that the polishing rate due to passage of time can be reduced and the variation is extremely small. And 17 201042019 34297pif can perform high-speed semiconductor substrate polishing. (pH) In the first embodiment, in order to obtain a sufficient polishing rate for the semiconductor substrate, the lower limit of the pH of the polishing liquid for a semiconductor substrate is 9 Å. In terms of obtaining a more excellent polishing speed, it is preferred to have a pH of 9.5 Μ. Further, in order to sufficiently suppress the decrease in the pH of the polishing liquid during storage or use, the upper limit of ρ 为 is 12 〇, and preferably 115 is preferably 11.0 or less. The pH can be adjusted, for example, by the addition amount of 12,4-triazole and/or a basic compound. Further, the pH of the polishing liquid for a semiconductor substrate can be measured by a pH meter (for example, manufactured by Yokogawa Electric Co., Ltd., Model pH 81). (1,2,4-trisodium and basic compounds)

第一實施形態之半導體基板用研磨液的重要特徵是併用1，2,4-三唑與驗性化合物。併用丨,2,4_三唑與驗性化合物對於獲得本發明之效果而言較為重要的理由具體尚不明確’但認為藉由使半導體基板用研磨液含有1，2,4_三唑與驗性化合物這兩者可達成下述事項1、事項2，這是用以起到本發明之效果的重要因素之一。 [事項1]可使鹼性化合物之添加量增多。 [事項2]可使半導體基板用研磨液之PH隨著時間之經過的變動減少。對上述事項1加以詳細說明。驗性化合物起到作為半導體基板之溶解劑之作用。因此，自獲得較高之研磨速度之觀點而言，驗性化合物之添加量越多越好。然而，例如 18 201042019 /pil 將研磨液之pH之目標值設定為n，添加氫氧化钟作為驗 . 性化合物之情形時，會造成半導體基板用研磨液之pH迅速上升。然而，若事先於半導體基板用研磨液中添加1A4_ 三唑，則1，2,4-三唑之pKai低至2·2，因此可抑制隨著鹼性化合物之添加而造成的半導體基板用研磨液之ρΗ上升之現象。由於此種理由，藉由併用丨又冬三唑與鹼性化合物’可增加鹼性化合物之量。〇若於研磨液中單獨含有1，2,4-三唑，則基本上沒有提高研磨速度之效果。為了提高砥磨速度，重要的是將m 三唑與起到作為溶解劑之作用的鹼性化合物併用。根據本發明者等人之研究可知：若藉由添加硫酸或鹽 . 酸等酸而代替1,2,4-三嗤，則雖然可增加鹼性化合物之量，但在此種情況下，未能充分獲得對於矽之研磨速度，或者調配後之pH降低之抑制效果較小。對上述事項2加以說明。於含有ι，2,4-三峻之研磨液 ◎ 中’即使自其調配起經過時間亦可使pH之降低極其小。在使用具有與1,2,4_三唑類似之結構之l,2,3-三唑 (pKaid.l)或 1H-苯幷三唑（pKai=8_2)代替 1，2,4-三唑之情形時，如上述事項1所說明那樣，可知雖然可以增加驗性化合物於研磨液中之添加量，但是調配後之pH降低之抑制效果小，而且不能獲得與鹼性化合物之添加量相符之研磨速度提高效果。而且，於使用咪唑化合物代替1,2,4-‘三唑之情形時，咪唑化合物之ρΚ^高至14.5，因此不能增加發揮作為溶解劑之作用的鹼性化合物之添加量，且調配 19 201042019 34Ζ^7ριί 後之pH降低之抑制效果亦小。自可充分獲得抑制研磨液之pH降低以及提高研磨速度之效果之方面而言，第一實施形態之半導體基板用研磨液中的1，2,4-三唑之添加量較佳的是〇j質量％以上，更佳的是0.25質;f %以上。而且，科於防止研磨粒子凝集等異常之方面而言，1,2,4-三唑之添加量較佳的是1〇質量0/〇以下，更佳的是7質量％以下，最佳的是5質量％以下。 ^外，研磨粒子之凝集並不能—概而言是僅僅因為以木坐之添加量，研磨粒子之粒徑或添加量亦可引起研磨粒子之凝集。自低臭味之方面而言，第一實施形態之半導體基板用研磨液所対讀性化合純佳較選自銨及氫氧匕四甲基録之-独上的含氮雜化合物、或者選 ^鉀^氫氧化納之—㈣上的無齡性化合物。該些化合物可單獨使用，或者使用多種。 σ (研磨粒子） =第-實施形態中，較佳的是使用二氧化秒體基板用研磨液中所含之研磨粒子。由此 : =速度。作為可使用之二㈣，可廣泛乳化發’具體而言例如可列舉：氣相法二氧膠體'^氧化石夕（C〇11〇idalsilica)、沈殿法二氧1 ，自谷易獲得高純度者之方面而言，較佳的β * 相法二氧化石夕或膠體二氧化石夕，自於水中之分難以產生傷痕等研磨缺陷之方面而言，更佳的二膠:二^ 20 201042019 /ριι 化矽。而且 — ㈣可視需要與其他研練子併用。 =-乳切併用之其他研磨粒子具體而化=二氧化鈽、二氧化鈦、氧⑽、有機聚合物^乳 _可獲付實用之研磨速度之方面而言，二氧次粒徑較佳的是5 nm以上，更佳的β 7 乂上I佳的疋7nm以上，特別佳斗疋nm u。而且’自容易抑制傷痕等研磨缺陷之產生之方面而言，二氧化碎之一次粒徑較佳的是綱⑽以An important feature of the polishing liquid for a semiconductor substrate according to the first embodiment is the use of 1,2,4-triazole in combination with an inspective compound. The reason why the use of ruthenium, 2,4-triazole and an organic compound is important for obtaining the effect of the present invention is not clear yet, but it is considered that the polishing liquid for a semiconductor substrate contains 1,2,4-triazole and Both of the test compounds can achieve the following items 1 and 2, which are one of important factors for exerting the effects of the present invention. [Item 1] The amount of the basic compound added can be increased. [Problem 2] The pH of the polishing liquid for a semiconductor substrate can be reduced with time. The above item 1 will be described in detail. The test compound functions as a solvent for the semiconductor substrate. Therefore, from the viewpoint of obtaining a higher polishing speed, the addition amount of the test compound is preferably as large as possible. However, for example, 18 201042019 /pil sets the target value of the pH of the polishing liquid to n, and when the oxidation clock is added as the test compound, the pH of the polishing liquid for the semiconductor substrate is rapidly increased. However, when 1A4_triazole is added to the polishing liquid for a semiconductor substrate in advance, the pKai of 1,2,4-triazole is as low as 2·2, so that polishing of the semiconductor substrate with the addition of the basic compound can be suppressed. The phenomenon that the liquid ρ Η rises. For this reason, the amount of the basic compound can be increased by using together the hydrazine and the triazole and the basic compound. 〇 If 1,2,4-triazole is contained alone in the polishing liquid, there is basically no effect of increasing the polishing rate. In order to increase the honing speed, it is important to use m triazole in combination with a basic compound which functions as a solvent. According to the study by the inventors of the present invention, if an acid such as sulfuric acid or a salt or an acid is added instead of 1,2,4-triazole, the amount of the basic compound can be increased, but in this case, The grinding speed for the crucible can be sufficiently obtained, or the effect of lowering the pH after the blending is less. The above item 2 will be explained. In the polishing liquid containing ι, 2, 4-trisole ◎, the pH reduction can be made extremely small even after the elapsed time from the preparation. In place of 1,2,4-triazole, using 1,2,3-triazole (pKaid.l) or 1H-benzotriazole (pKai=8_2) having a structure similar to 1,2,4-triazole In the case of the above, as described in the above item 1, it is understood that the amount of the test compound added to the polishing liquid can be increased, but the effect of suppressing the pH reduction after the preparation is small, and the amount of addition of the basic compound cannot be obtained. Grinding speed increases the effect. Further, when an imidazole compound is used in place of the 1,2,4-' triazole, the imidazole compound has a pH of up to 14.5, so that the amount of the basic compound which functions as a solvent can not be increased, and the compounding amount is 19 201042019 The inhibitory effect of pH reduction after 34Ζ^7ριί is also small. The addition amount of 1,2,4-triazole in the polishing liquid for a semiconductor substrate of the first embodiment is preferably 〇j from the viewpoint of suppressing the effect of lowering the pH of the polishing liquid and increasing the polishing rate. More than mass%, more preferably 0.25 mass; f% or more. Further, in order to prevent an abnormality such as aggregation of abrasive particles, the amount of 1,2,4-triazole added is preferably 1 〇 mass 0 / 〇 or less, more preferably 7% by mass or less, and most preferably It is 5% by mass or less. In addition, the agglomeration of the abrasive particles does not mean that, in general, the particle size or the amount of the abrasive particles may cause agglomeration of the abrasive particles simply because of the amount of addition of the wood. In terms of low odor, the polishing liquid for the semiconductor substrate of the first embodiment is preferably more pure than the nitrogen-containing compound selected from ammonium and hydrazine tetramethyl groups. ^ Potassium oxyhydroxide - (iv) an age-free compound. These compounds may be used singly or in combination of two or more. σ (abrasive particles) = In the first embodiment, it is preferred to use abrasive particles contained in the polishing liquid for a second-peroxide substrate. Thus: = speed. As the second (four) which can be used, it can be widely emulsified. Specifically, for example, a gas phase dioxygen colloid, a cerium oxide (C〇11〇idalsilica), a shoal method, and a high purity can be obtained from the valley. In terms of the preferred β* phase method, the dioxide dioxide or the colloidal silica dioxide, in terms of the difficulty in producing abrasive defects such as scratches in the water, the better two rubber: two ^ 20 201042019 /ριι Chemical. And — (d) can be used in conjunction with other researchers as needed. =-The other abrasive particles used for the milk cutting and the specificization = cerium oxide, titanium dioxide, oxygen (10), organic polymer emulsified _ in terms of practical polishing speed, the dioxin particle size is preferably 5 Above nm, better β 7 乂 I 佳 7nm or more, especially good 疋 u nm u. Further, from the viewpoint of easily suppressing the occurrence of grinding defects such as scratches, the primary particle diameter of the oxidized cullet is preferably (10)

OO

下，更佳的是loo nm以下，特別佳的是5〇 nm以下極其佳的是40 nm以下。於使二氧切之—次粒徑在上述範圍内之情形時，藉由依賴於粒徑之機械作用所產生之研磨促進效果、與倾著彳、粒徑狀粒子數增加所產生之研磨促進效果的組合，可最大程度地提高磨於第-實施形態中，所謂二氧化石夕之一粒徑，是指可由臟比表面積v而算出的粒子之平均直徑，根據利用氣體吸附法之吸附比表面積（稱為BET比表面積，下同）之測定，由以下之式（1)而算出：Next, it is better to be below loo nm, and particularly preferably below 5 〇 nm, and most preferably below 40 nm. In the case where the dioxo-secondary particle diameter is within the above range, the polishing promoting effect by the mechanical action depending on the particle diameter, and the polishing promotion by the increase in the number of the sputum and the particle-shaped particles are promoted. The combination of the effects can maximize the grinding in the first embodiment, and the particle diameter of the magnet dioxide is the average diameter of the particles which can be calculated from the dirty specific surface area v, and the adsorption ratio according to the gas adsorption method. The measurement of the surface area (referred to as BET specific surface area, the same below) is calculated by the following formula (1):

Dl = 6/ (pxV)…（1)。於式（1)中，D1表示粒子之暫時粒徑（單位：m)、 p表示粒子之密度（單位：kg/m3)、V表示BET比表面積 (單位：m2/g)。更具體而言’首先將研磨粒於真空冷凍乾燥機中進行乾燥，用研缽（磁性、100 ml)將其殘餘部分研碎而製成測疋用试樣’使用Yuasa-ionics股份有限公司製造之bet 比表面積測疋裝置（產品名Autosorb 6 )測定其BET比表 21 201042019 34297pit 二算Γ次，m。另外，於粒子為膠體二氧化石夕月7夺，粒子之笛度p為p==22〇〇 (kg/m3)。因此，若代人贿比表面積v(m2/g)，則成為： Dl-2.727xl〇6/V (m) =2727/V (nm) » 從而可求出一次粒捏。研磨粒子之添加量相對於研磨液整體較佳的是〇⑴ 質量％^上且5.0質量％以下，更佳的是（)()5質量％以上且 3曰〇質量％以下’進—步更佳的是Q丨f量％以上且^ 〇質置％以下。藉由使研磨粒子之添加量為〇〇1質量％以上，變得容易獲得充分之研磨速度。而且，藉由使研磨粒子之添加量為5.0質量％以下，變得料抑制研磨傷等缺陷之產生。 (其他成分）於第實施形悲中，除上述成分以外，可以在不損及上述研磨液之作用效果之範肋，於半導體基板用研磨液 =添加除水以外之溶劑、防蝕劑、氧化劑、水溶性高分子聚合物等通常添加於研磨液中之成分。 (保存形態）第一實施形態之半導體基板用研磨液可以將其成分濃度預先提尚之濃縮形態而進行保存。於使用研磨液時，將濃縮形態之研磨液用水等稀釋至本來之成分濃度而使用即了。另外，亦可以將半導體基板用研磨液之成分分為若干部分的分液形態而保存，在使用時將其等混合而使用。於第一實施形態中’抑制半導體基板用研磨液於調配 22 201042019 後pH降低之效果，不依據二氧化矽之添加量即可獲得。而且，於第一實施形態中，可使半導體基板用研磨液"之為規定之範圍，且增加作為溶解劑之鹼性化合物之添加量，因此可使有助於研磨之化學作用增強。其結果，即使減少作為研磨粒子之二氧化石夕之添加量’亦可獲得較高之研磨速度。 <第二半導體基板用研磨液> Ο 其次，作為第二發明之實施形態，對第二半導體基板用研磨液加以說明1外，關於與第一半導體基板用研磨液之說明重複之部分予以適宜省略。一於所述第-半導體基板用研磨液中，藉由併用m -坐與驗物貝（無論是有機驗性物質還是無機驗性物質 =)而獲得對於㈣言良好之研磨速度，藉由使用表面，由織鹽化而改質之改f二氧化树為研磨粒子，將其 ΐ無機雖㈣個，亦謂得對㈣而言良好之研磨速度0Dl = 6/ (pxV)...(1). In the formula (1), D1 represents a temporary particle diameter (unit: m) of the particles, p represents a density of the particles (unit: kg/m3), and V represents a BET specific surface area (unit: m2/g). More specifically, the abrasive particles were first dried in a vacuum freeze dryer, and the residue was ground in a mortar (magnetic, 100 ml) to prepare a sample for measurement. Using Yuasa-ionics Co., Ltd. The bet specific surface area measuring device (product name Autosorb 6) measures its BET ratio table 21 201042019 34297 pit two times, m. Further, in the case where the particles are colloidal silica, the flute p of the particles is p == 22 〇〇 (kg/m3). Therefore, if the specific surface area of the bribe is v (m2/g), it becomes: Dl-2.727xl〇6/V (m) = 2727/V (nm) » Thus, a single pinch can be obtained. The amount of the abrasive particles added is preferably 〇(1)% by mass and 5.0% by mass or less based on the entire polishing liquid, and more preferably ()() 5% by mass or more and 3% by mass or less. It is preferable that the amount of Q丨f is more than % and the mass of the 〇 is less than or equal to %. By adding the amount of the abrasive particles to 〇〇1% by mass or more, it is easy to obtain a sufficient polishing rate. In addition, when the amount of the abrasive particles added is 5.0% by mass or less, it is possible to suppress the occurrence of defects such as scratches. (Other components) In addition to the above-mentioned components, in addition to the above-mentioned components, the polishing liquid for a semiconductor substrate can be added to a solvent for a semiconductor substrate, a solvent other than water, an anticorrosive agent, or an oxidizing agent, without impairing the effect of the above-mentioned polishing liquid. A component which is usually added to a polishing liquid such as a water-soluble polymer. (Storage) The polishing liquid for a semiconductor substrate according to the first embodiment can be stored in a concentrated form in which the component concentration is previously raised. When the polishing liquid is used, the concentrated slurry is diluted with water or the like to the original component concentration and used. Further, the semiconductor substrate may be stored in a liquid-dispensing form in which the components of the polishing liquid are divided into a plurality of parts, and may be used by mixing them at the time of use. In the first embodiment, the effect of suppressing the pH reduction of the polishing liquid for a semiconductor substrate after blending 22 201042019 is obtained without depending on the amount of addition of cerium oxide. Further, in the first embodiment, the polishing liquid for a semiconductor substrate can be set to a predetermined range, and the amount of the basic compound added as a solvent can be increased, so that the chemical action contributing to polishing can be enhanced. As a result, a higher polishing rate can be obtained even if the amount of addition of the silica dioxide as the abrasive particles is reduced. <Second semiconductor substrate polishing liquid> Ο Next, as a second embodiment of the invention, the polishing liquid for the second semiconductor substrate will be described, and the description of the polishing liquid for the first semiconductor substrate will be repeated. It is suitable to omit. In the polishing liquid for the first-semiconductor substrate, a good polishing rate for (4) is obtained by using m-sitting and an object (whether an organic or inorganic substance) The surface is modified by sizing and sizing. The oxidized tree is an abrasive particle, and although it is (four), it is also a good grinding speed for (4).

人士士人^代伢一種半導體基板用研磨液，其 ΙίΓ峨鹽改f之改質二氧㈣、無機驗性化合旦。/、’〔改質一氧化石夕之含量為0.01質量％以上且L5質二9以上且12以下。於改質二氧化石夕、與 :^解劑的無機鹼性化合物的組合中，改二磨粒子）之表面電位最大程度地變大，因此可使研磨速度高速化。 (改質二氧化矽） 23 201042019 •34zy/pit 鉀[表面之改質’例如可使用減鉀[(A10(0H)2K]等銘化合物而進行。於改質中，例如於二氧化矽之分散加以卜推於门士 - L決"仗肀添加鋁酸鉀，於60〇c =進㈣流’祕使二氧切表面之卿離子化之-Si-〇-Al(〇H)2基。成為更合易可”之改質二氧化矽例如可 r而言，較佳的是改質氣相之方面而言，最佳的是改歸體二氧 2研磨缺^ 亦可視需要與其他研磨粒子併用。可 ^-乳化石夕 „研磨粒子具體而言例如可列舉氧化二7:=:用一氧化鈦、氧化鍅、有機聚合物等。、一、、另外’假設使用氫氧化四甲某餘笙劑之情形時，存在研磨粒子之胺:作為溶解磨速度提高效果之虞。而且，使用^二‘，，'法獲得研A person who uses a polishing liquid for a semiconductor substrate, which is modified by a salt, a modified dioxane (IV), and an inorganic test compound. /, '[The content of the modified nitric oxide is 0.01% by mass or more and the L5 is 2 or more and 12 or less. In the combination of the modified rare earth oxide and the inorganic basic compound of the catalyst, the surface potential of the second abrasive particles is maximally increased, so that the polishing rate can be increased. (modified cerium oxide) 23 201042019 • 34zy/pit Potassium [surface modification] can be carried out, for example, by using a compound such as potassium reduction [(A10(0H)2K]). In upgrading, for example, cerium oxide Disperse and push it to the gate - L decision " 仗肀 add potassium aluminate, at 60 〇 c = enter (four) flow 'secret dioxotomy surface of the ionized -Si-〇-Al (〇H) 2 For the modified sulphur dioxide, for example, it is preferred that in terms of reforming the gas phase, it is preferable that the modified dioxin 2 is not necessary. Other abrasive particles may be used in combination. Specific examples of the abrasive particles include oxidized two: 7: = titanium oxide, cerium oxide, organic polymer, etc., one, and another 'assumed to use four In the case of an enamel agent, there is an amine that grinds particles: as a solution to improve the dissolution rate. Moreover, using the method of ^2,,

石夕之情替藉由銘酸鹽化而改質之改質二氧化 ^ 、存在改質一氧化石夕（研磨粒D 變小’無法獲得研磨速度提高效果之虞。；之表面電位於第二實施形態中，所謂改質二氧疋指用ζ電位（zetap()tential)測定f f表面笔位，化㈣ξ電位。β位之值=3=改質二氧態。在較高的驗.咖中，改質二心 24 201042019 :二二電位之值較小之情形時，可認為是可消除電位之 t月者等人認為當可消除電位之化合物存在於改 Ο 於日本專㈣公昭57•助5號公報巾域 ί::抑制於研磨液之PH為1〇·5以上之範圍所產生乂解聚合而獲得研磨速度，但本發明之效果與ΐ: ::Τ7-58775號公報中記载之先前技術不同。於ΐ 併用編酸鹽化而改質之改質二氧化矽盘 :、機驗性化合物，而發揮出改質二氧化發（研磨粒^ 之研磨力’因此即使減少研磨粒子之添加量亦可獲付充分之研錢度。藉由織贱岐質之改質二Ζ 〇 rrt量相對於研磨·體較麵是_ Ϊ4%以上且下，貝進佳π的是⑽5 f量％以上且^質量％以 I路是αι質量％以上且g.8質量％以下。於，藉由使改質二氧化石夕之添加量為_質量％以即徒=谷祕得充分之研磨速度。而且，於本發明中， P使改貝一氧化石夕之添加量少可獲得充分之研磨速度。質罝/。以下，亦於可獲得實用之研磨速度之方面而 ==較佳的是5-以上，更佳的是上Π 之產生之方Γ二上。而併且？容易抑制傷痕等研磨缺陷 S，改質二氧化矽之—次粒徑較佳的是 25 201042019 34297pif 200 nm以下’更佳的是100 nm以下，特別佳的是5〇以下，極其佳的是40 nm以下。於使改質二氧化矽之一次粒徑為上述範圍内之情形時，藉由依賴於粒徑之機械作用所產生之研磨促進效果、與伴隨著小粒徑化之粒子數之增加所產生之研磨促進效果的組合，可最大程度地提高研^ 速度。另外，改質一氧化石夕之一次粒徑可藉由與第一半導體基板用研磨液中之二氧化矽之一次粒徑同樣之方式進行測定。 (無機驗性化合物）無機鹼性化合物可作為用以獲得研磨速度之溶解劑而，揮作用’且可使改質二氧化梦（研磨粒子）之表面電位取大化’因此可使研磨速度高速化。於低臭味之方面而言，，機驗性化合物較佳的是選自氫氧化鉀及氫氧化鈉之至少 -，。該些化合物可單獨使用，或者可使❹種。自獲得 2之研磨速度之觀點而言，無機驗性化合物之添加量越 ^越好’因此較佳的是0.01質量％以上，更佳的是〇〇5質上，、進—步更佳的是_質量％以上。而且，自抑甲人之增加所造叙表面城度純或者二氧化硬之解觀點而δ ’無機驗性化合物之含量較佳的是5質量。於^佳的是3質量％以下，特別佳的是1質量％以下。得對=二^形態中，1,2,4·三唾幷非必須構成，為了獲唑。；之更尚連之研磨速度，較佳的是更包含1,2,4·三 26 201042019 /pii 度’且可進—步減少隨z變得容易提高研磨速變動。其結果，可藉由古、a、、’i過所造成之研磨速度降低及低半導體基板之加工時口丄而更確實地減質穩定之半導體基板。 1 變4易、及加工品 oShi Xi's feelings are modified by the acidification of the acid dioxide, and there is a modified oxidized stone (the abrasive particles D become smaller), the grinding speed can not be improved. In the second embodiment, the modified dioxins refer to the zappa potential (zetap() tential) to measure the ff surface pen position, and the (four) zeta potential. The value of the beta position = 3 = the modified dioxygen state. In the coffee, the quality of the two hearts 24 201042019: when the value of the second potential is small, it can be considered as the potential to eliminate the potential of the month, such as the ability to eliminate the potential of the compound exists in the change in Japan (four) Gong Zhao 57 • Help No. 5 bulletin area ί:: The polishing rate is obtained by suppressing the polymerization of the polishing liquid at a pH of 1 〇·5 or more, but the effect of the present invention is as follows: ::Τ7-58775 The prior art of the record is different. In addition, the modified cerium oxide disk modified by the acidification is used as a machine-testing compound, and the modified oxidized hair (the grinding force of the abrasive particles) is exerted, so even if it is reduced The addition amount of the abrasive particles can also be fully paid for by the woven enamel. The amount of rrt is _ Ϊ 4% or more with respect to the surface of the polishing body, and is lower than that of 面 , , π π ( 10 10 10 10 10 10 10 10 10 10 π π π π π π π π π π π ^ ^ π ^ π π π π π π π π π By adding the amount of the modified sulphur dioxide to _ mass%, it is sufficient to achieve a sufficient polishing rate. Further, in the present invention, P is sufficient to increase the amount of smectite added to the oxidized stone. The polishing rate is 罝/. In the following, it is also possible to obtain a practical polishing speed == preferably 5 or more, more preferably the upper layer of the upper layer. Suppressing grinding defects S such as scratches, the secondary particle size of modified cerium oxide is preferably 25 201042019 34297pif below 200 nm 'more preferably below 100 nm, particularly preferably below 5 ,, extremely preferably 40 nm In the case where the primary particle diameter of the modified cerium oxide is within the above range, the polishing promoting effect by the mechanical action depending on the particle diameter and the increase in the number of particles accompanying the small particle diameter are The combination of the grinding-promoting effects produced can maximize the grinding speed. Further, the primary particle diameter of the modified nitric oxide can be measured in the same manner as the primary particle diameter of the ceria in the polishing liquid for the first semiconductor substrate. (Inorganic compound) The inorganic basic compound can be used as By using a solvent to obtain a polishing rate, the surface potential of the modified dioxide dioxide (abrasive particles) can be increased, and thus the polishing rate can be increased. In terms of low odor, The organic compound is preferably at least one selected from the group consisting of potassium hydroxide and sodium hydroxide. These compounds may be used singly or in the form of a ruthenium. From the viewpoint of obtaining a polishing rate of 2, an inorganic compound The amount of addition is as good as possible. Therefore, it is preferably 0.01% by mass or more, more preferably 〇〇5, and more preferably _% by mass or more. Moreover, the increase in the self-inhibition of the A person's surface is pure or the hardening of the oxidized view, and the content of the δ 'inorganic test compound is preferably 5 mass. It is preferably 3% by mass or less, and particularly preferably 1% by mass or less. In the case of ==2, 1,2,4·three saliva is not necessary, in order to obtain azole. Further, the grinding speed is more preferably included in 1, 2, 4·3 26 201042019 / pii degrees and the step-by-step reduction becomes easy to increase the grinding speed variation with z. As a result, the semiconductor substrate can be more reliably degraded by the reduction in the polishing speed caused by the ancient, a, and "i" and the low-order processing of the semiconductor substrate. 1 change 4 easy, and processed products o

於此情形時，1，2,4-三唑协楚_丄^ a 之添加量較佳的是與所述第= = f板用研磨液中量同樣之翻。縣板肖研磨液之添加 <第二半導體基板用研磨液> 其次，作為第三發明之實施用研磨液加以說明。另外，關於板 ^及第一+導體基板用研磨液之說明重複之部分予以適宜省略。第二實施雜之半導縣板科纽含有研磨粒子、 1，2,4-二唾」水雜高分子、祕化合物，pH為9以上且 12以下。藉由此種半導體基板用研磨液，可將半導體基板之表面研磨加工為凹凸較少之平滑表面。更詳細地加以說明，於第三實施形態中，藉由含有 I2,4-二唑’即使研磨液於pH為9以上且12以下之較高的驗性範圍内’亦可抑制pH之降低，因此可使隨時間經過所造成之研磨速度之降低及變動極其小，可進行穩定之半導體基板之拋光。而且，於第三實施形態中，可藉由穩疋之抛光而加工品質穩定之半導體基板。而且，於第三實施形態中’藉由水溶性高分子及1，2,4-三唑而減低基板表 27 201042019In this case, the amount of the 1,2,4-triazole-cobalt is preferably the same as that of the first == f-plate polishing liquid. Addition of the plate slab polishing liquid <Second semiconductor substrate polishing liquid> Next, the polishing liquid will be described as a third invention. In addition, the description of the plate and the polishing liquid for the first + conductor substrate will be omitted as appropriate. The second embodiment of the semi-conducting sylvestre sylvestre contains abrasive particles, 1,2,4-di-salt water-hybrid polymer, and a secret compound having a pH of 9 or more and 12 or less. With such a polishing liquid for a semiconductor substrate, the surface of the semiconductor substrate can be polished into a smooth surface having less irregularities. More specifically, in the third embodiment, even if the polishing liquid contains I2,4-diazole, the pH of the polishing liquid can be suppressed even if the pH is in the range of 9 or more and 12 or less. Therefore, the reduction and variation of the polishing rate caused by the passage of time can be made extremely small, and the polishing of the stable semiconductor substrate can be performed. Further, in the third embodiment, the semiconductor substrate of stable quality can be processed by stable polishing. Further, in the third embodiment, the substrate is reduced by the water-soluble polymer and 1,2,4-triazole.

面之凹凸’可將半導體基板之表面研磨加工為凹凸較少之平滑表面。 (1，2,4-三唑）另外’為了利用1，2,4·三唑而獲得上述效果，較佳的是1，2,4-三唑之含量相對於半導體基板用研磨液之總質量為0.001質量％以上且10質量％以下。 (水溶性高分子）半導體基板用研磨液所含有之水溶性高分子（水溶性聚合物）可列舉海藻酸（algin acid)、果膠酸（pectic acid)、叛曱基纖維素（carboxymethyl cellulose)、填脂（agar)、三仙膠（xanthan gum)、聚葡萄胺糖（chitosan)、曱基乙一醇聚葡萄胺糖、曱基纖維素、乙基纖維素、經丙基纖維素、經丙基曱基纖維素、經乙基纖維素、卡德蘭多糖 (curdlan )及聚三葡萄糖（pUiiuian )等多糖類；聚天門冬胺酸、聚麩胺酸、聚離胺酸、聚蘋果酸、聚曱基丙烯酸、聚曱基丙烯酸銨鹽、聚曱基丙烯酸鈉鹽、聚醯胺酸、聚馬來酸、聚伊康酸、聚富馬酸、聚(對苯乙烯羧酸）、聚乙烯基硫酸、聚丙烯酸、聚丙烯醯胺、胺基聚丙烯醢胺、聚丙烯酸銨鹽、聚丙烯酸鈉鹽、聚醯胺酸、聚醯胺酸銨鹽、聚醯胺酸鈉鹽及聚乙醛酸等多羧酸及其鹽；聚乙烯亞胺 (polyethylenimine)及其鹽；聚乙烯醇、聚乙烯吡咯烷酮及聚丙烯醛等乙烯系聚合物；聚乙二醇、聚丙二醇、聚丁二醇、乙二醇-丙二醇嵌段共聚物等。其中，較佳的是羧曱基纖維素、瓊脂、三仙膠、聚葡萄胺糖、曱基乙二醇聚葡 28 201042019 萄胺糖、曱基纖維素、乙基纖維素、躺基纖維素、經丙，甲基纖維素、經乙基纖維素、卡德蘭多糖及聚三葡萄糖等多糖類，聚丙烯醯胺、聚乙埽亞胺、聚乙烯醇、聚乙婦吼嘻烧酮及聚丙烯搭、聚乙二醇、聚丙二醇、聚丁二醇、乙二醇-丙二醇嵌段共㈣等非離子性高分子，更佳的是聚乙稀鱗_及其絲物。另外，上述水雜高分子（水溶性聚合物）可單獨使用，亦可將多種混合使用。而且，The unevenness of the surface can polish the surface of the semiconductor substrate into a smooth surface having less unevenness. (1,2,4-triazole) Further, in order to obtain the above effects by using 1,2,4·triazole, it is preferred that the content of 1,2,4-triazole is relative to the total amount of the polishing liquid for a semiconductor substrate. The mass is 0.001% by mass or more and 10% by mass or less. (Water-soluble polymer) The water-soluble polymer (water-soluble polymer) contained in the polishing liquid for a semiconductor substrate may, for example, be an algin acid, a pectic acid or a carboxymethyl cellulose. , agar, xanthan gum, chitosan, thioglycol polyglucamine, thiol cellulose, ethyl cellulose, propyl cellulose, C Polysaccharides such as fluorenyl cellulose, ethyl cellulose, curdlan and polytriglucose (pUiiuian); polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, Poly(methacrylic acid), ammonium poly(methacrylate), sodium polyacrylate, polyamic acid, polymaleic acid, polyisic acid, polyfumaric acid, poly(p-styrenecarboxylic acid), polyethylene Sulfuric acid, polyacrylic acid, polypropylene decylamine, amine polyacrylamide, ammonium polyacrylate, sodium polyacrylate, polylysine, ammonium polyamide, sodium polyamide, and polyacetaldehyde Polycarboxylic acid and its salts; polyethylenimine and its salts; An ethylene-based polymer such as vinyl alcohol, polyvinylpyrrolidone or polyacrylaldehyde; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol-propylene glycol block copolymer or the like. Among them, preferred are carboxymethyl cellulose, agar, santillac, polyglucosamine, decyl glycol polyglucose 28 201042019 urethane, decyl cellulose, ethyl cellulose, basal cellulose , C, methyl cellulose, ethyl cellulose, cardland polysaccharides and polytriglucose and other polysaccharides, polypropylene decylamine, polyethylenimine, polyvinyl alcohol, polyglycoside and Polypropylene, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol-propylene glycol block (four) and other nonionic polymers, more preferably polyethylene scales and their filaments. Further, the above-mentioned water-hybrid polymer (water-soluble polymer) may be used singly or in combination of two or more. and,

G 在將上述水溶性高分子中的多種混合而使用之情形時，較佳的是該齡物包含選自聚乙糾你·其共聚物之至少一種。、、本發明者等人認為··本發财之半導體基板表面凹凸之減低是由於半導縣板與水溶性聚合物之疏水部之疏水性相互作㈣造成水紐聚合物吸祕半導縣板表面上所引起的。即’吸赚半導體基録面之水雜聚合物，吸附於半導體基板表面之凹凸上，與凹部相比，更容易由研磨墊或研絲子崎去凸部之水雜聚合物，結果促進形成平滑之表面。因此，於使用無離子性基之非離子性水雜聚合物作為水雜聚合低凹凸之效果變顯著。丨月小于馮水溶性聚合物之添加f ’相對於研歧較麵是隱質里/。以上且1G質量％以下，更佳的是_質量％以上且 ^質量％以下。藉由使水溶性聚合物之添加量為議i質量 /〇以上’容易使減低凹凸之效果增大。而且，藉由使^溶性聚合物之添加量為10質量％以下，變得容易防止隨著添 29 201042019 /pil 加水溶性聚合物而造成研磨液之高黏度化及高黏度化所造成之流動性降低，且變得容易防止研磨粒子凝集。於通常情況下’若提高研磨液之溶解作用，則存在半導體基板表面之凹凸變大之傾向。然而，本發明之半導體基板用研磨液所含有之1，2,4-三唑與水溶性聚合物相比較差，但具有減低基板表面之凹凸的效果。因此，於本發明中，藉由併用1，2,4-三唾與水溶性聚合物，能夠以較高之研磨速度將半導體基板之表面研磨加工為凹凸較少之平滑面。 <第四半導體基板用研磨液> 其次，作為第四發明之實施形態，對第四半導體基板用研磨液加以說明。另外，關於與第一半導體基板用研磨液、第二半導體基板用研磨液及第三半導體基板用研磨液之說明重複之部分予以適宜省略。第四實施形態之半導體基板用研磨液含有研磨粒子、 1，2,4·三唾、水溶性高分子、鹼性化合物，所述ι，2,4_三唑之添加量為0.05質量％以上且〇5質量％以下，所述水溶性兩分子之添加量為0001質量％以上且〇j質量％以下， pH為9以上且12以下。第四實施形態特別適合用於半導體晶圓之製造步驟中之精加工研磨用途。即，是與對於矽基板之研磨速度相比，重點更在於消除矽基板上存在之凹凸、除去矽基板上殘存之異物（由研磨粒子及研磨墊之磨損所產生之磨損粉末等）及減低半導體基板之結晶缺陷的研磨液。 30 201042019 ^~r^y / (pH) . 於第四實施形態中，自減少由於異物附著於石夕基板表面等而造成之缺陷的觀點而言，pH為9以上，更佳的是 pH為9.5以上。而且，自抑制由於過度蝕刻所造成之缺陷之產生的觀點而言，pH為12以下，較佳的是n以下，更佳的是1〇·5以下。 (1,2,4-三唾） ❹ 於第四實施形態中，所述1,2,4-三唑之添加量為0 〇5 質量％以上且0.5質量。/〇以下。於容易獲得i，2,4•三唑所具有之pH穩定性或者由於作為溶解劑之鹼性化合物之增量而造成的研磨速度提高效果之方面、及獲得作為晶圓表面之粗度指標之霧度（HAZE，濁度）之改善效果之方面而言，添加量為0.05質量％以上，較佳的是〇·ι質量％以上。 • 另一方面’於避免變得無法獲得與添加量相符之霧度改善效果，另外可抑制研磨粒子凝集之方面而言，添加量為〇.5 質量％以下，更佳的是〇·4質量％以下，特別佳的是0 3質 ^ 量％以下。 (水溶性高分子）第四實施形態中，水溶性高分子（水溶性聚合物）之添加量為0.001質量％以上且0.1質量％以下之範圍。於充分獲得減低矽基板表面缺陷之效果的方面而言，添加量為 • 0‘⑻1質量％以上，較佳的是0.003質量％以上，更佳的是 • 0.005質量％以上，特別佳的是〇.〇1質量％以上。而且，於可抑制產生研磨之阻礙、缺陷之增加、霧度改善之阻礙等 31 201042019 34297pif 異常的方面而言’添加量為〇·1質量％以下，較佳的是〇〇8 質量％以下，更佳的是0.07質量％以下，特別佳的是〇 05 質量％以下，極其佳的是0.03質量％以下。另外，此處所謂矽基板上之缺陷，是指由於研磨粒子或研磨墊之磨損所產生之磨損粉末等異物、或者於矽基板上所產生之結晶缺陷或傷痕等之總稱。添加水溶性高分子而減低缺陷是藉由如下方式而獲知.水溶性高分子吸附於半導體基板表面，由此可防止由 1研磨粒子或研磨墊之磨損所產生之磨損粉末等異物之固著並且可抑制半導體基板表面之懸鍵（dangling bond) 或者晶體原生顆粒缺陷（Cristal〇riginatedParticle，C〇P) 所引起之特定方向之蝕刻。另外’霧度及缺陷之值，可以在對研磨結束後之矽基板表面進行清洗（例如以含有0.06%氫氧化銨之清洗液，使用通常之清洗刷進行6〇秒之清洗）後，使用市售之缺陷檢查裂置而進行測定。 — 具體而言，例如可以將以如下所述之條件而測定之值疋羲為霧度及缺陷。缺陷檢查裴置步驟條件槽案缺陷測定範圍 :LS6700 (日立電子工程公司製造） (測定參數）：VeMlOL :0.1 μιη〜3.0 μιη 投光條件：垂直如上所述’第四實施形態如半導體晶圓之製造步驟中之精加工研磨用途那樣，與對於矽基板之研磨速度相比， 32 201042019 /pu 重點更在於消除石夕基板上存在之微小凹凸以及減低缺陷。 • 因此’較佳的是使研磨粒子之添加量相對於研磨液整體為 0.05質量％以上且0.5質量％以下。如果研磨粒子之添加量為0.05質量％以上，則可消除凹凸；如果研磨粒子之添加量為0.5質量％以下，則可抑制矽基板被過度研磨。 <第五半導體基板用研磨液> 其次，作為第五發明之實施形態，對第五半導體基板〇用研磨液加以說明。另外，關於與第一半導體基板用研磨液、第二半導體基板用研磨液及第三半導體基板用研磨液之說明重複之部分予以適宜省略。第五實施形態之半導體基板用研磨液是含有研磨粒子、ι，2,4-三唑、水溶性高分子及鹼性化合物，所述m 二0坐之添加量為0.2質量％以上且3 〇質量％以下，所述水 ' 溶性高分子之添加量為〇.〇1質量％以上且0.2質量。/〇以下，pH為9以上且12以下之半導體基板用研磨液。 (pH) ® 於第五實施形態中，於獲得所述之對於矽之規定之研磨速度的觀點而言，所述pH為9以上，更佳的是pH為 9.5以上，進一步更佳的是PH為1〇.〇以上。而且，自抑制過度之蝕刻所造成之缺陷之觀點而言，所述pH為12以下，較佳的是Π以下。第五實施形態與第四半導體基板用研磨液相比，丨又孓 • 三唑之添加量多，且所述水溶性高分子之添加量亦多。由此可製成具有如下性質的半導體基板用研磨液：可獲得對 33 201042019 34297pif 於石夕基板之規定之研磨速度，且於表面具有凹凸之情形時可優先研磨凸部。特別是於進行了機械研削加工（研磨等）的矽基板之類的具有較高之階差的矽基板中，可以優先研磨所述階差之凸部，且除去於所述研削加工時產生之研削痕。若為此種半導體基板的研磨方法，則可以利用一個步驟進行在先前分為數個步驟進行的粗研磨，因此可減低粗研磨中產生之半導體基板之研磨損耗。由此亦可獲得使矽晶圓之再利用次數變得更多之效果。、另外，於所述粗研磨步驟中，於將粗晶圓之研磨量定義為L (nm)、將粗晶圓之初始階差定義為Rt〇 (nm)及將經粗研磨之粗晶圓之階差定義為Ru (nm)之情形時，較佳的是在滿足Rt0SLSRt〇xi3且研磨粗晶圓僅L(nm)時 (即，僅以初始階差的1.3倍以下的研磨量進行研磨），同時滿足 L/ (Rt0-Rtl) $1.3 及Rtl$1〇() (nm)。另外，最終的研磨量當然也可以為上述之範圍（〜紅訊/⑶以上。 &其中，所謂研磨量L是表示藉由研磨自粗晶圓除去之部分的厚度。而且’所謂初始階差〜是粗研磨前之粗晶圓表面之凸部與凹部之咼度差的最大值。所謂經粗研磨之粗=圓之階差Rtl是經粗研磨之粗晶圓表面之凸部與凹部之南度差的最大値。首另外’@17是表示第三半導體基板用研磨液〜第五半導體基板料餘巾的1，2,4_三錢水溶性高分子之含量 34 201042019 的圖表。如上所述，於第三半導體基板㈣磨液中，相對於半導體基板用研磨液之總質量，u，4•三奴含量較佳的是讀質量％以上且10質量％以下，水溶性高分子之含量較佳的是謂1質量％以上且1()1量％以下（圖17之第三半導體基板用研純之難的範圍）。而且，於第四半導& 基板用研舰中，婦於半導縣初研餘之總質量， 1,2,4-三峻之含量為0.05質量％以上且〇5質量％以下，水G When a plurality of the above water-soluble polymers are mixed and used, it is preferred that the age includes at least one selected from the group consisting of polyethylenic and its copolymers. The present inventors and the like believe that the reduction of the surface roughness of the semiconductor substrate of the present invention is due to the hydrophobic interaction between the semi-conducting plate and the hydrophobic portion of the water-soluble polymer (4). Caused by the surface of the board. That is, the water-hybrid polymer that absorbs the semiconductor base recording surface is adsorbed on the uneven surface of the surface of the semiconductor substrate, and the water-hybrid polymer of the convex portion is more easily removed by the polishing pad or the weaving wire than the concave portion, and the result is promoted. Smooth surface. Therefore, the effect of using a nonionic hydrophobic polymer having a nonionic group as a water heteropolymerization low unevenness becomes remarkable. The increase in the amount of water-soluble polymer f ’ is less than / in comparison with the research. The above is 1 G mass% or less, and more preferably _ mass% or more and ^ mass% or less. It is easy to increase the effect of reducing the unevenness by making the amount of the water-soluble polymer added to be equal to or higher than 〇. In addition, by adding the amount of the soluble polymer to 10% by mass or less, it is easy to prevent the fluidity caused by the high viscosity and high viscosity of the polishing liquid with the addition of the water-soluble polymer by the addition of 2010 201042019 /pil. It is lowered and it becomes easy to prevent agglomeration of the abrasive particles. In the normal case, when the dissolution of the polishing liquid is increased, the unevenness on the surface of the semiconductor substrate tends to increase. However, the 1,2,4-triazole contained in the polishing liquid for a semiconductor substrate of the present invention is inferior to the water-soluble polymer, but has an effect of reducing unevenness on the surface of the substrate. Therefore, in the present invention, by using 1,2,4-trisap and a water-soluble polymer in combination, the surface of the semiconductor substrate can be polished to a smooth surface having less irregularities at a higher polishing rate. <Finishing Liquid for Fourth Semiconductor Substrate> Next, a polishing liquid for a fourth semiconductor substrate will be described as an embodiment of the fourth invention. In addition, the description of the polishing liquid for the first semiconductor substrate, the polishing liquid for the second semiconductor substrate, and the polishing liquid for the third semiconductor substrate will be appropriately omitted. The polishing liquid for a semiconductor substrate according to the fourth embodiment contains abrasive particles, 1,2,4·three saliva, a water-soluble polymer, and a basic compound, and the amount of the iota, 2,4-triazole added is 0.05% by mass or more. Further, the amount of the water-soluble two molecules added is 0001% by mass or more and 〇j% by mass or less, and the pH is 9 or more and 12 or less. The fourth embodiment is particularly suitable for use in finishing polishing in the manufacturing steps of semiconductor wafers. In other words, compared with the polishing rate for the ruthenium substrate, the focus is on eliminating the irregularities existing on the ruthenium substrate, removing foreign matter remaining on the ruthenium substrate (wear powder generated by abrasion of the polishing particles and the polishing pad, etc.) and reducing the semiconductor. A polishing solution for crystal defects of a substrate. 30 201042019 ^~r^y / (pH) In the fourth embodiment, the pH is 9 or more, and more preferably the pH is from the viewpoint of reducing defects caused by adhesion of foreign matter to the surface of the substrate. 9.5 or more. Further, from the viewpoint of suppressing the occurrence of defects due to over-etching, the pH is 12 or less, preferably n or less, more preferably 1 Å or less. (1,2,4-three saliva) In the fourth embodiment, the amount of the 1,2,4-triazole added is 0 〇 5 mass% or more and 0.5 mass. /〇The following. It is easy to obtain the pH stability of i, 2, 4 • triazole or the improvement of the polishing speed due to the increase of the basic compound as a solvent, and obtain the roughness index as the surface of the wafer. In terms of the effect of improving the haze (HAZE, turbidity), the amount of addition is 0.05% by mass or more, preferably 〇·% by mass or more. • On the other hand, the amount of addition is 〇.5 mass% or less, and more preferably 〇·4 mass, in order to avoid the inability to obtain the haze improvement effect in accordance with the added amount, and to suppress the aggregation of the abrasive particles. Below %, particularly preferably 0 3 mass% or less. (Water-soluble polymer) In the fourth embodiment, the amount of the water-soluble polymer (water-soluble polymer) added is in the range of 0.001% by mass or more and 0.1% by mass or less. The amount of addition is 2.0 Å (8) 1% by mass or more, preferably 0.003 % by mass or more, more preferably 0.005% by mass or more, and particularly preferably 〇, in order to sufficiently obtain the effect of reducing the surface defects of the ruthenium substrate. .〇1% by mass or more. In addition, the amount of addition is 〇·1 mass% or less, and preferably 〇〇8 mass% or less, in terms of the occurrence of an abnormality such as an increase in defects, an increase in defects, and an improvement in haze. 31 201042019 34297pif More preferably, it is 0.07 mass% or less, and particularly preferably 〇05 mass% or less, and particularly preferably 0.03 mass% or less. Further, the term "defect" on the substrate as used herein refers to a foreign matter such as abrasion powder generated by abrasion of polishing particles or a polishing pad, or a crystal defect or a flaw generated on a substrate. The addition of a water-soluble polymer to reduce defects is known in the following manner. The water-soluble polymer is adsorbed on the surface of the semiconductor substrate, thereby preventing the adhesion of foreign matter such as abrasion powder generated by abrasion of the abrasive particles or the polishing pad and The etching in a specific direction caused by a dangling bond or a Cristal 〇 in in 。。。。。。。。。。。。。 In addition, the value of the haze and the defect can be cleaned after the surface of the substrate after the polishing is finished (for example, after cleaning with a cleaning solution containing 0.06% ammonium hydroxide and using a usual cleaning brush for 6 seconds). The defect inspection was sold and the measurement was carried out. — Specifically, for example, the value measured under the conditions described below can be reduced to haze and defects. Defect inspection setting step Condition slot defect measurement range: LS6700 (manufactured by Hitachi Electronic Engineering Co., Ltd.) (measurement parameter): VeMlOL: 0.1 μm to 3.0 μm Projection conditions: Vertical as described above 'Fourth embodiment as semiconductor wafer As for the finishing polishing use in the manufacturing step, compared with the polishing rate for the tantalum substrate, 32 201042019 /pu focuses on eliminating the micro unevenness existing on the Shih-hs substrate and reducing the defects. Therefore, it is preferable that the amount of the abrasive particles added is 0.05% by mass or more and 0.5% by mass or less based on the entire polishing liquid. When the amount of the abrasive particles added is 0.05% by mass or more, the unevenness can be eliminated, and if the amount of the abrasive particles added is 0.5% by mass or less, the ruthenium substrate can be prevented from being excessively polished. <Film for fifth semiconductor substrate> Next, as a fifth embodiment of the invention, a polishing liquid for a fifth semiconductor substrate will be described. In addition, the description of the polishing liquid for the first semiconductor substrate, the polishing liquid for the second semiconductor substrate, and the polishing liquid for the third semiconductor substrate will be appropriately omitted. The polishing liquid for a semiconductor substrate according to the fifth embodiment contains abrasive particles, iota, 2,4-triazole, a water-soluble polymer, and a basic compound, and the amount of the m 2 occupant is 0.2% by mass or more and 3 Å. The amount of the water-soluble polymer added is 〇.〇1% by mass or more and 0.2% by mass or less. / The following is a polishing liquid for a semiconductor substrate having a pH of 9 or more and 12 or less. (pH) ® In the fifth embodiment, the pH is 9 or more, more preferably 9.5 or more, and still more preferably PH, from the viewpoint of obtaining the predetermined polishing rate for ruthenium. It is 1〇.〇 or more. Further, from the viewpoint of suppressing defects caused by excessive etching, the pH is 12 or less, preferably Π or less. In the fifth embodiment, compared with the polishing liquid for the fourth semiconductor substrate, the amount of triazole added is large, and the amount of the water-soluble polymer added is also large. Thus, a polishing liquid for a semiconductor substrate having the following properties can be obtained: when the polishing rate specified for 33 201042019 34297pif on the Shishi substrate is obtained, and the surface has irregularities, the convex portion can be preferentially polished. In particular, in a tantalum substrate having a high step such as a tantalum substrate subjected to mechanical grinding (polishing, etc.), the convex portion of the step can be preferentially polished and removed in the grinding process. Grinding marks. In the case of the method of polishing such a semiconductor substrate, the rough polishing performed in a plurality of steps can be performed in one step, so that the polishing loss of the semiconductor substrate generated in the rough polishing can be reduced. Thereby, the effect of making the number of reuses of the wafer more frequent can be obtained. In addition, in the rough grinding step, the amount of grinding of the rough wafer is defined as L (nm), the initial step of the rough wafer is defined as Rt 〇 (nm), and the rough wafer is coarsely ground. When the step is defined as Ru (nm), it is preferable to polish Rt0SLSRt〇xi3 and grind the rough wafer only L (nm) (that is, grind only by a grinding amount of 1.3 times or less of the initial step difference) ), satisfying both L/(Rt0-Rtl) $1.3 and Rtl$1〇() (nm). Further, the final polishing amount may of course be in the above range (~Red/(3) or more. & wherein the polishing amount L is the thickness indicating the portion removed by the polishing from the rough wafer. Moreover, the so-called initial step difference ~ is the maximum value of the difference between the convex portion and the concave portion of the surface of the rough wafer before rough grinding. The step Rtl of the coarse-grained rough=circle is the convex portion and the concave portion of the rough-polished rough wafer surface. The maximum value of the south degree difference is the same as the content of the 1,2,4_three money water-soluble polymer of the third semiconductor substrate polishing material to the fifth semiconductor substrate material. In the third semiconductor substrate (four) grinding liquid, the content of the u, 4 • three slaves is preferably more than the read mass% and not more than 10% by mass based on the total mass of the polishing liquid for the semiconductor substrate, and the water-soluble polymer The content is preferably 1% by mass or more and 1% by volume or less (the range in which the third semiconductor substrate is difficult to be purely purified in Fig. 17). Further, in the fourth semiconducting & The total quality of the woman’s initial research in the semi-guided county, 1, 2, 4-three The amount is 0.05% by mass or more and 〇5% by mass or less, water

溶性高分子之含量為讀1質量％以上且0.3質#%以下。另外’於_五半導縣板料磨液巾，相躲半導體基板用研磨液之總質量，1，2,4·三唾之含量為G2 f量％以上且 3.0質量％以下’水溶性高分子之含量為〇〇1質量％以上且 0.2質量％以下。 <半導體基板的研磨方法> ，其次，舰用以上所㈣之第-半導體基板用研磨液〜第五半導體基板用研磨液而研磨半導體基板之表面的研磨方法加以說明。作為研磨方法之一例，例如一面將本實施形態之半導體基板用研磨液供給至研磨定盤之研磨布上，一面於將被研磨基板（半導體基板）按壓在研磨布之狀態下，使研磨定盤與被研磨基板相對運動而研磨半基板之表面。作為可於本實施形態的研磨方法中使用之研磨裝置，例如可使用通常的研磨裝置，所述研磨裝置具有：保持被研磨基板之固持器（holder)、可貼附研磨布（墊）且安農有轉速可變之馬達等的研磨定盤。研磨定盤上之研磨布並 35 201042019 無特別之限制’可使用通常之不織布、泡珠聚胺g旨（foamed polyurethane)、多孔氟樹脂（porous fluorineresin)等。於將半導體基板按壓在研磨布之狀態下使研磨布與被研磨基板相對運動時’具體而言使基板與研磨定盤之至少一者運動即可。除使研磨定盤旋轉以外，亦可藉由使固持器旋轉或搖動而進行研磨。而且，研磨方法可列舉使研磨定盤行星式旋轉之研磨方法、使帶狀之研磨布沿長度方向之一個方向直線狀運動之研磨方法等。另外，固持器可以是固定、旋轉、搖動之任意狀態。該些研磨方法如果是使研磨布與半導體基板相對運動，則可以根據被研磨基板或研磨裝置而適宜選擇。於進行研磨期間，較佳的是用泵等將半導體基板用研磨液連續地供給至研磨布。 <使用第一半導體基板用研磨液或第二半導體基板用研磨液之研磨方法> 本貝化形態之第一半導體基板用研磨液及第二半導體基板用研磨液，在使用如上所述之研磨方法對矽或於基板構成中包含矽之基板進行研磨之情形時，具有優異之^磨特性。其中對於矽或於基板構成中包含矽之基板之研磨速度優異。以下，對使用第一半導體基板用研磨液及第二半導體基板用研磨液之半導體基板的研磨方法之實施形態加以說明。 (石夕貫通電極背面研磨方法） 36 201042019 半導體1=3研圖13(e)說明活用第一性的研磨製程之—例。體基板用研磨液之研磨特方法並不限定於該例，本發明之半導體基板的研磨是表示發貫通電圖13㈤、圖13 (c) 於圖_剖面模式圖。 Ο Ο 用凹凸，’卿料導縣板1上形成有通孔次，用公知方法方式形成銅等配線用金屬2°其面（背面）n +導體基板1之形成有凹凸之面的相反機械作用，^ 13Hf °此時，由於#面研磨之較強之面產生森()所示㈣，在半導體基板1之背態之半ί體傷之矽損傷層3。最後，使用本實施形板1進彳研磨液，對上述矽損傷層3及半導體基 13 (c) = _，直至配_金屬2露出於背面，形成如圖 13 (C)所不之矽貫通電極。本實3之表面可存在微細之凹凸，但藉由使用法，板用研磨液之半導體基板的研磨方有凹凸之半導體基板亦可獲得良好之的半導’使用本實施形態之半導體基板用研磨液途中。*板的研磨方法可驗研磨半導縣板之各種用即1、本實施_是—種半導縣板的研磨方法，其是 ::、矽貝通電極的半導體基板的研磨方法’其包括：在石夕基板之財—個面上形成凹部之步驟；使金屬埋入至凹狀步驟’财基板之另__個面進行背面研磨之步驟； 37 201042019 34297pif 使用第一半導體基板用研磨液或第二半導體基板用研磨液，對另一個面進行研磨以使金屬露出之研磨步驟。而且，於此種矽貫通電極之背面研磨中，於最終階段應用精加工研磨之情形時’亦可使用第三半導體基板用研磨液或第四半導體基板用研磨液。 (矽晶圓製造步驟之研磨方法）使用圖14及圖15 (a)、圖15 (b)、圖15 (c)、圖15 (d)說明活用第一半導體基板用研磨液及第二半導體基板用研磨液之研磨特性的研磨製程之另外一例。圖14是通常的矽晶圓之加工技術之流程。矽晶圓是經過包含對矽單晶進行切片之步驟（slicing)、磨削步驟或研磨步驟、触刻步驟等的步驟而加工為晶圓形狀。上述磨削步驟或研磨步驟進行機械研削’因此會對矽結晶造成結晶缺陷等損傷。因此’在後續之蝕刻步驟中’通常是消除此種損傷以及某種程度上消除表面之凹凸。 ^然而，即使是經過蝕刻步驟後之矽晶圓，仍未實現所明之用以製造半導體裝置所需的充分程度之平坦性以及消除結晶缺陷等損傷。因此，通常如圖15 (a)、圖15 (b)、圖15⑷、圖15 U)所示那樣，經過多階段之研磨步驟而獲得平坦之矽晶圓。於圖15。）、圖15(1))、圖15(c)、 =15⑷中表示了⑷至（b)、（b)至（c)這2個階 ::粗：磨（粒切削）步驟以及（c) i⑷之精加工研室，、’、,研磨）步驟’但該研磨步驟因晶祕商或晶圓之、、’及（_e)而不同，亦存在需要更多階段之情況。 38 201042019 W · ^ i ^ ΛΛ. 所述粗研磨是一面依序將使用之研磨布之硬度由硬切換為柔軟一面進行研磨，一面減少膜厚一面緩緩消除凹凸及損傷。於精加工研磨步驟中，基本上無需對於石夕之研磨速度，不新產生缺陷，是用以除去粗研磨時附著之研磨粒子，消除微小之凹凸，使晶圓鏡面化的研磨步驟。此處，第一半導體基板用研磨液及第二半導體基板用研磨液適於上述粗研磨。即，本實施形態是包括將對矽單〇晶晶塊進行切片而所得的矽晶圓磨削或研磨後，對該矽晶圓進行蝕刻，準備粗晶圓之步驟；使用第一半導體基板用研磨液或第一半導體基板用研磨液，對粗晶圓進行研磨之粗研磨步驟的半導體基板的研磨方法。 (矽晶圓再生之研磨方法）而且，所述第一半導體基板用研磨液及第二半導體基板用研磨液活用對於矽之較高的研磨速度，可適宜使用於研磨再生晶圓之方法中。以下’對研磨再生晶圓之方法加以說明。 ΰ 通常情況下，於由矽晶圓製造半導體元件之各要素步驟中，為了進行製程測試，使用大量的晶圓作為測試晶圓。此種測試晶圓可列舉於平坦之矽基板上形成有絕緣膜或金屬膜等各種膜的測試晶圓。製造該些測試晶圓之目的在於廣泛用於如下情形：研究用於在石夕基板上形成各種膜之最佳條件之情形；研究於矽基板上塗層光阻膜並曝光時之最佳條件之情形；定期對所述各最佳條件進行監控 (monitoring)之情形；評價研磨液對於在矽基板上形成= 39 201042019 34297pif 各種膜的研磨特性之情形等。 °亥些測咸晶圓為了再次利用為測試晶圓，需進行再生處理。作為再生處理，通常是藉由濕式蝕刻而除去所述各種膜等附著物，經過粗研磨及精加工研磨步驟而再次獲得平坦之晶圓。而且，所述測試晶圓存在於回到再生步驟之前附有較大之傷痕或者於評價時形成凹凸之情形。於此情形時，通常是藉由研削加工而除去傷痕或凹凸，對其進^ 粗研磨及精加工研磨，由此而再次獲得平坦之晶圓。本發明之半導體基板用研磨液中，第一半導體基板用 =磨液及第二半導體基板用研磨液可適宜對此種再生 if?研磨。即’本實施形態是-種半導體基板的研括:用ί再利用之半導體基板的研磨方法，其包第-半導耆物之梦晶圓進行濕式侧之步驟；使用經濕 ::趙基㈣研一磨之步 = 研：:研=!體基板用研磨液或第四半導雜基板用板用體基:用研磨液中’第三半導體基物，且pH為似以及驗性化合 2以下之半導體基板用研磨液含有 201042019 水溶性高分子，從而可消除矽表面之凹凸。 .而且，於第三半導體基板用研磨液中，為了調節研磨 ‘速度或者改變欲消除之凹凸之目標尺寸，而使三吐、水溶性rfj分子之添加置或佳化’且視需要控制pH等，由此可獲得第四半導體基板用研磨液。以下，對使用第三半導體基板用研磨液或第四半導體基板用研磨液之半導體基板的研磨方法的實施形態加以說明。〇 (矽晶圓製造步驟之研磨方法）如上所述’為了獲得平坦之矽晶圓，通常如圖15(a)、圖15 (b)、圖15 (c)、圖15 (d)所示那樣經過粗研磨（粗切削）步驟及精加工研磨（最終研磨）步驟。此處，第三半導體基板用研磨液及第四半導體基板用研磨液是與對於矽基板之研磨速度相比，重點更在於消除矽基板上存在之凹凸及除去矽基板上殘存之異物（由研磨粒子及研磨墊之磨損所產生之磨損粉末等）的研磨液，特別適合於矽晶圓〇之製造步驟中的精加工研磨用途。即，本實施形態是一種半導體基板的研磨方法，其包括：將對矽單晶晶塊進行切片而所得的矽晶圓磨削或研磨後，對該矽晶圓進行蝕刻，準備粗晶圓之步驟；對粗晶圓進行研磨之粗研磨步驟；使用第三半導體基板用研磨液或第四半導縣板用研磨液，對粗研磨步驟㈣晶圓進—步進行研磨之精加工研磨步驟々另外’於對粗晶圓進行研磨之粗研磨步驟中，亦可使用第-半導體基板用研磨液或第二半導體基板用研磨液。 201042019 34297pit (矽晶圓再生之研磨方法）而且’第三半導體基板用研磨液前述之獲得再生心St 1 P本實施形態是一種半導體基板的研磨方二疋用於再·之半導體基板的研磨方法，其包括進行濕絲刻之步驟；對經濕式二研磨磨步驟；使用第三半導體基板用 :曰圓進-步進行研磨之精加工研磨步驟。另外 ‘ ΐϊίΐΓ圓進行研磨之粗研磨步驟中，亦可使用第二、 +導體基板用研磨液或第二半導體基板料磨液。情幵4外較利用之矽基板之表面具有凹凸或傷痕之 =體基板用研磨液進行研磨之步驟之前，具有機械研削之：且、=於矽之研磨速度相比，為了減低矽基板上 :半導體美二用面之微小凹凸而獲得高度之鏡面而使用第 ^ 研磨液或第四半導體基板用研磨液之情形用錄程錄的研錄，㈣較佳的是小於料c糾狀之硬度（AstoC硬度）㈣㈣第五半導體基板用本貝把开人1之半導體基板用研磨液中，第五半導體基 42 201042019 板用研磨液與第四半導體基板用研磨液相比，可以一面消除表面之凹凸一面獲得對於矽之某種程度的研磨速度。由此可優先研磨具有比較大之凹凸之半導體基板的凸部。另外，於後述之研磨方法中，亦可使用第三半導體基板用研磨液代替第五半導體基板用研磨液。於以下，對使用第五半導體基板用研磨液之半導體基板的研磨方法之實施形態加以說明。The content of the soluble polymer is 1% by mass or more and 0.3% by mass or less. In addition, the total mass of the polishing liquid for the semiconductor substrate is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The content of the molecule is 〇〇1% by mass or more and 0.2% by mass or less. <Method of Polishing Semiconductor Substrate> Next, a grinding method for polishing the surface of the semiconductor substrate with the polishing liquid to the fifth semiconductor substrate for the fourth to fourth semiconductor substrate will be described. As an example of the polishing method, for example, the polishing liquid for a semiconductor substrate of the present embodiment is supplied to a polishing cloth of a polishing platen, and the polishing substrate is pressed while the substrate (semiconductor substrate) to be polished is pressed against the polishing cloth. The surface of the half substrate is polished by moving relative to the substrate to be polished. As a polishing apparatus which can be used in the polishing method of the present embodiment, for example, a general polishing apparatus having a holder for holding a substrate to be polished and attaching a polishing cloth (pad) can be used. A grinding plate for a motor with a variable speed. Grinding of the polishing cloth on the platen 35 201042019 There is no particular limitation. A general non-woven fabric, a foamed polyurethane, a porous fluororesin, or the like can be used. When the polishing substrate is pressed against the substrate to be polished while the semiconductor substrate is pressed against the polishing pad, it is preferable to move at least one of the substrate and the polishing plate. In addition to rotating the polishing plate, it is also possible to perform grinding by rotating or shaking the holder. Further, the polishing method may be a polishing method in which the polishing plate is rotated in a planetary manner, or a polishing method in which a belt-shaped polishing cloth is linearly moved in one direction in the longitudinal direction. Alternatively, the holder can be in any state of being fixed, rotating, or rocking. These polishing methods can be suitably selected depending on the substrate to be polished or the polishing apparatus if the polishing cloth is moved relative to the semiconductor substrate. During the polishing, it is preferred to continuously supply the polishing liquid for the semiconductor substrate to the polishing cloth with a pump or the like. <A method of polishing a polishing liquid for a first semiconductor substrate or a polishing liquid for a second semiconductor substrate> The polishing liquid for a first semiconductor substrate and the polishing liquid for a second semiconductor substrate of the present invention are used as described above The polishing method has excellent rubbing characteristics for the case where the crucible or the substrate including the crucible in the substrate structure is polished. Among them, the polishing rate of the substrate including ruthenium or ruthenium in the substrate structure is excellent. Hereinafter, an embodiment of a method of polishing a semiconductor substrate using a polishing liquid for a first semiconductor substrate and a polishing liquid for a second semiconductor substrate will be described. (Shi Xi through electrode back grinding method) 36 201042019 Semiconductor 1 = 3Fig. 13 (e) illustrates an example of a first-time polishing process. The method of polishing the polishing liquid for a bulk substrate is not limited to this example, and the polishing of the semiconductor substrate of the present invention is shown in Fig. 13 (5) and Fig. 13 (c). Ο Ο 凹凸 , , ' 卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿卿The action, ^ 13Hf ° at this time, due to the strong surface of the #surface grinding, which is shown in (4), the damage layer 3 is damaged in the back state of the semiconductor substrate 1. Finally, the squeegee layer 3 and the semiconductor substrate 13 (c) = _ are used to form the ruthenium-damping layer 3 and the semiconductor-based layer 13 (c) = _, until the y-metal 2 is exposed on the back surface, forming a through-hole as shown in Fig. 13 (C). electrode. Although the surface of the present invention 3 may have fine irregularities, the semiconductor substrate having the unevenness in the polishing of the semiconductor substrate for the polishing liquid for the plate can also obtain a good semiconductor semiconductor. On the way. *The grinding method of the plate can be used to inspect the various types of the semi-conducting plate. 1. This embodiment is a grinding method for a semi-conducting plate, which is: a method of polishing a semiconductor substrate of a mussel-passing electrode. : a step of forming a concave portion on a surface of a stone substrate; a step of embedding a metal into a concave step to perform back grinding on another surface of the substrate; 37 201042019 34297pif using a polishing liquid for a first semiconductor substrate Or a polishing step of the second semiconductor substrate polishing liquid to polish the other surface to expose the metal. Further, in the case of performing the finish polishing in the back surface polishing of the tantalum through electrode, the third semiconductor substrate polishing liquid or the fourth semiconductor substrate polishing liquid may be used. (The polishing method of the wafer manufacturing step) The polishing liquid for the first semiconductor substrate and the second semiconductor will be described with reference to FIGS. 14 and 15(a), 15(b), 15(c), and 15(d). Another example of the polishing process for the polishing characteristics of the polishing liquid for the substrate. Figure 14 is a flow chart of a conventional tantalum wafer processing technique. The tantalum wafer is processed into a wafer shape by a step including slicing, grinding, or polishing, and a step of slicing a single crystal. The above-mentioned grinding step or polishing step is mechanically grounded, so that crystal defects or the like are caused to damage to the ruthenium crystal. Therefore, 'in the subsequent etching step' is usually to eliminate such damage and to some extent eliminate the unevenness of the surface. ^ However, even after the etching process, the wafer is not subjected to the sufficient degree of flatness required to fabricate the semiconductor device and to eliminate damage such as crystal defects. Therefore, as shown in Fig. 15 (a), Fig. 15 (b), Fig. 15 (4), and Fig. 15 U), a flat silicon wafer is obtained through a multi-stage polishing step. In Figure 15. ), Fig. 15 (1)), Fig. 15 (c), = 15 (4) show the two steps (4) to (b), (b) to (c): coarse: grinding (grain cutting) step and (c) ) The finishing process of i(4), ',, grinding' step 'but the grinding step differs depending on the crystal quotient or wafer, 'and (_e)), and there are cases where more stages are required. 38 201042019 W · ^ i ^ ΛΛ. The rough grinding is performed by sequentially changing the hardness of the polishing cloth used from the hard surface to the soft side, and gradually reducing the thickness and reducing the unevenness and damage. In the finishing polishing step, the polishing speed is not substantially required, and no defects are newly generated. This is a polishing step for removing the abrasive particles adhered during the rough polishing, eliminating minute irregularities, and mirroring the wafer. Here, the first semiconductor substrate polishing liquid and the second semiconductor substrate polishing liquid are suitable for the above-described rough polishing. That is, in the present embodiment, the step of grinding or polishing the tantalum wafer obtained by slicing the tantalum single crystal ingot, etching the tantalum wafer to prepare a rough wafer, and using the first semiconductor substrate A polishing method of a semiconductor substrate in a rough polishing step of polishing a rough wafer by a polishing liquid or a polishing liquid for a first semiconductor substrate. (Drying method for wafer regeneration) The polishing liquid for the first semiconductor substrate and the polishing liquid for the second semiconductor substrate can be suitably used in a method of polishing a wafer by utilizing a higher polishing rate for germanium. The following is a description of the method of polishing the wafer. ΰ Normally, a large number of wafers are used as test wafers for process testing in the steps of fabricating semiconductor components from germanium wafers. Such a test wafer can be exemplified by a test wafer in which various films such as an insulating film or a metal film are formed on a flat germanium substrate. The purpose of manufacturing these test wafers is to be widely used in the following cases: to study the optimum conditions for forming various films on the Shih-Xin substrate; to study the optimum conditions for coating the photoresist film on the tantalum substrate and exposing it In the case of monitoring the respective optimum conditions on a regular basis; the case where the polishing liquid is formed on the ruthenium substrate for the formation of the polishing characteristics of various films of 139 201042019 34297pif, and the like. In order to reuse the test wafer, it is necessary to carry out regeneration treatment. As the regeneration treatment, deposits such as the respective films are usually removed by wet etching, and a flat wafer is again obtained by the rough polishing and finishing polishing steps. Moreover, the test wafer exists in the case where a large flaw is attached before returning to the regeneration step or irregularities are formed at the time of evaluation. In this case, the scratch or the unevenness is usually removed by the grinding process, and the rough grinding and the finishing grinding are performed, thereby obtaining a flat wafer again. In the polishing liquid for a semiconductor substrate of the present invention, the polishing liquid for the first semiconductor substrate and the polishing liquid for the second semiconductor substrate can be suitably used for such regeneration. That is, the present embodiment is a semiconductor substrate: a polishing method for a semiconductor substrate that is reused, and a step of performing wet-side on a dream wafer containing a first-semiconducting material; using a wetness: Zhao Base (4) Research and grinding step = Research:: Research =! Body substrate polishing liquid or fourth semiconductor substrate for plate substrate: using a 'third semiconductor substrate in the polishing liquid, and the pH is similar and the test compound The polishing liquid for a semiconductor substrate of 2 or less contains a 201042019 water-soluble polymer, thereby eliminating irregularities on the surface of the crucible. Further, in the polishing liquid for a third semiconductor substrate, in order to adjust the polishing speed or change the target size of the unevenness to be eliminated, the addition or optimization of the three-dissolved and water-soluble rfj molecules is performed, and the pH is controlled as needed. Thus, a polishing liquid for a fourth semiconductor substrate can be obtained. Hereinafter, an embodiment of a method of polishing a semiconductor substrate using a polishing liquid for a third semiconductor substrate or a polishing liquid for a fourth semiconductor substrate will be described. 〇 (The method of polishing the wafer fabrication step) As described above, 'in order to obtain a flat wafer, it is usually as shown in Fig. 15 (a), Fig. 15 (b), Fig. 15 (c), and Fig. 15 (d). This is followed by a rough grinding (rough cutting) step and a finishing grinding (final grinding) step. Here, the polishing liquid for the third semiconductor substrate and the polishing liquid for the fourth semiconductor substrate are more important than the polishing rate for the ruthenium substrate, and the foreign matter remaining on the ruthenium substrate is removed and the foreign matter remaining on the ruthenium substrate is removed (by polishing) The polishing liquid of the particles and the abrasion powder generated by the abrasion of the polishing pad is particularly suitable for the finishing polishing application in the manufacturing process of the crucible wafer. That is, the present embodiment is a method of polishing a semiconductor substrate, comprising: grinding or polishing a tantalum wafer obtained by slicing a single crystal ingot, and etching the tantalum wafer to prepare a rough wafer. a step of rough grinding the coarse wafer; a polishing process using the third semiconductor substrate polishing liquid or the fourth semi-conductive plate polishing liquid, and the coarse grinding step (four) wafer polishing step 々 Further, in the rough polishing step of polishing the rough wafer, the polishing liquid for the first semiconductor substrate or the polishing liquid for the second semiconductor substrate may be used. 201042019 34297pit (Drying method for wafer wafer regeneration) Further, the third semiconductor substrate polishing liquid obtains the regenerative core St 1 P. This embodiment is a polishing method for a semiconductor substrate. And comprising the step of performing wet-wetting; the step of performing a wet-type two-grinding; and the step of finishing using a third semiconductor substrate: a round-step grinding process. Further, in the rough polishing step of polishing the second layer, the second or + conductor substrate polishing liquid or the second semiconductor substrate material grinding liquid may be used. In the case of the surface of the substrate, which has irregularities or scratches, the surface of the substrate is polished by a polishing liquid, and is mechanically ground: in addition to the polishing rate of the crucible, in order to reduce the thickness of the substrate: In the case where the semiconductor fine film is used to obtain a high degree of specularity, and the polishing liquid for the fourth polishing liquid or the fourth semiconductor substrate is used, it is preferable to use the recording of the recording method. (4) It is preferable that the hardness is smaller than that of the material c ( (4) (4) In the polishing liquid for semiconductor substrate of the fifth semiconductor substrate, the fifth semiconductor substrate 42 201042019 The polishing liquid for the plate can eliminate the unevenness of the surface as compared with the polishing liquid for the fourth semiconductor substrate. One side obtains a certain degree of polishing speed for the crucible. Thereby, the convex portion of the semiconductor substrate having the relatively large unevenness can be preferentially polished. Further, in the polishing method to be described later, the polishing liquid for the third semiconductor substrate may be used instead of the polishing liquid for the fifth semiconductor substrate. Hereinafter, an embodiment of a method of polishing a semiconductor substrate using a polishing liquid for a fifth semiconductor substrate will be described.

圖16(a)是矽晶圓之通常的再生步驟流程。為了再利用而，时之㈣S1，在進行了接受檢查後，經過用以除去附著物之濕式蝕刻步驟、用以消除比較大之凹凸之研磨步驟而成為粗晶圓。以規定之方法對該粗晶圓進行清洗後，於粗研磨步驟中分為多階段（第一次研磨、第二次研磨……）而進行粗研磨，進一步經過精加工研磨步驟、清洗步驟而製成再生晶圓而出貨。然而現狀疋藉由研磨後之多階段的粗研磨，會必要程度以上軸切晶圓。目此，為了減減種「研磨損耗更有效率地再利用矽晶圓，尚需要加以改善。、另-方面’藉由使用第五半導體基板用研磨液，可提供-種可進行此種改善之先前所沒有的新型研磨方法。即’本實施職是-種半導縣板的研磨方法，其是用於 ^利用之半導縣板的研磨方法，其包括：對附著有附物之石夕晶圓進行濕式侧後，對^圓進行研磨 =曰=步驟；使用第五半導體基板用研磨液，對所述粗晶圓進仃研磨之粗研磨步驟。 43 201042019 34297pif 若為此種半導體基板的研磨方法，則可以將先前分為數個步驟進行的粗研磨以一個步驟來進行（參照圖16 (b))，因此可減低在粗研磨中產生的半導體基板的研磨損耗。由此亦可獲得可使矽晶圓的再利用次數變多的效果。另外，於所述粗研磨步驟中，於將粗晶圓之研磨量定義為L (nm)、將粗晶圓之初始階差定義為Rt〇 (nm)及將 '、-!粗研磨後之粗晶圓之階差定義為R”（nm)之情形時，較佳的是在滿足Rt0$LSRt0xi.3且研磨粗晶圓僅l (nm) 時（即，僅以初始階差的1·3倍以下的研磨量進行研磨），同時滿足 L/ (Rt0-Rtl) $1.3 及 Rtl^l〇〇 (nm)。另外，最終的研磨量當然也可以為上述之範圍（RtQSL訊。χ1.3) 以上。 ,而且’較佳的是於上述之半導體基板的研磨方法中，亦可更包含使用研磨液對粗研磨步驟後之粗晶圓進行研磨 =精加工研磨步驟’所述研磨液含有研磨粒子、1，2,4-三、水溶性高分子、鹼性化合物，pH為 9以上且12以下。此可將半導體基板之表面以高速而精加工研磨加工為凹凸較少之平滑表面。另外’較佳的是於上述之半導體基板的研磨方法中， :更包含使用研磨液對粗研磨少驟後之粗晶圓進行研磨唑;^加工研磨步驟，所述研磨液含有研磨粒子、1,2,4-三才火，性鬲分子、鹼性化合物，戶斤述1,2,4-三峻之含量〇目^於半導體基板用研磨液之總質量為〇.〇5質量0/〇以上且 •質量％以下，所述水溶性高分子之含量相對於半導體基 44 201042019 板用研磨液之總質量為〇〇〇1質量％以上且〇1質量〇/〇以 . 下，PH為9以上且12以下。由此可將半導體基板之表面更確實地以高速而精加工研磨加工為凹凸較少之平滑表面0 而且’第五半導體基板用研磨液亦可適宜應用於所述之TSV背面研磨方法中。通常情況下，TSV背面並不要求電路面（活性面）那樣的平坦性，因此在實施一階段之機〇械研削後’使用第五半導體基板用研磨液進行TSV背面研磨，由此可獲得充分耐實用之TSV基板。於先前，TSV之背面研磨，在進行研磨之前經過多階段之機械研削步驟，但藉由本發明之方法可使TSV之製造步驟大幅簡略化。 .而且，於第五半導體基板用研磨液中，為了一面消除由於研磨專而在表面產生之某種程度大小之凹凸一面獲得對於矽之某種程度的研磨速度，較佳的是研磨墊具有某種裎度之硬度’例如較佳的是用ASKER橡膠硬度計c型而 Q 測定之硬度（Asker C硬度）是60度以上，更佳的是7〇度以上，進一步更佳的是80度以上。藉由具有該些硬度而具有如下之傾向：容易獲得良好之研磨速度，於凹凸之消除性亦優異。藉由此種研磨方法，理想的是變得無需多階段之粗研磨’因此提供一種包含一個階段之粗研磨的半導體晶圓的研磨方法或者包含一個階段之粗研磨與一個階段之精加工 •研磨的半導體晶圓的研磨方法。實例 45 201042019 3429/pit 但本發明m阳〜對本發明加以更詳細之說明明並不限定於該些實例。兄月〈第一半導體基板用研磨液> (實例1〜實例8) [半導體用研磨液之調製] -唾依=下之順序，以表1情示之添加量調配⑴ ^例物、及作為研磨粒子之膠體二氧切，調裏實例1〜實例8之各半導體用研磨液。物，Μ八〜//的純水巾，於其巾添加鹼性化合部分:：;二=:5;"之膠趙二氧切，剩餘八進订观以使其成為總計1GG質量％。 (實例9及實例1〇) 、 [半導體用研磨液之調製] 依照以下之順序，以表2中所示之添加二嗤、驗性化合物、及作為㈣私2 置郷从4- ㈣似〇旬，，為磨粒子之膠體二氧化石夕，調製實例9及@例U)之各半導體用研磨液。於各研磨液之調製中，首先使於研磨液整體之5G質量μ 解相虽物，其次分散一巾，於其巾添加驗性化合心以純水進行調配以使其成為餘 [pH 測；t] 磨液之枝測定實例1〜實例1G之各半導體用研 46 201042019 (ΡΗ之測定方法） pH計：橫河電機股份有限公司製造之Model pH81 权正.中性鱗酸鹽pH緩衝液pH 6.86 (25〇C )及棚酸鹽邱標準溶液（pH9.18) (25°C)之2點校正測定溫度：25艺Fig. 16 (a) is a flow chart of a normal regeneration step of a germanium wafer. For re-use, the fourth (S) S1 is subjected to the inspection, and is subjected to a wet etching step for removing the deposits, and a grinding step for eliminating relatively large irregularities to become a rough wafer. After the coarse wafer is cleaned by a predetermined method, it is divided into a plurality of stages (first polishing, second polishing, etc.) in the coarse grinding step to perform rough grinding, and further subjected to a finishing grinding step and a washing step. It is made into recycled wafers and shipped. However, the current situation is that the wafer is axially cut to the extent necessary by the multi-stage coarse grinding after grinding. Therefore, in order to reduce the kind of "polishing loss, the yttrium wafer is reused more efficiently, and improvement is needed. On the other hand, by using the polishing liquid for the fifth semiconductor substrate, it is possible to provide such improvement. A new grinding method that has not been used before. That is, the present embodiment is a grinding method for a semi-conducting plate, which is a grinding method for a semi-conducting plate used for use, and includes: a stone attached with an appendage After the wafer is subjected to the wet side, the round is polished = 曰 = step; the fifth semiconductor substrate is used for the rough polishing step of the coarse wafer. 43 201042019 34297pif If such a semiconductor In the method of polishing the substrate, the rough polishing which has been previously divided into several steps can be performed in one step (see FIG. 16(b)), so that the polishing loss of the semiconductor substrate generated during the rough polishing can be reduced. The effect of increasing the number of times of recycling of the germanium wafer is obtained. Further, in the rough grinding step, the amount of polishing of the rough wafer is defined as L (nm), and the initial step of the rough wafer is defined as Rt〇(nm) and will ', -! When the step of roughing the rough wafer is defined as R" (nm), it is preferable to satisfy Rt0$LSRt0xi.3 and grind the rough wafer only l (nm) (ie, only Grinding is performed at a polishing amount of 1.3 times or less of the initial step, and both L/(Rt0-Rtl) $1.3 and Rtl^l〇〇(nm) are satisfied. Further, the final amount of polishing may of course be in the above range (RtQSL, χ 1.3) or more. Further, it is preferable that the polishing method of the semiconductor substrate described above further includes polishing the coarse wafer after the rough polishing step using a polishing liquid = finishing polishing step, wherein the polishing liquid contains abrasive particles, 2, 4-3, a water-soluble polymer, a basic compound, and a pH of 9 or more and 12 or less. This allows the surface of the semiconductor substrate to be finished at a high speed and polished to a smooth surface with less convexities. Further, it is preferable that in the above-described polishing method of the semiconductor substrate, the method further comprises: performing a polishing argon on the rough wafer after the coarse polishing using a polishing liquid; and processing the polishing step, wherein the polishing liquid contains abrasive particles, 1 , 2,4-three fire, sex 鬲 molecules, basic compounds, the content of 1,2,4-three squad, the total mass of the polishing liquid for semiconductor substrates is 〇.〇5质量0/〇 In the above and below the mass%, the content of the water-soluble polymer is 〇〇〇1% by mass or more based on the total mass of the polishing liquid for the semiconductor substrate 44 201042019, and 〇1 mass 〇/〇. Above and below 12. As a result, the surface of the semiconductor substrate can be more accurately processed at a high speed and polished to a smooth surface having a small unevenness. The polishing liquid for the fifth semiconductor substrate can be suitably applied to the TSV back surface polishing method. In general, the back surface of the TSV does not require the flatness of the circuit surface (active surface). Therefore, after the first-stage mechanical grinding is performed, the TSV back grinding is performed using the polishing liquid for the fifth semiconductor substrate. Practical TSV substrate. Previously, the back side of the TSV was ground and subjected to a multi-stage mechanical grinding step prior to grinding, but the manufacturing steps of the TSV were greatly simplified by the method of the present invention. Further, in the polishing liquid for a fifth semiconductor substrate, in order to eliminate a certain degree of polishing speed for a certain degree of unevenness generated on the surface by polishing, it is preferable that the polishing pad has a certain polishing speed. For example, it is preferable to use the ASKER rubber hardness tester type c and the hardness (Asker C hardness) measured by Q is 60 degrees or more, more preferably 7 degrees or more, and still more preferably 80 degrees or more. . By having such hardness, there is a tendency that a good polishing rate is easily obtained and the unevenness is excellent. With such a grinding method, it is desirable to eliminate the need for multi-stage rough grinding' thus providing a grinding method comprising a stage of coarsely ground semiconductor wafer or a coarse grinding with one stage and one stage of finishing and grinding A method of polishing a semiconductor wafer. EXAMPLES 45 201042019 3429/pit However, the present invention is not limited to these examples. Brothers <The first polishing liquid for semiconductor substrates> (Examples 1 to 8) [Preparation of polishing liquid for semiconductors] - The order of the following is based on the addition amount of Table 1 (1) ^, and As the colloidal dioxotomy of the abrasive particles, each of the polishing liquids for semiconductors of Examples 1 to 8 was adjusted. The pure water towel of the Μ8~//, the alkaline compound part is added to the towel::; two =: 5; " the glue Zhao dioxo cut, the remaining eight into the order to make it a total of 1 GG mass% . (Example 9 and Example 1), [Preparation of polishing liquid for semiconductors] According to the following procedure, the addition of the diterpene, the test compound, and the (4) private 2 are shown in Table 2 from 4-(tetra) In order to prepare the colloidal silica dioxide of the particles, the polishing liquid for each of the semiconductors of Example 9 and @Example U) was prepared. In the preparation of each polishing liquid, the 5G mass μ of the entire polishing liquid is first disintegrated, and then a towel is dispersed, and the greening is added to the napkin to be mixed with pure water to make it a residue [pH measurement; t] Grinding liquid branch measurement Example 1 to Example 1G for each semiconductor use 46 201042019 (Measurement method of ΡΗ) pH meter: Model pH81 manufactured by Yokogawa Electric Co., Ltd. Quanzheng. Neutral sulphate pH buffer pH 6.86 (25〇C) and shed acid standard solution (pH9.18) (25 °C) 2 points calibration temperature: 25 art

磁力授拌器（magnetic stirrer) : As One公司製造之 HS-30D ΟMagnetic stirrer : HS-30D manufactured by As One

測定順序：於使用長徑約 4 cm、短徑約0.5 cm之以氟树月曰塗層之攪拌子（stirring bar) ’以500 rpm攪拌研磨液之狀態下進行pH之測定。測定時期：調配之後、靜置一曰後、另外，上述「調配之後」是表示在上述半導體用研磨液之°周整（调配）完成後小於1小時的時間内，「靜置一日後」是表示在上述半導體用研磨液之調整配靜置24小時〜25小時，下同。疋珉设將調配之後的各半導體用研磨液之pH示於表i及表 2。而且’將調配後靜置一日後的各半導體用研磨液以及自調配之後測定之pH的變化量示於表i。 [半導體基板之研磨1] 至研磨的實例1之半導體基板用研磨液供給 ^磨^盤之研磨布上…面於將半導體基板按壓在研對於半導體基板而相對性旋轉由此對+導體基板之表面進行研磨。而且，以 1同樣之料’使賴配之後的實例2〜實例8之各ς磨液 47 201042019 34297pif 對半導體基板進行研磨。研磨條件之詳細情況如下所示。 (研磨條件1) 研磨裝置：Nano Factor公司製造之FACT-200型研磨布：NITTAHAAS公司製造之IC-1010 研磨定盤轉速： 80 rpm 固持器轉速：無驅動裝置（自由旋轉）研磨壓力：33.83 kPa (345 gf/cm2) 研磨液供給量：16ml/min 研磨時間： 5 min 半導體基板（被研磨物）：2 cm見方之矽晶圓（p型 <100> ) [半導體基板之研磨2] 同樣地’一面將調配之後的實例9及實例1〇之半導體基板用研磨液供給至研磨定盤之研磨布上，一面於將半導體基板按壓在研磨布上之狀態下，使研磨定盤相對於半導體基板而相對性旋轉，由此對半導體基板之表面進行研磨。研磨條件之詳細情況如下所示。 (研磨條件2) 研磨裝置：Applied Materials公司製造之MIRRA 研磨布：NITTA HAAS公司製造之IC-1010 研磨定盤轉速：93 rpm 固持器轉速：87 rpm 研磨壓力：20.7 kPa 研磨液供給量：200ml/min 48 201042019 研磨時間：3 min 半導體基板（被研磨物）：200 mm矽晶圓（P型<l〇〇 >) [清洗] 研磨後’利用聚乙烯醇製刷及超音波水進行半導體基板之清洗。清洗後，用旋轉乾燥器（Spin dryer)使半導體基板乾燥。 [調配之後的研磨速度之測定] 使用調配之後的實例1〜實例1〇之各半導體用研磨液，以上述方法對矽晶圓進行研磨後，測定隨著研磨的矽晶圓之重量的減少量。而且，由重量之減少量、晶圓面積、石夕之比重及研磨時間測定研磨速度（單位：nm/min)。另外’於矽晶圓之重量測定中使用分析用電子天平（Mettler 公司製造之AB104 )。測定溫度為25°C，測定濕度為40%RH 以上。矽比重為2.33。 [靜置一日後的研磨速度之測定] 以與使用調配之後的實例1〜實例8之各半導體用研磨液之情形同樣的方法’測定使用靜置一日後的實例1〜實例8之各半導體用研磨液之情形時的研磨速度。 [表面粗糙度評價] 使用調配之後的實例9及實例1〇之各半導體用研磨液，以上述方法對矽晶圓進行研磨後，使用階差/表面粗糙微細形狀測定裝置，以下述條件測定矽晶圓之研磨面的算術平均粗键度。 49 201042019 34297pit'Measurement procedure: The pH was measured while stirring the slurry at 500 rpm using a stirring bar of a fluoroporous sapphire coating having a long diameter of about 4 cm and a short diameter of about 0.5 cm. The measurement period: after the preparation, after standing for one time, and after the above-mentioned "mixing", it means that the time after the completion of the above-mentioned semiconductor polishing liquid is less than one hour, "after one day of standing" is It is shown that the adjustment of the above-mentioned semiconductor polishing liquid is allowed to stand for 24 hours to 25 hours, the same applies hereinafter. The pH of each of the semiconductor polishing liquids after the preparation is shown in Tables i and 2. Further, the amount of change in pH of each of the semiconductor polishing liquids after one day of conditioning and after the self-adjustment was shown in Table i. [Polishing of Semiconductor Substrate 1] The polishing liquid for the semiconductor substrate of Example 1 to be polished is supplied to the polishing cloth of the polishing disk, and the surface of the polishing substrate is pressed against the semiconductor substrate to be relatively rotated, thereby the + conductor substrate. The surface is ground. Further, the semiconductor substrate was polished by the respective honing liquids 47 201042019 34297pif of Examples 2 to 8 after the same material. The details of the polishing conditions are as follows. (Grinding condition 1) Grinding device: FACT-200 type grinding cloth manufactured by Nano Factor: IC-1010 manufactured by NITTAHAAS Grinding plate speed: 80 rpm Retainer speed: no drive (free rotation) Grinding pressure: 33.83 kPa (345 gf/cm2) Serving liquid supply amount: 16 ml/min Grinding time: 5 min Semiconductor substrate (abrasive material): 2 cm square 矽 wafer (p type <100>) [Semiconductor substrate polishing 2] On the other hand, the polishing liquid for the semiconductor substrate of Example 9 and Example 1 after the preparation was supplied to the polishing cloth of the polishing plate, and the polishing plate was pressed against the semiconductor while the semiconductor substrate was pressed against the polishing cloth. The substrate is relatively rotated to thereby polish the surface of the semiconductor substrate. The details of the polishing conditions are as follows. (Grinding condition 2) Grinding device: MIRRA grinding cloth manufactured by Applied Materials: IC-1010 manufactured by NITTA HAAS Grinding plate rotation speed: 93 rpm Retainer rotation speed: 87 rpm Grinding pressure: 20.7 kPa Serving liquid supply amount: 200 ml/ Min 48 201042019 Grinding time: 3 min Semiconductor substrate (abrasive): 200 mm wafer (P type <l〇〇>) [Cleaning] After grinding, using a polyvinyl alcohol brush and ultrasonic water for semiconductor Cleaning of the substrate. After washing, the semiconductor substrate was dried with a spin dryer. [Measurement of polishing rate after preparation] Using the polishing liquid for each of the semiconductors of Examples 1 to 1 after the preparation, the silicon wafer was polished by the above method, and the weight reduction of the polished silicon wafer was measured. . Further, the polishing rate (unit: nm/min) was measured from the amount of weight reduction, the wafer area, the specific gravity of the stone, and the polishing time. In addition, an analytical electronic balance (AB104 manufactured by Mettler Corporation) was used for the weight measurement of the wafer. The measurement temperature was 25 ° C, and the measured humidity was 40% RH or more. The specific gravity is 2.33. [Measurement of the polishing rate after one day of standing] The same method as in the case of using the polishing liquids for semiconductors of Examples 1 to 8 after the preparation was used, and the semiconductors of Examples 1 to 8 after one day of standing were measured. The polishing rate in the case of the slurry. [Evaluation of Surface Roughness] Using the polishing liquid for each of the semiconductors of Example 9 and Example 1 after the preparation, the silicon wafer was polished by the above method, and then the step/surface roughness fine shape measuring apparatus was used, and the following conditions were measured. The arithmetic mean coarse key of the polished surface of the wafer. 49 201042019 34297pit'

階差/表面粗糙度/微細形狀測定裝置：KLA Tencor公司製造之P16-OF 測定模式：粗糖度（Roughness) 測定長度：200 μιη 測定速度：5 μιη/sec 測定荷重：1 mg 將實例1〜實例8之評價結果示於表1，將實例9及實例10之評價結果示於表2。 [表1] 實例 1 2 3 4 5 6 7 8 研磨粒子添加量 (wt% ) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 0.5 1，2,4-三唑 (wt% ) 1.0 1.0 1.0 1.0 0.5 0.25 1.0 1.0 驗性化合物化合物名 TMAH TMAH TMAH TMAH TMAH TMAH KOH TMAH 添加量 (wt%) 0.18 0.59 1.15 1.61 0.57 0.35 0.89 1.08 調配之後的研磨液pH 9.00 10.00 11.00 12.00 11.00 11.00 11.00 11.00 調配之後的研磨速度 (nm/min ) 258 378 451 479 408 386 429 411 靜置一日後的研磨液 _PH 9.02 10.00 10.95 11.85 10.85 10.79 10.93 10.91 靜置一日後的研磨速度 (nm/min) 255 390 451 464 400 390 414 415 研磨液pH之變化量 0.02 0.00 -0.05 -0.15 -0.15 -0.21 -0.07 -0.09 TMAN :氫氡化四甲基銨，KOH :氫氧化鉀 50 201042019 JHZy/ρχι [表2] 實例 9 10 研磨粒子添加量 (wt% ) 0.5 1.0 1,2,4-三唑 (wt% ) 1.0 1.0 驗性化合物化合物名 KOH KOH 添加量 (wt%) 0.71 0.78 調配之後的研卜磨液pH 11.00 11.00 調配之後的研磨速度 (nm/min) 598 784 算術平均粗糙度（A) 22.3 22.7 KOH :氫氧化鉀 ο (比較例1〜比較例14) 依照以下順序’以表3、表4中所示之添加量調配下述表3、表4中所示之驗性化合物、及作為研磨粒子之膠體二氧化♦’調製比較例1〜比較例14之各半導體基板用研磨液。於各研磨液之調製中，首先將驗性化合物添加至〇相當於研磨液整體之50質量％的純水中，其次分散入一次粒徑為35 nm之膠體二氧化矽，剩餘部分以純水進行調配以使其成為總计100質1 %。另外，比較例1 ^比較例14 之各研磨液之任一種中均不含1,2,4-三嗤。以與實例1同樣之方法，測定調配之後的比較例1〜比較例14之各半導體用研磨液之pH、靜置一日後的各半導體用研磨液之pH、及調配之後靜置一日後的pH之變化量。將測定結果示於表3、表4。以與實例1同樣之方法，測定使用調配之後的比較例 51 201042019 /ριι 1〜比較例H之各半導體用研磨液之情形時的研磨速度。而且，以與實例1同樣之方法，測定使用靜置—日後的比較例1〜比較例14之各半導體用研磨液之情形時的研磨速度。將測定結果示於表3、表4。 [表3] 比較例 1 2 3 4 5 6 7 研磨粒子添加量 (wt%) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 驗性化合物化合物名 TMAH TMAH TMAH TMAH TMAH KOH KOH 添加量 (wt% ) 0.0012 0.004 0.018 0.097 0.34 0.001 0.0037 調配之後的研磨液pH 8.00 9.00 10.00 11.00 12.00 8.00 9.00 調配之後的研磨速度 (nm/min) 107 152 302 345 385 129 166 靜置一日後的研磨液pH 7.92 8.80 9.59 10.20 10.98 7.88 8.59 靜置一日後的研磨速度 (nm/min) 103 111 239 312 283 120 125 研磨液pH之變化量 -0.08 -0.20 -0.41 -0.80 -1.02 -0.12 -0.41 TMAN :氫氧化四甲基銨，KOH : 52 201042019 [表4] 比較例 8 9 10 11 12 13 14 研磨粒子添加量 (wt%) 3.0 3.0 3.0 3.0 0.5 1.0 2.0 驗性化合物化合物名 KOH KOH KOH KOH KOH KOH KOH 添加量 (wt% ) 0.016 0.06 0.23 0.59 0.056 0.057 0.059 調配之後的研磨液pH 10.00 11.00 12.00 13.00 11.00 11.00 11.00 調配之後的研磨速度 (nm/min) 311 359 393 451 295 317 322 靜置一日後的研磨液pH 9.37 10.04 10.82 11.36 9.89 9.89 9.96 靜置一日後的研磨速度 (nm/min) 249 329 366 385 263 285 298 研磨液pH之變化量 -0.63 -0.96 -1.18 -1.64 -1.11 -1.11 -1.04 Ο (比較例15〜比較例18) 依照以下順序’以表5中所示之添加量調配下述表5 2 =之具有pKa(此處之pKa為㈣。下同）之化合物、 =各膠體二氧切，調製比較例15〜比較例〇研磨液。於各研磨液之調製中，將亘水卜於齡添加驗性化合物。意-欠八f之5〇質量/〇的純咖之膠體二氧切，剩餘部分以纯；;散入一次粒徑⑽ 總計100質量％。另外，比較例/進仃調配以使其成為液之任一種♦均不含丨,2,4_三唑。比較例18之各研磨 (比較例19) 依照以下順序，以表5中唑、及作為研磨粒子之膠體之添加量調配1，2,4-三匕石夕，調製比較例19之半 53 201042019 導體基板用研磨液。於研磨液之調製中，將丨質量％之 1，2,4-二峻溶解於相當於研磨液整體之％質量。的純水中，於其中分散入一次粒徑為35 nm<膠體二氧化矽，剩餘部分以純水進行調配以使其成為總計1〇〇質量％。另外，於比較例19之研磨液中不含驗性化合物。以與實例1同樣之方法，測定調配之後的比較例15〜比較例19之各半導體用研磨液之pH、靜置一日後的各半導體用研磨液之pH、及調配之後靜置一日後的pH之變化量。將測定結果示於表5。以與實例1同樣之方法，測定使用調配之後的比較例 15〜比較例19之各半導體用研磨液之情形時之研磨速度。而且，以與實例1同樣之方法，測定使用靜置一日後的比較例15〜比較例19之各半導體用研磨液之情形時之研磨速度。將測定結果示於表5。 54 201042019 [表5] 比較例 15 16 17 18 ] 研磨粒」 (wi P添加量 t%) 3.0 3.0 3.0 3.0 3Ό~ 具有pKa之化合物化合物名味'•坐 1，2,3-苯幷二唑截果酸硫酸 1,2 4- — 〇4< pKai 14.5 8.2 3.4 -3 T? 添加量 (wt%) 1 1 1 1 1 鹼性化合物化合物名 TMAH TMAH TMAH KOH ---— 添加量 (wt%) 0.03 0.78 1.4 1.43 —— 調配之後的研磨液pH 11.00 11.00 11.00 11.00 ~~Τδδ~~~ 調配之後的研磨速度 (nm/min) 386 215 一 451 343 161 靜置一日後的研磨液pH 10.20 10.22 10.25 10.33 7 no 靜置一日後的研磨速度 (nm/min ) 354 198 426 315 160~~' 研磨液pH之變化量 -0.80 -0.78 -0.75 -0.67 ^ __ oToT^ 1MAH ·氫氧化四曱基錢，K〇h ·· (比較例20) 依照以下順序，以表6中所示之添加量調配下述表6 〇巾所7^之驗性化合物、及作為研練子之膠體二氧化石夕，調製比較例20之半導體基板用研磨液。於研磨液之調製中’首先將祕化合物添加至相當於研磨液整狀％質量 %的純水中，其次分散入一次粒徑為17 nm之膠體二氧化石夕剩餘科以純水進行調配以使其成為總計應質量 %。另外’比較例2〇之研磨液中不含1，2,4_三唑。實例1同樣之方法，測定調配之後的比較例20 研磨液之ΡΗ、使用調配之後的比較例20之半研磨液之情形時的研磨速度。而且，以與實例9及 55 201042019 J42y/pit 實例10同樣之方法，測定使用比較例20之半導體用研磨液進行研磨後的石夕晶圓之研磨面之算術平均粗縫度。將測定結果及算術平均粗链度示於表6。 [表6] 比較例 20 研磨粒子添加量 0.5 (wt% ) 驗性化合物化合物名 KOH 添加量 0.056 (wt%) 調配之後的研磨液pH 11.00 調配之後的研磨速度 279 (nm/min ) 算術平均粗糙度（A) 33.2 :氫氧化鉀於圖1中表示實例1〜實例4及比較例1〜比較例η 之各研磨液於調配之後的pH、靜置一日後的各研磨液之 pH變化量。於圖2中表示實例1〜實例4及比較例1〜比較例11之各研磨液於調配之後的pH及研磨速度、以及各研磨液之靜置一日後的pH及研磨速度。於圖3中表示實例及比較例之各研磨液中之研磨粒（二氧化矽）之添加量、與調配之後靜置一日後的各研磨液之pH變化量的關係。另外’於圖1〜圖3中，「TA」是含有1,2,4-三唑之實例，除此之外之標記是不含1,2,4-三唑之比較例。而且，「TMAH」表示含有氫氧化四曱基銨，「KOH」表示含有氫氧化鋅。如上所述，實例1〜實例8之半導體基板用研磨液含 56 201042019 有二氧化石夕及I，#三嗤，且含有驗性化合物雖化合物之氫氧化四甲基銨、或者作為無機驗性化合物之氫氧化鉀)。而且’於實例卜實例8之半導體基板用研磨液中，鹼性化合物之含量為（Π質量％以上，？11為9以上且12以下。可知於此種實例1〜實例8中，與調配之後的pH與各實例相同之比較例相&，研磨液之調配之後的研磨速度與靜置一日後的研磨速度並無較大不同，且靜置 ❹ 日後的PH變化量亦極其小。因此，可知本發明之半導體基板用研磨液可對矽進行高速研磨，且其研磨速度穩定。另一方面，比較例1〜比較例5與實例1〜實例6同樣地含有氫氧化四甲基銨作為溶解劑。然而，比較例丨〜比較例5之pH藉由添加非常少量之氫氧化四曱基銨而變為與實例基本相同。可知於此種比較例1〜比較例5中，與 • 實例相比研磨速度慢，且研磨液之調配之後與靜置一曰後的pH變化量亦大，靜置一日後的研磨速度亦降低。而且，比較例6〜比較例14含有氫氧化鉀作為溶解〇劑。與上述比較例同樣地，比較例6〜比較例14之PH藉由添加非常少量之氫氧化鉀而變得與實例基本相同。可知於此種比較例6〜比較例14中，與實例相比研磨速度慢，且研磨液之調配之後與靜置一日後的pH變化量亦大，靜置一日後的研磨速度亦降低。而且，於比較例6〜比較例 ’ 14中’與使用氫氧化四曱基銨作為溶解劑之研磨液相比， . 存在靜置一日後的pH變化量變大之傾向。而且，比較例15添加相同之唑系之咪唑代替ι,2,4_三 57 201042019 342y/pif 口坐。^匕較例15中，pKa高至14 5，因此藉由添加非常少量之氫氧化四甲基銨而變為與實例3相同之pH。可知於比較例15中，與實例3相比研磨速度慢，而且雖然使用了與 1’2,4-二唑相同之唑系，但研磨液之調配之後與靜置一日後的pH變化I亦大，靜置一日後的研磨速度亦降低。於比較例16中，添加相同之唑系之苯幷三唑代替1，2,4-三唑。於比較例16中，pKa為8 2，與並不添加 1，2,3-苯幷三唑之情形相比，氫氧化四甲基銨之可添加量多。然而，可知於比較例16中，與實例3相比研磨速度慢， 2磨液之調配之後與靜置一日後的pH變化量亦大^靜&置 —曰後的研磨速度亦降低。於比較例17及比較例18中，添加酸代替ι，2,4_三唾。於添加蘋果酸之比較例17中，與未添加蘋果酸之情形相比’氫氧化四甲基銨之可添加之量多，且與實例3相比可添加之量亦多。可知於比較例17中，研磨速度與實例3 相同’但研磨液之調配之後與靜置一日後的pH /變化量亦大，靜置一日後的研磨速度亦降低。於添加硫酸之比較例 18中，與未添加硫酸之情形相比，氫氧化鉀之可添加之量多’且與實例7相比可添加之量亦多。然而，可知於比較 =18中，與實例7相比研磨速度慢，研磨液之調配之後與靜置一日後的pH變化量亦大，靜置一日後的研磨速度亦降低。比較例19是單獨含有1，2,4·三唑之研磨液。可知於比較例19中，未發現研磨液之調配之後與靜置一日後的 58 201042019 ，研磨速度Lb，但研磨速度低至不足· nm/min，且單獨以I，2,4-二唑基本上無研磨速度提高之效果。而且，若將實例9及實例1〇與比較例20加以比較， _ 則可知藉由使研磨液含有1，2,4-三唑，可抑制研磨結束後之表面粗糙。 <第一半導體基板用研磨液> [ζ電位測定用研磨液之調製] ❸ 於相當於半導體用研磨液整體之50質量％的純水中添加鹼性化合物（氫氧化鉀）直至ρΗ成為9。其次，添加〇.5質量°/❶之表面經鋁酸鹽改質之改質膠體二氧化矽作為研磨粒（研磨粒子）後，以純水進行調配以使其成為總計 95質量％。添加鹼性化合物（氫氧化鉀）直至阳成為a，剩餘部分以純水進行調配以使其成為總計1〇〇質量％。以此種方式進行而調配ζ電位測定用研磨液C。 θ 添加至ζ電位測定用研磨液C中之改質膠體二氧化矽疋以如下方式而獲得的：於二氧化矽之分散液中添加鋁酸 U 鉀[(Α1〇(〇Η)2Κ]，於60〇C以上進行回流，使二氧化矽表面之石夕醇基成為更容易離子化之_Si_〇_A1(〇H)2基。除使用表7中所示研磨粒及鹼性化合物以外，以與^ 電位測定用研磨液C同樣之方法，分別調製ζ電位測定用研磨液八、：6、〇、五、卜0、：《。另外，表7中所示之磨粗岣購自研磨粒廠商。 [ζ電位之測定] 於以下之測定條件下，測定各ζ電位測定用研磨液中 59 201042019 ^4Zy/pit 之研磨粒之ζ電位。測定原理：雷射都卜勒法（laser doppler method ) ζ 電位測定裝置：ZETASIZER3000HS (MALVERN 製造）Step/surface roughness/fine shape measuring device: P16-OF manufactured by KLA Tencor Co., Ltd. Measurement mode: Roughness Determination length: 200 μηη Measurement speed: 5 μιη/sec Determination of load: 1 mg Example 1 to example The evaluation results of 8 are shown in Table 1, and the evaluation results of Example 9 and Example 10 are shown in Table 2. [Table 1] Example 1 2 3 4 5 6 7 8 Addition amount of abrasive particles (wt%) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 0.5 1,2,4-triazole (wt%) 1.0 1.0 1.0 1.0 0.5 0.25 1.0 1.0 Test Compound compound name TMAH TMAH TMAH TMAH TMAH TMAH KOH TMAH Addition amount (wt%) 0.18 0.59 1.15 1.61 0.57 0.35 0.89 1.08 The pH of the slurry after blending 9.00 10.00 11.00 12.00 11.00 11.00 11.00 11.00 Grinding speed after blending (nm/min) 258 378 451 479 408 386 429 411 Grinding solution after one day of standing _PH 9.02 10.00 10.95 11.85 10.85 10.79 10.93 10.91 Grinding speed after one day of standing (nm/min) 255 390 451 464 400 390 414 415 Change in pH of the slurry Amount 0.02 0.00 -0.05 -0.15 -0.15 -0.21 -0.07 -0.09 TMAN : Hydrogenated tetramethylammonium, KOH : Potassium hydroxide 50 201042019 JHZy/ρχι [Table 2] Example 9 10 Addition amount of abrasive particles (wt%) 0.5 1.0 1,2,4-triazole (wt%) 1.0 1.0 Detective compound compound name KOH KOH Addition amount (wt%) 0.71 0.78 Grinding solution after blending pH 11.00 11.00 Grinding speed after compounding (nm/min ) 598 784 Arithmetic Mean Roughness (A) 22.3 22.7 KOH : Potassium hydroxide ο (Comparative Example 1 to Comparative Example 14) The following experimental examples shown in Tables 3 and 4 were prepared in the following order, and the test compounds shown in Tables 3 and 4 below were prepared and polished. Colloidal Dioxide of Particles ♦ 'The polishing liquid for each semiconductor substrate of Comparative Example 1 to Comparative Example 14 was prepared. In the preparation of each polishing liquid, the test compound is first added to pure water equivalent to 50% by mass of the entire polishing liquid, and secondly dispersed into colloidal ceria having a primary particle diameter of 35 nm, and the remainder is pure water. The formulation was made so that it became a total of 100% by mass. Further, in each of the polishing liquids of Comparative Example 1 and Comparative Example 14, none of 1,2,4-triazole was contained. The pH of each of the semiconductor polishing liquids of Comparative Examples 1 to 14 after the preparation, the pH of each of the semiconductor polishing liquids after one day of standing, and the pH after standing for one day after the preparation were measured in the same manner as in Example 1. The amount of change. The measurement results are shown in Tables 3 and 4. The polishing rate in the case of using the polishing liquid for each semiconductor of Comparative Example 51 201042019 / ριι 1 to Comparative Example H after the preparation was measured in the same manner as in Example 1. Further, in the same manner as in Example 1, the polishing rate in the case of using the respective semiconductor polishing liquids of Comparative Example 1 to Comparative Example 14 after standing still was measured. The measurement results are shown in Tables 3 and 4. [Table 3] Comparative Example 1 2 3 4 5 6 7 Addition amount of abrasive particles (wt%) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Detective compound compound name TMAH TMAH TMAH TMAH TMAH KOH KOH Addition amount (wt%) 0.0012 0.004 0.018 0.097 0.34 0.001 0.0037 Grinding pH after compounding 8.00 9.00 10.00 11.00 12.00 8.00 9.00 Grinding speed after preparation (nm/min) 107 152 302 345 385 129 166 Serving pH after one day of rest 7.92 8.80 9.59 10.20 10.98 7.88 8.59 Resting Grinding speed after one day (nm/min) 103 111 239 312 283 120 125 Change in pH of the slurry -0.08 -0.20 -0.41 -0.80 -1.02 -0.12 -0.41 TMAN : Tetramethylammonium hydroxide, KOH : 52 201042019 [Table 4] Comparative Example 8 9 10 11 12 13 14 Addition amount of abrasive particles (wt%) 3.0 3.0 3.0 3.0 0.5 1.0 2.0 Quantitative compound name KOH KOH KOH KOH KOH KOH KOH Addition amount (wt%) 0.016 0.06 0.23 0.59 0.056 0.057 0.059 pH of the slurry after blending 10.00 11.00 12.00 13.00 11.00 11.00 11.00 Grinding speed after compounding (nm/min) 311 359 393 451 295 317 322 pH of the slurry after one day of rest 9.37 10.04 10.82 11.36 9.89 9.89 9.96 Grinding speed after one day of standing (nm/min) 249 329 366 385 263 285 298 Change in pH of the slurry -0.63 -0.96 -1.18 -1.64 -1.11 -1.11 -1.04 Ο (Comparative Example 15 to Comparative Example 18 The following Table 5 was used in the following order to formulate the following table 5 2 = compound having pKa (where pKa is (4). the same below), = colloidal dioxotomy, and preparation of Comparative Example 15~ Comparative example 〇 polishing liquid. In the preparation of each polishing liquid, the test compound is added to the water. Meaning - owe 5 f of 5 〇 mass / 〇 pure coffee colloidal dioxotomy, the remainder is pure;; scattered primary particle size (10) total 100% by mass. In addition, the comparative example/introduction was formulated so as to be any one of the liquids ♦ all of which were free of hydrazine, 2,4_triazole. Each of the polishing of Comparative Example 18 (Comparative Example 19) In the following procedure, 1,2,4-triterpene was prepared by adding the amount of the azole in Table 5 and the colloid as the abrasive particles, and the half of Comparative Example 19 was prepared. A polishing liquid for a conductor substrate. In the preparation of the polishing liquid, the mass% of 1,2,4-di is dissolved in the % by mass of the entire polishing liquid. In the pure water, a primary particle diameter of 35 nm < colloidal ceria is dispersed therein, and the remaining portion is blended with pure water to make it a total of 1% by mass. Further, the test compound of Comparative Example 19 contained no test compound. In the same manner as in Example 1, the pH of each of the semiconductor polishing liquids of Comparative Examples 15 to Comparative Examples after the preparation, the pH of each of the semiconductor polishing liquids after one day of standing, and the pH after standing for one day after the preparation were measured. The amount of change. The measurement results are shown in Table 5. The polishing rate in the case of using the respective polishing liquids for semiconductors of Comparative Examples 15 to 19 after the preparation was measured in the same manner as in Example 1. Further, in the same manner as in Example 1, the polishing rate in the case of using the polishing liquid for each of the semiconductors of Comparative Example 15 to Comparative Example 19 after one day of standing was measured. The measurement results are shown in Table 5. 54 201042019 [Table 5] Comparative Example 15 16 17 18 ] Abrasive grain" (wi P addition amount t%) 3.0 3.0 3.0 3.0 3Ό~ Compound compound with pKa name '•Sit 1,2,3-benzoxadiazole Truric acid sulfate 1,2 4- - 〇4<pKai 14.5 8.2 3.4 -3 T? Adding amount (wt%) 1 1 1 1 1 Basic compound compound name TMAH TMAH TMAH KOH --- — Adding amount (wt% ) 0.03 0.78 1.4 1.43 ——The pH of the slurry after blending 11.00 11.00 11.00 11.00 ~~Τδδ~~~ Grinding speed after compounding (nm/min) 386 215 451 343 161 The pH of the slurry after one day of standing is 10.20 10.22 10.25 10.33 7 no Grinding speed after one day of standing (nm/min) 354 198 426 315 160~~' Change in pH of the slurry -0.80 -0.78 -0.75 -0.67 ^ __ oToT^ 1MAH ·Hydroxide K〇h·· (Comparative Example 20) In the following procedure, the following inspected compounds of Table 6 and the colloidal silica dioxide as a researcher were prepared in the amounts shown in Table 6. The polishing liquid for a semiconductor substrate of Comparative Example 20 was prepared. In the preparation of the slurry, the secret compound is first added to the pure water corresponding to %% by mass of the slurry, and then dispersed into the colloidal silica with a primary particle size of 17 nm. The remainder is formulated with pure water. Make it a total mass %. Further, the polishing liquid of Comparative Example 2 does not contain 1,2,4-triazole. In the same manner as in the example 1, the polishing rate in the case of the polishing liquid of Comparative Example 20 after the preparation and the half of the polishing liquid of Comparative Example 20 after the preparation were measured. Further, in the same manner as in Example 9 and 55 201042019 J42y/pit Example 10, the arithmetic mean rough degree of the polished surface of the Shihwa wafer after polishing using the semiconductor polishing liquid of Comparative Example 20 was measured. The measurement results and the arithmetic mean thick chain degree are shown in Table 6. [Table 6] Comparative Example 20 Addition amount of abrasive particles 0.5 (wt%) Test compound Compound name KOH Addition amount 0.056 (wt%) Grinding liquid pH after blending 11.00 Grinding speed after compounding 279 (nm/min) Arithmetic mean roughness Degree (A) 33.2: Potassium hydroxide Fig. 1 shows the pH of each of the polishing liquids of Examples 1 to 4 and Comparative Examples 1 to η after the preparation, and the pH change of each polishing liquid after one day of standing. Fig. 2 shows the pH and polishing rate of each of the polishing liquids of Examples 1 to 4 and Comparative Examples 1 to Comparative Example 11, and the pH and polishing rate after one day of standing of each polishing liquid. Fig. 3 shows the relationship between the amount of the abrasive grains (cerium oxide) added to each of the polishing liquids of the examples and the comparative examples, and the amount of change in the pH of each polishing liquid after one day of standing after the preparation. Further, in Fig. 1 to Fig. 3, "TA" is an example containing 1,2,4-triazole, and the other label is a comparative example containing no 1,2,4-triazole. Further, "TMAH" means tetramethylammonium hydroxide and "KOH" means zinc hydroxide. As described above, the polishing liquid for a semiconductor substrate of Examples 1 to 8 contains 56 201042019, which has a disulfide oxide and I, #三嗤, and contains an organic compound of tetramethylammonium hydroxide as an organic compound, or as an inorganic test. Potassium hydroxide of the compound). Further, in the polishing liquid for a semiconductor substrate of Example 8, the content of the basic compound is (% by mass or more, and 11 is 9 or more and 12 or less. It is known that in the examples 1 to 8 and after the compounding The pH of the comparative example is the same as that of the respective examples, and the polishing rate after the preparation of the polishing liquid is not significantly different from the polishing rate after the standing one day, and the amount of change in pH after the standing day is extremely small. It is understood that the polishing liquid for a semiconductor substrate of the present invention can be subjected to high-speed polishing of ruthenium and the polishing rate thereof is stable. On the other hand, Comparative Examples 1 to 5 contain tetramethylammonium hydroxide as a solvent in the same manner as in Examples 1 to 6. However, the pH of the comparative example to the comparative example 5 was substantially the same as the example by adding a very small amount of tetradecylammonium hydroxide. It is understood that in the comparative examples 1 to 5, The polishing rate was slower than the polishing rate, and the amount of pH change after the slurry was adjusted and after standing was also large, and the polishing rate after one day of standing was also lowered. Further, Comparative Examples 6 to 14 contained potassium hydroxide as a dissolution enthalpy. In the same manner as in the above Comparative Example, the pH of Comparative Example 6 to Comparative Example 14 was substantially the same as that of the example by adding a very small amount of potassium hydroxide. It is understood that in Comparative Examples 6 to 14 It is slower than the polishing rate, and the amount of pH change after the preparation of the polishing liquid and after one day of standing is also large, and the polishing rate after one day of standing is also lowered. Moreover, in Comparative Example 6 to Comparative Example '14' and the use of hydroxide Compared with the polishing liquid of tetrakisyl ammonium as a solvent, there is a tendency that the amount of pH change after one day of standing is increased. Moreover, in Comparative Example 15, the same azole-based imidazole is added instead of ι, 2, 4_3 57 201042019 342y /pif mouth sitting. ^ 匕 In Example 15, the pKa is as high as 14 5, so the pH is the same as that of Example 3 by adding a very small amount of tetramethylammonium hydroxide. It is known in Comparative Example 15, and examples. 3 is slower than the polishing rate, and although the same azole system as 1'2,4-diazole is used, the pH change I after the preparation of the polishing liquid and after one day of standing is also large, and the polishing speed after one day of standing still Also reduced. In Comparative Example 16, the same azole type benzoquinone was added. Instead of 1,2,4-triazole, in Comparative Example 16, the pKa was 8 2, and the amount of tetramethylammonium hydroxide added was compared with the case where 1,2,3-benzotriazole was not added. However, it can be seen that in Comparative Example 16, the polishing rate was slower than that of Example 3, and the amount of pH change after the mixing of the two grinding liquids and after one day of standing was also large, and the polishing speed after the setting was also lowered. In Comparative Example 17 and Comparative Example 18, an acid was added instead of ι, 2, 4_three saliva. In Comparative Example 17 in which malic acid was added, compared with the case where malic acid was not added, 'tetramethylammonium hydroxide was used. The amount that can be added is large, and the amount added can be increased as compared with Example 3. It can be seen that in Comparative Example 17, the polishing rate is the same as in Example 3, but the pH/change amount after the preparation of the polishing liquid and after one day of standing is also Large, the grinding speed after a day of standing is also reduced. In Comparative Example 18 in which sulfuric acid was added, the amount of potassium hydroxide which can be added was larger than that in the case where no sulfuric acid was added, and the amount which can be added was larger than that of Example 7. However, it can be seen that in the comparison = 18, the polishing rate was slower than that of the example 7, and the amount of pH change after the preparation of the polishing liquid and after one day of standing was also large, and the polishing rate after one day of standing was also lowered. Comparative Example 19 is a polishing liquid containing 1,2,4·triazole alone. It can be seen that in Comparative Example 19, the polishing rate Lb was not found after the preparation of the polishing liquid and after the rest of the day, but the grinding speed was as low as less than nm/min, and the I, 2,4-diazole alone was basically used. There is no effect of increasing the grinding speed. Further, when Example 9 and Example 1A were compared with Comparative Example 20, it was found that by making the polishing liquid contain 1,2,4-triazole, the surface roughness after the completion of the polishing can be suppressed. <Preparation of the polishing liquid for the first semiconductor substrate> [Preparation of the polishing liquid for measuring the zeta potential] 碱性 Adding a basic compound (potassium hydroxide) to the pure water corresponding to 50% by mass of the entire polishing liquid for semiconductors until ρΗ becomes 9. Next, the modified colloidal ceria having a surface of 〇.5 mass ° / 经 was modified with aluminate as abrasive grains (abrasive particles), and then blended with pure water to make it 95% by mass in total. The basic compound (potassium hydroxide) was added until the yang became a, and the remainder was formulated with pure water so as to be a total of 1% by mass. In this manner, the polishing liquid C for zeta potential measurement is prepared. θ is added to the modified colloidal cerium oxide in the slurry C for zeta potential measurement by adding U potassium acid [(Α1〇(〇Η)2Κ] to the dispersion of cerium oxide, Reflowing at 60 〇C or higher makes the oxalate group on the surface of the cerium oxide _Si_〇_A1(〇H) 2 group which is more easily ionized. Except the abrasive grains and basic compounds shown in Table 7 In the same manner as the polishing liquid C for measuring the potential, the polishing liquid for the measurement of the zeta potential was prepared, respectively: 6, 6, 〇, 五, 卜0, and ". In addition, the rough grinding shown in Table 7 was purchased. From the abrasive manufacturer. [Measurement of zeta potential] Under the following measurement conditions, the zeta potential of the abrasive grains of 59 201042019 ^4Zy/pit in the polishing liquid for zeta potential measurement was measured. Principle of measurement: Laser Doppler method ( Laser doppler method ) 电位 Potential measuring device: ZETASIZER3000HS (manufactured by MALVERN)

測定溫度：25°C 分散介質之折射率：1.331 分散介質之黏度：0.893 cP [表7]Measurement temperature: 25 ° C Refractive index of the dispersion medium: 1.331 Viscosity of the dispersion medium: 0.893 cP [Table 7]

~A 研磨粒~A abrasive grain

BB

C 未經改質之勝體二氮化石》驗性化合物ζ電位（mV)C unmodified swelled body di-nitride" test compound zeta potential (mV)

KOH -68.3 ^經改質之膠體二氳化石》 ~TMAH -68.6 經鋁酸鹽改質之改質膠體二氧化 __矽 K0H -65.3 經鋁酸鹽改質之改質膠體二氧化矽 TMAH -54.4KOH -68.3 ^ modified colloidal diterpene fossils ~ TMAH -68.6 modified colloidal dioxide oxidized by aluminate __矽K0H -65.3 modified colloidal cerium oxide TMAH modified by aluminate 54.4

具有磺酸基之 ^化矽 KOH -62.7矽 KOH -62.7 with sulfonic acid group

(實例11〜實例16) 磨液之調製] 改質之二氣化石順序、’、以表8中所示之添加量調配鋁酸鹽製實例11〜述表8中所示之無機鹼性化合物，調所示之「鉋 1之各半導體用研磨液。另外，表8中邱硬鹽改質之-每膠體二氧化矽，鱼、—虱化矽」是經鋁酸鹽改質之改質 ” 过（電位測定用研磨液C中所添加之 60 201042019 改質膠體二氡化矽相同。於各研磨液之調製中，首先於相當於研磨液整質量％的純水巾添加作為無麟性化合物之氫氧化卸以使 pH成為9。其次，分散入經鋁酸鹽改質之改質膠體二氧化〇夕作為研磨粒，以純水進行調配以使其成為總計95質量 ^。、進-步添加氫氧化鉀以使其成為所期望之pH，剩餘^ 刀以純水進行調配以使其成為總計100質量％。(Examples 11 to 16) Modification of the grinding liquid] The modified two-gas fossil sequence, ', the addition of the aluminate as shown in Table 8 to the inorganic basic compound shown in Example 11 to Table 8 In addition, the polishing liquid for each semiconductor of Plane 1 is shown. In addition, in Table 8, the hardening of Qiu hard salt - per colloidal cerium oxide, fish, bismuth telluride is modified by aluminate.过 (60 201042019 added to the polishing liquid C for potential measurement is the same as the modified colloidal bismuth bismuth bismuth. In the preparation of each polishing liquid, first added to the pure water towel corresponding to the mass % of the polishing liquid as a non-lining property. The hydrogen peroxide of the compound is removed to adjust the pH to 9. Secondly, the modified colloidal cerium oxide modified by the aluminate is dispersed as fine particles in the form of pure water to make it a total of 95 mass%. Potassium hydroxide was added in such a manner as to have a desired pH, and the remaining knives were formulated in pure water to make it 100% by mass in total.

(實例17) 冰紘表=所示，以相當於研磨液整體之50質量％的純水 ^量％之U，4-三峻’於其中添加氫氧化钟直至PH .Γ 。其次，分散入經鋁酸鹽改質之改質膠體二氧化矽、，、、、研磨粒，以純水進行調配以使其成為總計％質量。/〇。添加氫氧化鉀直至pH成為u，剩餘部分以純水進行調配 =使其成為總計1Q〇質量％。以此種方式進行而調製實 17之半導體基板用研磨液。 [PH測定] 藉由以下之方法測定實例U〜實例17之各半導體用研磨液之pH。將各半導體用研磨液之？11示於表8。 (PH之測定方法） pH計：橫河電機股份有限公司製造⑽制邱“ 校正：♦性磷酸鹽pH緩衝液pI1 6 86 (25。〇及硼酸(Example 17) Hail Table = As shown, U, 4-Sanjun, which is equivalent to 50% by mass of pure water of the entire slurry, was added thereto to a pH of Γ. Next, the modified colloidal cerium oxide, yttrium oxide, alumina granules, and the abrasive granules are dispersed in pure water to make them a total of % by mass. /〇. Potassium hydroxide was added until the pH became u, and the remainder was formulated with pure water = making it a total of 1 Q 〇 mass %. In this manner, the polishing liquid for a semiconductor substrate of the semiconductor 17 is prepared. [pH measurement] The pH of each of the semiconductor polishing liquids of Examples U to 17 was measured by the following method. What is the use of the polishing fluid for each semiconductor? 11 is shown in Table 8. (Measurement method of PH) pH meter: manufactured by Yokogawa Electric Co., Ltd. (10) Qiu "Calibration: ♦ Phosphate pH buffer pI1 6 86 (25. Niobium and boric acid

鹽Ρίί標準溶液（PH 9.18) (25°C )之2點校正測定溫度： 25〇CSalt Ρίί standard solution (pH 9.18) (25 ° C) 2 points calibration measurement temperature: 25 〇 C

磁力攪拌器·· As One公司製造之HS-30D 61 201042019 34297pif 士匕測定順序：於使用長徑約4 cm、短徑約〇 5 cm之以 H塗^之攪拌子，以則rpm麟研磨液之狀態下進行測定時期：研磨液之調配之後 [半導體基板之研磨] 一面將調配之後的實例n之半導體基板用研磨液供給至研磨定盤之研磨布上，一面於將半導體基板按壓在研磨布上之狀態下，使研磨定盤相對於半導體基板而相對性方疋轉，由此對半導體基板之表面進行研磨。而且，以與實例11同樣之方法，使用調配之後的實例12〜實例17之各研磨液對半導體基板進行研磨。研磨條件之詳細情況如所示。 (研磨條件）研磨裝置：Nano Factor公司製造之faCT_2〇〇型研磨布.NITTA HAAS公司製造之IC-1 〇 1 〇研磨定盤轉速：80rpm 固持器轉速：無驅動裝置（自由旋轉）研磨壓力：33.83 kPa (345 gf/cm2) 研磨液供給量：16 ml/min 研磨時間：5 min 半導體基板（被研磨物广2 cm見方之矽晶圓（p <100> ) [清洗] 研磨後’利用聚乙烯醇製刷及超音波水進行半導體美 62 201042019 J^y /pu 板之清洗。清洗後，用㈣辆H使半導體基 [研磨速度之測定] μ 使用調配之後的實例11〜實例17之各半導_研磨液，以上述方法_晶®進行研磨後，測定隨著研磨的石夕晶圓之重量的減少量。而且’由重量之減少量、晶圓面積、矽之比重及研磨時間測定研磨速度（單位：nm/min)。將 o 測定結果示於表2。另外’ _晶κ之重量測定中使用分析用電子天平（Mettler公司製造之ABl〇4)。測定溫产 25。(：，測定濕度為40%RH以上。矽比重為2幻。'皿又’、、、 [表 8] ,。〇實例 11 鋁酸鹽改質之二氧一次粒徑 (nm) 17 化矽添加量 (Wt%) 0.5— 1.2,4-三〇坐添加量（wt%) 驗性化合物化合物名添加量 (wt% ) 氫氧化卸 ~αΪ8~ 研膚液pri iff·麻；条痒(nm/mir» ^ 9.0 氫氧化鉀 0^59 0.5 0 0 t^Sfb Γβΐ ~~Ϊ6~ 17 35 17 ~~〇J~ ~〇J~ ~~0~~ —1·0~ SL氧化 035 氫氧化鉀 089 10.0 氫氧化鉀 ΪΛ5 氫氧化 If 057Magnetic Stirrer·· HS-30D manufactured by As One Company 201042019 34297pif Judgement Measurement Sequence: Use a stirrer with a long diameter of about 4 cm and a short diameter of about 5 cm to apply H, and then use rpm Lin slurry. The measurement period is performed: after the preparation of the polishing liquid [polishing of the semiconductor substrate], the polishing liquid for the semiconductor substrate of the example n after the preparation is supplied onto the polishing cloth of the polishing plate, and the semiconductor substrate is pressed against the polishing cloth. In the upper state, the polishing platen is rotated relative to the semiconductor substrate, whereby the surface of the semiconductor substrate is polished. Further, in the same manner as in Example 11, the semiconductor substrate was polished using the respective polishing liquids of Examples 12 to 17 after the preparation. The details of the grinding conditions are as shown. (Grinding conditions) Grinding device: faCT_2〇〇 type abrasive cloth manufactured by Nano Factor. IC-1 manufactured by NITTA HAAS 〇1 〇 Grinding plate speed: 80 rpm Retainer speed: no drive (free rotation) Grinding pressure: 33.83 kPa (345 gf/cm2) Serving solution supply: 16 ml/min Grinding time: 5 min Semiconductor substrate (grinding material 2 cm square 矽 wafer (p <100>) [Cleaning] After grinding Polyvinyl alcohol brush and ultrasonic water for semiconductor beauty 62 201042019 J^y / pu board cleaning. After cleaning, use (four) H to make the semiconductor base [measurement of grinding speed] μ use after the deployment of examples 11 to 17 Each semi-conductive liquid was polished by the above method _ Crystal®, and the amount of reduction with respect to the weight of the polished shi-ray wafer was measured, and 'the amount of reduction by weight, the area of the wafer, the specific gravity of the ruthenium, and the polishing time The polishing rate (unit: nm/min) was measured, and the results of o measurement are shown in Table 2. In addition, an analytical electronic balance (ABl〇4 manufactured by Mettler Co., Ltd.) was used for the measurement of the weight of the _crystalline κ. :, the measured humidity is 40% RH Above, the specific gravity is 2 illusion. 'Dish and ',,, [Table 8], 〇 Example 11 Aluminate modified dioxin primary particle size (nm) 17 Hydrazine addition amount (Wt%) 0.5- 1.2 , 4-Triterpenoid addition amount (wt%) Quantitative compound compound name addition amount (wt%) Hydroxide dehydration ~αΪ8~ Skin pri iff hemp; strip itching (nm/mir» ^ 9.0 potassium hydroxide 0 ^59 0.5 0 0 t^Sfb Γβΐ ~~Ϊ6~ 17 35 17 ~~〇J~ ~〇J~ ~~0~~ —1·0~ SL Oxidation 035 Potassium Hydroxide 089 10.0 Potassium Hydroxide ΪΛ5 Hydroxide If 057

(比較例21〜比較例27) 依照以下順序，以表9、表1G中所示之添加约 9、表10中所示之未經改質之膠體二氧化表物，調製比較例2i〜比較例27之各半導體用研磨液1 外，表9、表10中所示之二氧化石夕均蹲自研磨_商。 63 201042019 34297pif 於各研練之_巾，首先_ # 質量⑽純水中添加驗性化合物直至pH成為= 政入未經改質之膠體二氧切作為研練，以財進 =使，成為總計95質量％。進—步添加驗性化 ^ 二 =·剩餘部分以純水進行調配以使其成為總 (比較例28) 如表10所示’於相當於研磨液整體之 =1質量Μ，4·三唾，於其中添^ PH成為9。其次，分散人未經改質之膠體二氧切作為研行調配时其成為總計95質量％。添加氫 =S pH成為n ’剩餘部分以純水進行調配以使其 ^狀計1〇〇質量％。以此種方式進行而調製比較例28之半導體基板用研磨液。 (比較例29〜比較例32) _依照以下順序’以表1Q中所示之添加量調配表10中所不之改質二氧切及齡化合物，調製比較例29〜例32之各半導體用研磨液。曰於各研磨液之調製中，首先於相當於研磨液整體之5〇，量％的純水中添加鹼性化合物直至pH成為9。其次，分散入經改質之改質膠體二氧化♦作為研練，以純水進^ 調配以使其成為總計95質量。/°。進-步添加祕化合物直成為η，剩餘部分以純水進行調配以使其 100質量％。 64 201042019 以與實例11同樣之方法，測定調配之後的比較例21 〜比較例32之各半導體用研磨液之讲。將測定結果示於表9、表10。以例11同樣之方法，測定使用調配之後的比較例 21〜比杈例32之*切體用研磨液之情形時的研磨速度。將測定結果示於表9、表1〇。於圖6中表示實例11〜實例14及比較例21〜比較例 24之各研磨液之pH與研磨速度。 [表9] 比幸 21 22 23 24 25 26 二氧化矽表面改質未經改質未經改質条經改質未經改質 i經改質未經改質一次粒徑 (nm) 17 17 17 17 17 35 研磨粒添加量 (wt% ) 0.5 0.5 0.5 0.5 5.0 0.5 驗性彳 :合物氫氧化鉀氫氧化鉀氫氧化钾氫氧化鉀氫氧化钟氫氧化 1,2,4-三。坐添加量（wt%) 0 0 0 0 0 茨τ 0 研磨液pH 9.0 10.0 1L0~~ ~12_〇 ~n〇~ ~12.0 研磨速度（rnn/min) 151 280 —----- 329」 355 426 321 65 201042019 34297pif [表 10] 比孝之例 27 28 29 3〇~~~ *31 —---- -—氧化呀表面改質未經改質未經改質磺酸基磺酸基 J 1 胺基 32 -欠粒徑 (nm) 17 17 17 17 17 — 17 ^ 研磨粒添加量 (wt%) 0.5 0.5 0.5 0.5 0.5 '—---- 0.5 瞰性化合物 1，2,4-三嗤添加量（wt%) 研磨液pH 研磨速度（nm/min) 氫氧化四甲基銨 0 11.0 311 氫氧化鉀 1 1Ϊ.0 475 氫氣化鉀 0 11.0 229 虱氧化四甲基銨 0 11.0 55 氫氧化鉀 0 11.0 282 氫氧化四甲基錢 "~0~~~~ 11.0^ 可確認於實例11〜實例l4、實例l6以及比較例21〜比較例24、比較例26、比較例27、比較例29〜比較例32 中’將研磨粒之添加量及pH同樣之實例與比較例進行對比之情形時’實例之研磨速度總是高於比較例之研磨速度。可確認即使實例17之研磨粒之添加量及pH小於比較例25，實例17之研磨速度亦高於比較例25之研磨速度。而且可確認實例17及比較例28均含有1，2,4-三唑，即使兩者之研磨粒的一次粒徑、添加量及pH相等’實例17之研磨速度亦高於比較例28之研磨速度。 <第三半導體基板用研磨液> (實例18〜實例24) [半導體用研磨液之調製] 依照以下順序’以表11中所示之添加量調配研磨粒 66 201042019, 子、水溶性高分子（水溶性聚合物）、1，2,4“η 化合物，調製實例18〜實例24之各半導許一坐、及鹼性各研磨液之調製中，使用尺值不同之三種用研磨液。於 (PVP一Κ15、PVP K30、潰―K90) 。各細聚合物。其中，表示為K15等之K值是與八，為水溶性性特性值，是藉由毛細管黏度計所測定之，相關之黏黏度值。；25°0下之相對 Ο(Comparative Example 21 to Comparative Example 27) The unmodified colloidal dioxide oxidation tables shown in Table 9 and Table 1G were added as shown in Table 9 and Table 1G to prepare Comparative Example 2i~Comparative In the case of each of the polishing liquids 1 for semiconductors of Example 27, the silica stones shown in Tables 9 and 10 were self-grinding. 63 201042019 34297pif In each training _ towel, first _ # quality (10) pure water added test compound until the pH becomes = politically unmodified colloidal dioxotomy as a training, with Caijin = make, become the total 95% by mass. Step-by-step addition of testability ^ 2 = The remaining part is formulated with pure water to make it total (Comparative Example 28) As shown in Table 10, 'the equivalent of the whole liquid = 1 mass Μ, 4 · three saliva , add ^ PH to become 9. Secondly, when the unmodified colloidal dioxo prior was prepared as a formulation, it became 95% by mass in total. The addition of hydrogen = S pH became n ′ The remaining portion was formulated in pure water to have a mass ratio of 1% by mass. The polishing liquid for a semiconductor substrate of Comparative Example 28 was prepared in this manner. (Comparative Example 29 to Comparative Example 32) _ The modified dioxobic and aged compounds not shown in Table 10 were prepared in the following order, and the semiconductors of Comparative Examples 29 to 32 were prepared. Slurry. In the preparation of each polishing liquid, a basic compound is first added to pure water corresponding to 5% by volume of the entire polishing liquid until the pH becomes 9. Secondly, it is dispersed into the modified modified colloidal dioxide ♦ as a training, and is blended with pure water to make it a total of 95 masses. /°. Further, the secret compound was added to become η, and the remainder was formulated with pure water to make it 100% by mass. 64 201042019 In the same manner as in Example 11, the polishing liquids for semiconductors of Comparative Examples 21 to 32 after the preparation were measured. The measurement results are shown in Tables 9 and 10. In the same manner as in Example 11, the polishing rate in the case of using the polishing liquid for Comparative Example 21 to Comparative Example 32 after the preparation was measured. The measurement results are shown in Table 9 and Table 1〇. The pH and polishing rate of each of the polishing liquids of Examples 11 to 14 and Comparative Examples 21 to 24 are shown in Fig. 6 . [Table 9] Bixing 21 22 23 24 25 26 Surface modification of cerium oxide has not been modified. The modified strip has not been modified. It has not been modified. It has been modified without modification. Primary particle size (nm) 17 17 17 17 17 35 Addition amount of abrasive grains (wt%) 0.5 0.5 0.5 0.5 5.0 0.5 Detective hydrazine: potassium hydroxide potassium hydroxide potassium hydroxide potassium hydroxide hydrogen peroxide 1,2,4-tri. Sitting amount (wt%) 0 0 0 0 0 tz 0 Grinding solution pH 9.0 10.0 1L0~~ ~12_〇~n〇~ ~12.0 Grinding speed (rnn/min) 151 280 —----- 329” 355 426 321 65 201042019 34297pif [Table 10] Example of filial piety 27 28 29 3〇~~~ *31 —---- -- Oxidation surface modification without modification without modified sulfonic acid sulfonate group J 1 Amino 32 - Undersize (nm) 17 17 17 17 17 - 17 ^ Addition amount of abrasive particles (wt%) 0.5 0.5 0.5 0.5 0.5 '----- 0.5 Vision compound 1,2,4-trimium Adding amount (wt%) Grinding liquid pH Grinding speed (nm/min) Tetramethylammonium hydroxide 0 11.0 311 Potassium hydroxide 1 1Ϊ.0 475 Potassium hydrogen hydride 0 11.0 229 Tetramethylammonium oxide 0 11.0 55 Hydroxide Potassium 0 11.0 282 tetramethyl hydroxy hydroxide "~0~~~~ 11.0^ It can be confirmed in Example 11 to Example l4, Example 16 and Comparative Example 21 to Comparative Example 24, Comparative Example 26, Comparative Example 27, Comparative Example In the case of 29 to Comparative Example 32, the case where the addition amount of the abrasive grains and the pH were the same as those of the comparative example was always higher than the polishing rate of the comparative example. It was confirmed that even if the addition amount and pH of the abrasive grains of Example 17 were smaller than that of Comparative Example 25, the polishing rate of Example 17 was higher than that of Comparative Example 25. Further, it was confirmed that both of Example 17 and Comparative Example 28 contained 1,2,4-triazole, even if the primary particle diameter, the addition amount, and the pH of the abrasive grains of the two were equal. The polishing rate of Example 17 was higher than that of Comparative Example 28. speed. <Layer Liquid for Third Semiconductor Substrate> (Examples 18 to 24) [Preparation of polishing liquid for semiconductor] The abrasive particles 66 were prepared in the following order in the following order: 201042019, high water solubility Molecular (water-soluble polymer), 1, 2, 4" η compound, preparation of each of the semi-conducting examples of Examples 18 to 24, and the preparation of alkaline slurry, using three kinds of polishing liquids having different sizing values (PVP Κ15, PVP K30, ―-K90). Each fine polymer. Among them, the K value expressed as K15 and the like is the water solubility characteristic value, which is determined by a capillary viscometer. Correlation viscosity value; relative relatives at 25°0

於各研磨液之調製中，首先使124 = =酮（PW)溶解於相#於研磨_=== 二;：;中添加驗性化合物直至阳成為：入0.5貝里％之一次粒徑為17 nm 、刀政純水進行調配以使其成為總計9 ^化石夕後’以化合物直至成為所期望之PH，剩餘部分。以使其成為總計100質量％。 π以純水進订調配以 [pH測定] 18〜實例24之各半導體用磨液之pH示於表11。藉由以下之方法測定實例研磨液之pH。將各半導體用研 (PH之測定方法）In the preparation of each polishing liquid, first, 124 = = ketone (PW) is dissolved in the phase # in the grinding _=== two;:; add the test compound until the yang becomes: the initial particle size of 0.5 mils is 17 nm, Knife Pure Water was formulated to make it a total of 9 ^ fossils after the compound until the desired pH, the remainder. In order to make it a total of 100% by mass. π was formulated in pure water to adjust the pH of each of the semiconductor grinding liquids [pH measurement] 18 to Example 24 shown in Table 11. The pH of the example slurry was determined by the following method. For each semiconductor (measurement method of PH)

PH 5十.橫河電機股份有限公司製造之如ipH8i 抆正.中性磷酸鹽pH緩衝液ρΉ 6 86 (25°C)及硼酸農邱檩準溶液（，.⑻⑵以之2點校正測定溫度：25°CPH 5 X. Yokogawa Electric Co., Ltd. manufactured such as ipH8i 抆正. Neutral phosphate pH buffer ρΉ 6 86 (25 ° C) and boric acid Nong Qiu quasi-solution (, (8) (2) with 2 points to determine the temperature :25°C

磁=攪拌器：AsOne公司製造之JJS-30D 測疋順序：於使用長徑約4 cm、短徑約0.5 cm之以氟 67 201042019 34297pif 樹脂塗層之攪拌子，以5〇〇 rpm攪拌研磨液之狀態下進行 pH之測定。測定時期：研磨液之調配之後（另外，所謂調配之後， - 是表示在半導體用研磨液之調整（調配）完成後小於丨小時的時間内，下同。） [半導體基板之研磨] 仏一面將調配之後的實例18之半導體基板用研磨液供給至研磨定盤之研磨布上，一面於將半導體基板按壓在研 ◎ ^布上之狀態下，使研磨定盤相對於半導體基板而相對性旋轉，由此對半導體基板之表面進行研磨。而且，以與實例18同樣之方法，使用調配之後的實例丨9〜實例％之各研磨液對半導體基板進行研磨。研磨條件之詳細情況如下所示。 (研磨條件）研磨裝置：Nano Factor公司製造之FACT-200型研磨布：NITTAHAAS公司製造之IC-1010 研磨定盤轉速：80 rpm 〇固持器轉速：無驅動裝置（自由旋轉）研磨墨力.33.83 kPa (345 gf/cm2) 研磨液供給置：16ml/min 研磨時間：5 min 半導體基板（被研磨物）：2 cm見方之矽晶圓（p型 <100> ) [清洗] 68 201042019 研磨後，利用聚乙烯醇製刷及超音波水進行半導體基板之清洗。清洗後，用旋轉乾燥器使半導體基板乾燥。 [研磨速度之測定] . 使用調配之後的實例18〜實例24之各半導體用研磨液，以上述方法對矽晶圓進行研磨後，測定隨著研磨的矽晶圓之重量的減少量。而且，由重量之減少量、晶圓面積、石夕之比重及研磨時間算出研磨速度（單位：nm/min)。將算出結果示於表11。另外，於矽晶圓之重量測定中使用分析用電子天平（Mettler公司製造之AB104)。測定溫度為 25°C ’測定濕度為40%RH以上。矽比重為2.33。 [表面粗縫度評價] 使用實例18〜實例24之研磨液，以上述方法對石夕晶圓進行研磨後，使用階差/表面粗糙度/微細形狀測定裝置’以下述條件測定矽晶圓之研磨面的算術平均粗糙度。將測定結果示於表11。 (測定條件） ◎ 階差/表面粗糙度/微細形狀測定裝置：KLA Tencor公Magnetic = agitator: JJS-30D manufactured by AsOne Co., Ltd. Measured sequence: using a stirrer with a long diameter of about 4 cm and a short diameter of about 0.5 cm with a fluorine 67 201042019 34297pif resin coating, stir the slurry at 5 rpm The pH was measured in the state. Measurement period: After the preparation of the polishing liquid (in addition, after the preparation, - means that the time after the adjustment (mixing) of the semiconductor polishing liquid is completed is less than 丨 hours, the same applies.) [Polishing of the semiconductor substrate] After the polishing liquid for the semiconductor substrate of Example 18 after the preparation was supplied to the polishing cloth of the polishing platen, the polishing plate was relatively rotated with respect to the semiconductor substrate while the semiconductor substrate was pressed against the polishing substrate. Thereby, the surface of the semiconductor substrate is polished. Further, in the same manner as in Example 18, the semiconductor substrate was polished using each of the polishing liquids of Examples -9 to Instance % after the preparation. The details of the grinding conditions are as follows. (Grinding conditions) Grinding device: FACT-200 type abrasive cloth manufactured by Nano Factor: IC-1010 manufactured by NITTAHAAS Grinding plate rotation speed: 80 rpm 〇 Holder rotation speed: no drive (free rotation) Grinding ink force. 33.83 kPa (345 gf/cm2) Grinding solution supply: 16 ml/min Grinding time: 5 min Semiconductor substrate (abrasive): 2 cm square wafer (p-type <100>) [Cleaning] 68 201042019 After grinding The semiconductor substrate is cleaned by a polyvinyl alcohol brush and ultrasonic water. After washing, the semiconductor substrate was dried with a rotary dryer. [Measurement of polishing rate] Using the respective polishing liquids for semiconductors of Examples 18 to 24 after the preparation, the silicon wafer was polished by the above method, and the amount of reduction in the weight of the polished silicon wafer was measured. Further, the polishing rate (unit: nm/min) was calculated from the amount of weight reduction, the wafer area, the specific gravity of the stone, and the polishing time. The calculation results are shown in Table 11. In addition, an analytical electronic balance (AB104 manufactured by Mettler) was used for the weight measurement of the wafer. The measurement temperature was 25 ° C. The measured humidity was 40% RH or more. The specific gravity is 2.33. [Evaluation of Surface Roughness] Using the polishing liquids of Examples 18 to 24, the Shiki wafer was polished by the above method, and then the step/surface roughness/fine shape measuring device was used to measure the wafer under the following conditions. The arithmetic mean roughness of the ground surface. The measurement results are shown in Table 11. (Measurement conditions) ◎ Step/surface roughness/fine shape measuring device: KLA Tencor

司製造之P16-GF 測定模式：粗縫度（Roughness) 測定長度：200 μιη 測定速度：5 μιη/sec 測定荷重：1 mg 69P16-GF measurement mode: Roughness Determination length: 200 μηη Measurement speed: 5 μιη/sec Determination of load: 1 mg 69

201042019 /piJL201042019 /piJL

[表 11] 實例 18 19 20 21 22 23 24 研磨粒子種類膠體二氧化矽膠體二氧化矽膠體二氧化矽膠砬二氧_ 化矽膠體二氧一化矽膠體二氧化石夕膠體二C 彳卜石々粒子添加量 (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 水溶聚合物種類 PVPK15 PVPK30 PVP_K90 PVPK30 PVPJC30 PVPK30 PVP_K30 性聚添加量 (wt%) 0.05 0.05 0.05 0.01 0.10 0.05 0.05 合物 1，2,4-二唑添加量（wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5— 驗性化合物 nt 1&. ^ r\U 氫氧化鉀 11 鼠氧化鉀 1 1 氫氧化鉀氫氧化卸氫氧化卸― 氫氧化四甲基銨氫氧化鉀 ^^您狀pn 研磨速度 248 Π ~227~~~ 11 11 11 11 9 (nm/min ) ΟΛ 9 205 364 202 222 128 具《平吟租糙度（人） ^ ΛΠ Λ 23.7 22.9 25.5 22.8 24.1 23.3 最大问度 (Α) Ζ4 /.U 230.3 ---^ 227.1 ------ 243.5 230.5 234.1 23〇4~ (比較例33) 依照以下順序，以矣η丄 ^中所枕研練二所枕添，量娜下述表及無機鹼性化合物，調分子二溶性聚合物）、外，於比較例33之研^H33之半導_研磨液。另於比較例幻之研Ϊ 2添加三峻。之50質量％的純水中調製中，於相當於研磨液整體 (PVP一K30)，於1中六.05質量0/〇之聚乙烯0比咯燒_ 一、添加氣氧化鉀直至pH成為9。其次， 70 201042019 /pii 二散入0.5貝量/〇之一次粒控為17 n扭之膠體二氧化石夕後^純水進行調配以使其成為總計95質量％。接著，添加氫氧化卸直至成為所期望之PH，剩餘部分以純水進行調配以使其成為總計100質量％。 (比較例34) 依照以下财，以表u巾所^添加量娜下述表 o o ^制ΓίΤ之研磨粒子、m三唾、及無機祕化合物，调衣比較例2之半導體用研磨液。綱。另外’於比較例34之研磨液中並未添加聚乙烯料院於比較例34之研磨液之調製中，於相加質，:峨水中溶解〇.5質量❶/邮中添加虱乳化卸直至pH成為9。其次分散入〇 5 之一次粒控為17 nm之膠體_氧〇㈣甘# 化錢，輯水進行調配使八成為、.悤汁95質量％。接著，添所期望之pH，剩餘部分以純 ^化卸直至成為 l0〇tt〇/〇0 ”機水進㈣配以使其成為總計 (比較例35) 序’以表12中所示之添加_-^ 中所不之研磨粒子及無機之半導體用研磨液。另外，於比条 1二物補比較例35 U4-三嗤及聚乙㈣略_。X彳5之研磨液並未添加買重此屯水添加氩氣化釺直至pH成為9。其次， 71 201042019 分散入0·5質量％之一次粒徑為17 nm之膠體二氧化石夕後=純水進行調配以使其成為總計95質量％。接著，添加氫氧化鉀直至成為所期望之pH，剩餘部分以純水進行調配以使其成為總計100質量％。以與實例18同樣之枝，測定味例33〜比較例35 之各半導體用研磨液之pH及研磨速度、以及使用比較例 33〜比較例35之各研磨液進行研磨後的半導體基板表面之算術平均《I度及最大高度。將測定結果示於表12。 [表 12][Table 11] Example 18 19 20 21 22 23 24 Abrasive particle type colloidal cerium oxide colloidal cerium oxide colloidal cerium oxide cerium dioxide _ hydrazine colloidal dioxin hydrazine colloidal dioxide oxidized silica gel celite II C 彳石々 Particle addition amount (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Water soluble polymer type PVPK15 PVPK30 PVP_K90 PVPK30 PVPJC30 PVPK30 PVP_K30 Addition amount (wt%) 0.05 0.05 0.05 0.01 0.10 0.05 0.05 Compound 1,2,4- 2 Addition amount of azole (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - test compound nt 1&. r rU potassium hydroxide 11 mouse potassium oxide 1 1 potassium hydroxide hydroxide dehydration and dehydration - tetramethyl hydroxide Ammonium oxyhydroxide ^^ Your shape pn Grinding speed 248 Π ~227~~~ 11 11 11 11 9 (nm/min ) ΟΛ 9 205 364 202 222 128 With "flatness and roughness (person) ^ ΛΠ Λ 23.7 22.9 25.5 22.8 24.1 23.3 Maximum degree of question (Α) Ζ4 /.U 230.3 ---^ 227.1 ------ 243.5 230.5 234.1 23〇4~ (Comparative example 33) According to the following sequence, pillows in 矣η丄^ Studying the second pillow, the amount of the following table and inorganic alkaline compounds, Molecular two-insoluble polymer), an outer, semiconductive _ polishing solution in Comparative Example 33 of RESEARCH of ^ H33. In addition to the comparative example of the illusion of research 2 add three stern. In the preparation of 50% by mass of pure water, it corresponds to the whole of the polishing liquid (PVP-K30), and in the middle of 6.05 mass 0 / 〇 of the polyethylene 0 than the sizzling _ a, adding potassium sulphate until the pH becomes 9. Next, 70 201042019 /pii 2 scattered 0.5 lbs/〇 of the first granule control is 17 n twisted colloidal silica dioxide and then pure water is formulated to make it a total of 95% by mass. Subsequently, the water was removed by hydrogenation until the desired pH was obtained, and the remainder was adjusted with pure water to make it 100% by mass in total. (Comparative Example 34) A polishing liquid for a semiconductor of Comparative Example 2 was prepared by adding the following particles to the polishing particles, the m-salt, and the inorganic secret compound in the following table. Outline. In addition, in the polishing liquid of Comparative Example 34, no addition of the polyethylene material to the preparation of the polishing liquid of Comparative Example 34 was carried out, and the addition was carried out, and the enthalpy was dissolved in 峨5. The pH becomes 9. Secondly, it is dispersed into 胶5. The granule is controlled by a colloid of 17 nm. _ Oxygen 〇 (4) 甘# 钱 , , 化化化化化化辑辑辑辑辑辑辑辑辑辑辑辑辑辑Next, the desired pH is added, and the remaining portion is removed by pure purification until it becomes l0〇tt〇/〇0" machine water (4) is matched to make it total (Comparative Example 35) Order 'Addition as shown in Table 12_ -^ In the case of abrasive particles and inorganic semiconductor polishing liquids, in addition to the comparison with the strip 1 and the comparative example 35 U4-three and polyethylene (four) slightly _. X彳5 slurry is not added to buy weight This hydrazine is added with argon vaporized hydrazine until the pH becomes 9. Secondly, 71 201042019 is dispersed in 0.5% by mass of colloidal silica with a primary particle diameter of 17 nm, and then pure water is formulated to make it a total of 95 masses. Then, potassium hydroxide was added until the desired pH was obtained, and the remainder was blended with pure water to make it 100% by mass in total. The same semiconductors as in Example 18 were used to measure the semiconductors of the taste examples 33 to 35. The arithmetic mean "I degree and maximum height" of the surface of the semiconductor substrate after polishing using the pH and polishing rate of the polishing liquid and the respective polishing liquids of Comparative Examples 33 to 35 are shown in Table 12. [Table 12] ]

可確認於實例19中，與除不含丨，2,4三唑以外其它與實例19相同之比較例33相比，研磨速度高，算術平均^ 糙度及最大高度小。可確認於比較例34、比較例35中，與實例18〜實例24相比，算術平均粗糙度及最大高戶較大。由以上可確認：於本發明十，可以較高之研磨 72 201042019 半導體基板之表面研磨加工為凹凸較少之平滑表面。 <第四半導體基板用研磨液> (實例25〜實例36) [半導體用研磨液之調製] Ο Ο 依照以下順序，以表13中所示之添加量調配研磨粒子、水溶性高分子（水溶性聚合物）、1>2，冬三唑、及鹼性，合物，調製實例25〜實例36之各半導體用研磨液。於各研磨液之調製中，使用聚乙烯吡咯烷鲷（ρνρ—κ3〇)作 Ϊ水溶性聚合物。Κ值是與分子量相關之黏性特性值，是轉由毛細管黏度計所測定之於25°c下之相對黏度值。於各研磨液之調製中’首先使U4_ (PVP) f ί L 3中添加驗性化合物直至PH成為9。其次，分散之一次粒徑為17 nm之膠體二氧化石夕後，以化人物ΐΓΓί使其成為總計95質量％。接著，添加驗性使望《ρΗ，剩餘部分以純水進行調配以使具成為總計100質量％。 [PH測定] 以與實例18同樣之方式測定實例奋導體用研磨液之pH。將各半導體用〜貝例36之各半 [粒研磨半導體基板之調整Γ磨液之PH示於表13。以下述條件對直徑為3〇〇 mm 整表面經粗研磨之料θ8Ι。切4細研磨，調研磨晶圓· 300 mm石夕晶圓 73 201042019 ^^fzy/pn 研磨機：Reflexion ( Applied Materials 公司製造）研磨定盤轉速：123rpm 固持器轉速：117 rpm 研磨壓力：13.7kPa 研磨液供給量：250ml/min 研磨墊：SUBA600 ( NITTA HAAS公司製造）研磨液：二氧化矽研磨粒（一次粒徑為17 nm) 〇.5〇/。、氫氧化四曱基銨（以下稱為「TMAH」）、pH為10.5 研磨時間：90 sec [半導體基板之研磨] 一面將調配之後的實例25之半導體基板用研磨液供給至研磨定盤之研磨布上，一面於將半導體基板按壓在研磨布上之狀態下，使研磨定盤相對於半導體基板而相對性說轉，由此對半導體基板之表面進行研磨。而且，以與實例25同樣之方法，使用調配之後的實例26〜實例36之各研磨液對半導體基板進行研磨。研磨條件之詳細情況如下所示。 (研磨條件）研磨晶圓：上述所製成之粗研磨後之3〇〇 mm石夕晶圓研磨機：Reflexion (Applied Materials 公司製造）研磨定盤轉速：123 rpm 固持器轉速：117 rpm 研磨壓力：9.7kPa 研磨液供給量：250ml/min 74 201042019 /pu 研磨墊：Supreme RN-H Pad 30.5，，D PJ ; CX01 ( NITTA HAAS公司製造）研磨時間：10 min [清洗] 以下述條件清洗所述研磨後之晶圓。清洗機：MESA (Applied Materials 公司製造）清洗液：氫氧化銨〇.〇6vol°/0 刷清洗時間：60 sec [缺陷數及霧度值之測定] 使用實例25〜實例36之研磨液，以上述方法對石夕⑤ 圓進行研磨，加以清洗後’使用下述裝置測定表示為缺陷數及霧度（HAZE)值之值。將測定結果示於表13。缺陷檢查裝置：LS6700 (日立電子工程公司製造）步驟條件檔案（測定參數）：VeMlOL 缺陷測定範圍：0.1 μιη〜3.0 投光條件：垂直 75 201042019 34297pif [表 13]It was confirmed that in Example 19, the polishing rate was high, and the arithmetic mean roughness and the maximum height were small as compared with Comparative Example 33 which was the same as Example 19 except that no ruthenium or 2,4 triazole was contained. It was confirmed that in Comparative Example 34 and Comparative Example 35, the arithmetic mean roughness and the maximum height were larger than those of Examples 18 to 24. From the above, it can be confirmed that in the tenth aspect of the present invention, the polishing can be performed at a higher rate. 72 201042019 The surface of the semiconductor substrate is polished to a smooth surface having less unevenness. <Finishing liquid for fourth semiconductor substrate> (Examples 25 to 36) [Preparation of polishing liquid for semiconductors] Ο 调 In accordance with the following procedure, the abrasive particles and the water-soluble polymer are blended in the amounts shown in Table 13 ( The water-soluble polymer), 1 > 2, winter triazole, and basic compound, each of the polishing liquids for semiconductors of Examples 25 to 36 was prepared. In the preparation of each polishing liquid, polyvinylpyrrolidinium (ρνρ-κ3〇) was used as the water-soluble polymer. The enthalpy value is the viscosity characteristic value associated with the molecular weight, which is the relative viscosity value measured by the capillary viscometer at 25 ° C. In the preparation of each slurry, the test compound was first added to U4_(PVP) f ί L 3 until the pH became 9. Next, after dispersing the colloidal silica having a primary particle diameter of 17 nm, it was made into a total of 95% by mass. Next, the test was added to make it "pΗ, and the remaining portion was blended with pure water so that the mass became 100% by mass in total. [pH measurement] The pH of the example polishing liquid for the conductor was measured in the same manner as in Example 18. Each of the semiconductors was used in each of the half of the examples 36. [The pH of the honing liquid for the grain-polished semiconductor substrate is shown in Table 13. The coarsely ground material θ8Ι was obtained on the entire surface having a diameter of 3 μm under the following conditions. Cut 4 fine grinding, adjust the grinding wafer · 300 mm Shi Xi Wafer 73 201042019 ^^fzy/pn Grinder: Reflexion (manufactured by Applied Materials) Grinding plate speed: 123rpm Retainer speed: 117 rpm Grinding pressure: 13.7kPa Serving fluid supply: 250 ml/min Grinding pad: SUBA600 (manufactured by NITTA HAAS) Grinding fluid: cerium oxide abrasive grains (primary particle size: 17 nm) 〇.5〇/. , tetrakisyl ammonium hydroxide (hereinafter referred to as "TMAH"), pH: 10.5, polishing time: 90 sec [grinding of semiconductor substrate] The polishing liquid for the semiconductor substrate of Example 25 after the preparation was supplied to the polishing of the polishing plate On the cloth, the surface of the semiconductor substrate is polished by relatively rotating the polishing platen against the semiconductor substrate while the semiconductor substrate is pressed against the polishing cloth. Further, in the same manner as in Example 25, the semiconductor substrate was polished using the respective polishing liquids of Examples 26 to 36 after the preparation. The details of the grinding conditions are as follows. (Grinding conditions) Grinding wafer: The above-mentioned rough-milled 3〇〇mm Shihwa wafer grinder: Reflexion (Applied Materials) Grinding plate speed: 123 rpm Retainer speed: 117 rpm Grinding pressure : 9.7 kPa Supply of slurry: 250 ml/min 74 201042019 /pu Abrasive pad: Supreme RN-H Pad 30.5,, D PJ ; CX01 (manufactured by NITTA HAAS) Grinding time: 10 min [Cleaning] The above conditions were washed. Grinded wafer. Washing machine: MESA (manufactured by Applied Materials) Washing liquid: Ammonium hydroxide 〇.〇6vol°/0 Brush cleaning time: 60 sec [Determination of defect number and haze value] Using the polishing liquid of Example 25 to Example 36, In the above method, the Shi Xi 5 circle was polished, and after washing, the values indicated as the number of defects and the haze (HAZE) were measured using the following apparatus. The measurement results are shown in Table 13. Defect inspection device: LS6700 (manufactured by Hitachi Electronic Engineering Co., Ltd.) Step condition file (measurement parameter): VeMlOL Defect measurement range: 0.1 μηη~3.0 Projection conditions: vertical 75 201042019 34297pif [Table 13]

0.025 1，2,4-三唑添加量（wt0/〇) 驗性化合物 0.1 氫氧化四曱基銨0.025 1,2,4-triazole addition amount (wt0/〇) test compound 0.1 tetradecyl ammonium hydroxide

研磨液pH 缺陷 22500 氫氧化四甲基銨 14625 氫氧化四甲基銨氫氧化四甲基銨氫氡化四甲基錄氫氧化四甲基銨霧度 132 132 11679 —134— 12567 23624 18253 —155 — 135 145 研磨實例一次粒徑 (ran) 31 17 32 17 33 17 34 17 35 17 36 Ϊ7 子水添加重 (wt% ) 聚合物種類 03 PVP K30 0.3 ΡΛΛΡ 0.3 0.3 0.3 0.3 溶性聚添加量 (wt% ) 0.025 Γ ν 厂一r〇U 0.025 rVP_K30 0.025 PVPK30 0.025 PVP_K30 0.025~~ PVP_K30 ~~〇025~~ 合物 1,2,4-三唑添加量（wt%) 0.5 1.0 0.2 0.2 ~~02~ 02~~ 驗性化合物氫氧化四曱基鍵氫氧化四曱基銨氫氧化鉀氫氧化敍氫氧化四甲某^餘氫氧化四研磨液pH 10 10 10 10 1 曱基録缺陷 15532 15325 15667 11234 ~~Ϊ352Γ~ —-i_ 霧度 136 ------- 137 148 135 ----1 18897 76 201042019 . (比較例36〜比較例39) [半導體用研磨液之調製] 依照以下順序’以表14中所示之添加量調配研磨粒子、水溶性高分子（水溶性聚合物）、1，2,4-三吐、及驗性化合物’調製比較例36〜比較例39之各半導體用研磨液。於各研磨液之調製中’使用聚乙烯η比!7各烧酮（pVp K3〇) 0 作為水溶性聚合物。κ值是與分子量相關之黏性特性值，是藉由毛細管黏度計所測定之於2 5它下之相對黏度值。於各研磨液之調製中，首先使^4·三唑及聚乙烯吡嘻烧嗣（PVP)溶解於相當於研磨液整體之5〇質量％的純水中，於其中添加鹼性化合物直至拆1成為9。其次，分散入〇_3質量％之一次粒徑為17 nm之膠體二氧化矽後以純水進行調配以使其成為料95質量％。接著，添加鹼性化合物直至成為所期望之pH，剩餘部分以純水進行調配以使其成為總計1 〇〇質量％。乂'、實例25同樣之方法，測定比較例36〜比較例39 之各半導體用研磨液之pH、以及使用比較例36〜比較例 39之各研磨液的研磨後之石夕晶圓纟面之缺陷數及霧度値。將測定結果示於表14。 77 201042019 /pi 丄 [表 14] 比幸. 乏例 36 37 38 39 研磨粒千一二欠粒禮Λ nm J 真 17 17 17 17 办加重 (wt%) 0.3 —... 0.3 0.3 0.3 水溶性聚合物聚合物種類法h喜鱗 PVP K30 PVP K30 PVP K30 添刀〇置 (wt% ) 0.025 1.00 0.025 1，2,4-二。坐添加 1 (wt%) 0.2 -----—___ - 0.2 02 驗性化合物氣氧化四氫氧化四曱基銨氫氧化四甲基锻氫氧化鉀研磨液pH ---— ' 10 缺陷以上 10 10 13 27467 測定極限以上測定極限以 μ 霧度測定極限以上 194 測定極限以上測定極限以上可確認於實例25〜實例36中，與味例36〜比較例 39相比，缺陷數少，且成為表面粗糙度之指標的霧度值小，且可消除凹凸。 <第五半導體基板用研磨液> (實例37〜實例44) [半導體用研磨液之調製] 依照以下順序，以表15中所示之添加量調配研磨粒子、水溶性高分子（水溶性聚合物）、1，2,4_三唑、及鹼性化合物，調製實例37〜實例44之各半導體用研磨液。於各研磨液之調製中’使用使用K值不同之三種聚乙稀π比略烧_ (PVP_K15、PVP_K30、PVP一Κ90)之任—種作為水溶性聚合物。K值是與分子量相關之黏性特性值，是^由 78 201042019 毛細管黏度計所測定之於饥下之相對黏度值。於各研磨液之調製中，首先使u，4_三，酮（m>)溶解於相當於研磨液整體之5q === 水中’於其中添加驗性化合物直至pH成為9 n〇八坤入〇.5質量％之—次粒徑為17 nm之膠體二氧^德= 純水進行調配以使其成為總計95質量％。，Grinding solution pH defect 22500 tetramethylammonium hydroxide 14625 tetramethylammonium hydroxide tetramethylammonium hydroxide hydroquinone tetramethylammonium hydroxide tetramethylammonium haze 132 132 11679 —134— 12567 23624 18253 —155 — 135 145 Grinding example Primary particle size (ran) 31 17 32 17 33 17 34 17 35 17 36 Ϊ7 Sub-water addition weight (wt%) Polymer type 03 PVP K30 0.3 ΡΛΛΡ 0.3 0.3 0.3 0.3 Solubility polyaddition (wt% ) 0.025 Γ ν Factory-r〇U 0.025 rVP_K30 0.025 PVPK30 0.025 PVP_K30 0.025~~ PVP_K30 ~~〇025~~ 1,2,4-triazole addition (wt%) 0.5 1.0 0.2 0.2 ~~02~ 02 ~~ Authentic Compounds Tetrahydrocarbyl Hydroxide, Tetramethylammonium Hydroxide, Potassium Hydroxide, Hydroxide, Hydroxide, Tetrahydrate, Residual Hydroxide, 4 Grinding Liquid, pH 10 10 10 10 1 曱Base Record Defect 15532 15325 15667 11234 ~ ~Ϊ352Γ~ —-i_ Haze 136 ------- 137 148 135 ----1 18897 76 201042019 . (Comparative Example 36 to Comparative Example 39) [Modulation of semiconductor polishing liquid] In the following order The addition amount shown in Table 14 is formulated with abrasive particles and water-soluble polymer ( Water-soluble polymer), 1,2,4-three-discharge, and test compound 'The polishing liquid for each semiconductor of Comparative Example 36 to Comparative Example 39 was prepared. In the preparation of each polishing liquid, a polyethylene η ratio of 7 ketone (pVp K3 〇) 0 was used as a water-soluble polymer. The κ value is the viscous property value associated with the molecular weight, which is the relative viscosity value measured by the capillary viscometer below 25 . In the preparation of each polishing liquid, first, the tetrazole and the polyvinylpyrrolidone (PVP) are dissolved in pure water corresponding to 5 mass% of the entire polishing liquid, and a basic compound is added thereto until it is removed. 1 becomes 9. Next, the colloidal ceria having a primary particle diameter of 17 nm was dispersed in 〇3 mass%, and then blended with pure water to make it 95% by mass. Next, the basic compound was added until the desired pH was obtained, and the remainder was blended with pure water to make it a total of 1% by mass. In the same manner as in Example 25, the pH of each of the polishing liquids for semiconductors of Comparative Examples 36 to 39 and the polishing of the polishing liquids of Comparative Examples 36 to 39 were used. The number of defects and the haze. The measurement results are shown in Table 14. 77 201042019 /pi 丄[Table 14] 幸幸. The lack of 36 37 38 39 abrasive grains 千 1-2 欠 Λ Λ nm j 真 17 17 17 17 to increase (wt%) 0.3 —... 0.3 0.3 0.3 water soluble Polymer polymer type method h hi scale PVP K30 PVP K30 PVP K30 Add knife set (wt%) 0.025 1.00 0.025 1,2,4-two. Sit 1 (wt%) 0.2 ------___ - 0.2 02 Detective compound gas oxidized tetramethylammonium hydroxide tetramethyl hydride potassium hydroxide slurry pH --- - ' 10 defects above 10 10 13 27467 The measurement limit is equal to or higher than the measurement limit of the haze measurement limit of 194. The measurement limit is equal to or higher than the measurement limit. In Examples 25 to 36, the number of defects is smaller than that of the taste examples 36 to 36. The surface roughness index has a small haze value and can eliminate irregularities. <Film liquid for fifth semiconductor substrate> (Examples 37 to 44) [Preparation of polishing liquid for semiconductor] The abrasive particles and water-soluble polymer (water-soluble polymer) were prepared in the following order in the amounts shown in Table 15 Each of the semiconductor polishing liquids of Examples 37 to 44 was prepared by using a polymer, a 1,2,4-triazole, and a basic compound. As the water-soluble polymer, any of the three kinds of polyethylenes having a different K value and slightly sinter _ (PVP_K15, PVP_K30, PVP-90) was used in the preparation of each polishing liquid. The K value is the viscosity characteristic value associated with the molecular weight, which is the relative viscosity value measured by the 78 201042019 capillary viscometer for hunger. In the preparation of each polishing liquid, first, u, 4_3, ketone (m>) is dissolved in 5q === water corresponding to the whole of the polishing liquid, and the test compound is added thereto until the pH becomes 9 n〇8k into 5. 5 mass% - colloidal dioxos having a sub-particle size of 17 nm = pure water was formulated so as to be 95% by mass in total. ,

所期望之PH，剩餘部分以純便具成為總計100質量％。 [pH測定] 以與實例18同樣之方式進行而測定實例37〜實例44 之各半導體用研磨液之pH。將各半導體用研磨液之pH* 於表15。 [半導體基板之研磨] 一面將調配之後的實例37之半導體基板用研磨液供給至研磨定盤之研磨布上，一面於將半導體基板按壓在研磨布上之狀態下’使研磨定盤相對於半導體基板而相對性旋轉’由此對半導體基板之表面進行研磨。而且，以與實例37同樣之方法，使用調配之後的實例38〜實例44之各研磨液對半導體基板進行研磨。研磨條件之詳細情況如下所示。 (研磨條件）研磨晶圓：研磨後之300 mm石夕晶圓研磨機：Reflexion ( Applied Materials 公司製造）研磨定盤轉速：123 rpm 79 201042019 J4zy/pit 固持器轉速：117 rpm 研磨壓力：13,7 kPa 研磨液供給量：250 ml/min 研磨墊：MH-S15C (NITTAHAAS公司製造） [清洗] 以下述條件清洗所述研磨後之晶圓。清洗機：MESA ( Applied Materials 公司製造）清洗液：氫氧化銨0.06 vol% 刷清洗時間：60 sec [研磨速度之測定] 以上述方法對矽晶圓進行研磨後，測定隨著研磨的石夕晶圓之重量的減少量。而且，由重量之減少量、晶圓面積 (706.5 cm2)、矽之比重及研磨時間算出研磨速度（單位[ nm/min)。另外，於矽晶圓之重量測定中使用分析用電子天平（Mettler公司製造之AB104)。測定溫度為25°c，測定濕度為40%RH以上。矽比重為2.33。將測定結果示於表 15。、 [表面粗糙度評價] 以上述方法對矽晶圓進行研磨後，使用階差/表面粗糙度/微細形狀測定裝置’於以下之條件下進行石夕晶圓之研磨面之缺陷評價。另外，將粗晶圓之目標研磨量設為L(nm)、將粗晶圓之初始階差（最大高度）設為Rt() (nm)及將經粗研磨之粗晶圓之階差（最大高度）設為Rti (nm)。將測定結果示於表15。 201042019 (測定條件）The desired pH, the remainder is 100% by mass in total. [pH measurement] The pH of each of the polishing liquids for semiconductors of Examples 37 to 44 was measured in the same manner as in Example 18. The pH of each of the semiconductor polishing liquids is shown in Table 15. [Polishing of the semiconductor substrate] While supplying the polishing liquid for the semiconductor substrate of Example 37 after the preparation to the polishing cloth of the polishing plate, the polishing plate is opposed to the semiconductor while the semiconductor substrate is pressed against the polishing cloth. The substrate is relatively rotated 'to thereby polish the surface of the semiconductor substrate. Further, in the same manner as in Example 37, the semiconductor substrate was polished using the respective polishing liquids of Examples 38 to 44 after the preparation. The details of the grinding conditions are as follows. (Grinding conditions) Grinding wafer: 300 mm after grinding, Grinding wafer grinder: Reflexion (manufactured by Applied Materials) Grinding and fixing speed: 123 rpm 79 201042019 J4zy/pit Retainer speed: 117 rpm Grinding pressure: 13, 7 kPa Supply of polishing liquid: 250 ml/min. Abrasive pad: MH-S15C (manufactured by NITTAHAAS) [Cleaning] The polished wafer was cleaned under the following conditions. Washing machine: MESA (manufactured by Applied Materials) Cleaning solution: ammonium hydroxide 0.06 vol% Brush cleaning time: 60 sec [Measurement of polishing speed] After polishing the tantalum wafer by the above method, the stone was measured with the grinding The amount of reduction in the weight of the circle. Further, the polishing rate (unit: [nm/min) was calculated from the weight reduction amount, the wafer area (706.5 cm2), the specific gravity of the crucible, and the polishing time. In addition, an analytical electronic balance (AB104 manufactured by Mettler) was used for the weight measurement of the wafer. The measurement temperature was 25 ° C, and the measured humidity was 40% RH or more. The specific gravity is 2.33. The measurement results are shown in Table 15. [Evaluation of Surface Roughness] After the silicon wafer was polished by the above method, the defect evaluation of the polishing surface of the Shixi wafer was carried out under the following conditions using the step/surface roughness/fine shape measuring apparatus. In addition, the target polishing amount of the rough wafer is set to L (nm), the initial step (maximum height) of the rough wafer is set to Rt () (nm), and the step of coarsely grinding the coarse wafer ( The maximum height is set to Rti (nm). The measurement results are shown in Table 15. 201042019 (measurement conditions)

階差/表面粗糙度/微細形狀測定裝置：KLA Tencor公司製造之P16-OF 測定模式：粗糙度（Roughness) 測定長度：5 mm 測定荷重：1 mg [表 15]Step/surface roughness/fine shape measuring device: P16-OF manufactured by KLA Tencor Co., Ltd. Measurement mode: Roughness Determination length: 5 mm Measuring load: 1 mg [Table 15]

實例 37 38 39 40 研磨粒子一次粒徑 (nm) 36 17 17 17 添加量 (wt% ) 0.5 0.5 0.5 0.5 水溶性聚合物聚合物種類 PVP—K15 PVPK30 PVP—K90 PVP_K30 添加量 (wt% ) 0.05 0.05 0.05 0.01 1，2,4-三唑添加量（加％) 0.5 0.5 0.5 α5 驗性化合物氫氧化鉀氫氧化鉀氫氧化鉀氫氧化鉀研磨液pH 11 11 11 11 覆面研磨速度 (nm/min ) 218 205 192 372 最大南度 Rt (nm) 研磨前 (Rt〇) 1083 1077 1065 1082 研磨後 (Rti) 70 59 58 72 L (nm) 1233 1250 1153 1220 L/ (Rt〇-Rt,) 1.22 1.23 1.14 1.21 81 201042019 j4/v/pit 實例 41 42 43 44 研磨粒子一次粒徑 (ran) 17 17 17 36 添加量 (wt% ) 0.5 0.5 0.5 0.5 水溶性聚合物聚合物種類 PVP—K30 PVP—K30 PVP_K30 PVP_K30 添加量 (wt% ) 0.10 0.05 0.05 0.05 1,2,4-三。坐添加量（'^%) 0.5 0.5 0.5 0.5 驗性化合物氫氧化鉀氫氧化四曱基銨氫氧化鉀氫氧化鉀研磨液pH 11 11 9 11 覆面研磨速度 (nm/min ) 168 210 128 201 最大南度Rl (nm) 研磨前 (Rto) 1088 1059 1074 1077 研磨後 (RtO 52 48 49 57 L (nm) 1179 1227 1264 1286 L/ (Rto-RtO 1.14 1.21 1.23 1.26 (比較例40〜比較例42) [半導體用研磨液之調製] 依照以下順序，以表16中所示之添加量調配研磨粒子、1,2,4-三嗤、及驗性化合物，調製比較例40〜比較例 42之各半導體用研磨液。於各研磨液之調製中，首先使1，2,4-三唑溶解於相當於研磨液整體之50質量％的純水中，於其中添加鹼性化合物直至pH成為9。其次，於比較例40中，分散入0.5質量％之一次粒徑為36 nm之膠體二氧化石夕後，以純水進行調配以使其成為總計95質量％。接著，添加驗性化合物直 82 201042019 ±LZ 7" ° 41 ^? °·5 -人祖住為7 nm之膠體二氧化矽後，以其成為總計95曾吾。/。鮮使㈣夕u質接鹼性化合物直至成為所 ❸ j旦。之pH，剩餘部分以純水進行調配以使其成為總計_ 貝里/〇。於比較例42中，分散入〇·5質量％之一次粒徑為二nm之賴二氧化機，以純錢行細喊其成為總計95質量％。接著’添加驗性化合物直至成為所期望之 PH，剩餘部分以純水進行調配以使其成為總計 100質量 %。另外，於比較例比較例42中並未添加ls2,4_三唑。' 以與實例37同樣之方法，進行比較例4〇〜比較例42 之各半導體用研磨液之pH測定、以及使用比較例4〇〜比較例42之各研磨液對矽晶圓進行研磨時之研磨速度測定、及表面粗糙度評價。將測定結果示於表16。Example 37 38 39 40 Abrasive particles Primary particle size (nm) 36 17 17 17 Addition amount (wt%) 0.5 0.5 0.5 0.5 Water-soluble polymer polymer type PVP-K15 PVPK30 PVP-K90 PVP_K30 Addition amount (wt%) 0.05 0.05 0.05 0.01 1,2,4-triazole addition amount (plus %) 0.5 0.5 0.5 α5 Detective compound potassium hydroxide potassium hydroxide potassium hydroxide potassium hydroxide slurry pH 11 11 11 11 coating grinding speed (nm/min) 218 205 192 372 Maximum south degree Rt (nm) Before grinding (Rt〇) 1083 1077 1065 1082 After grinding (Rti) 70 59 58 72 L (nm) 1233 1250 1153 1220 L/ (Rt〇-Rt,) 1.22 1.23 1.14 1.21 81 201042019 j4/v/pit Example 41 42 43 44 Abrasive particles primary particle size (ran) 17 17 17 36 Addition amount (wt%) 0.5 0.5 0.5 0.5 Water-soluble polymer polymer type PVP-K30 PVP-K30 PVP_K30 PVP_K30 Adding amount (wt%) 0.10 0.05 0.05 0.05 1,2,4-three. Addition amount ('^%) 0.5 0.5 0.5 0.5 Detective compound potassium hydroxide hydroxide tetradecyl ammonium hydroxide potassium hydroxide slurry pH 11 11 9 11 coating grinding speed (nm / min) 168 210 128 201 maximum South R1 (nm) before grinding (Rto) 1088 1059 1074 1077 After grinding (RtO 52 48 49 57 L (nm) 1179 1227 1264 1286 L/ (Rto-RtO 1.14 1.21 1.23 1.26 (Comparative Example 40 to Comparative Example 42) [Preparation of polishing liquid for semiconductors] The polishing particles, 1,2,4-triazole, and the test compound were blended in the amounts shown in Table 16 in the following order, and the semiconductors of Comparative Examples 40 to 42 were prepared. In the preparation of each polishing liquid, first, 1,2,4-triazole is dissolved in pure water corresponding to 50% by mass of the entire polishing liquid, and a basic compound is added thereto until the pH becomes 9. In Comparative Example 40, 0.5% by mass of colloidal silica having a primary particle diameter of 36 nm was dispersed, and then blended with pure water to make it a total of 95% by mass. Then, an intumescent compound was added 82 201042019 ±LZ 7" ° 41 ^? °·5 - Colloidal dioxide oxidation of 7 nm After that, it becomes a total of 95. I have a basic compound until the pH is reached, and the remainder is blended with pure water to make it a total _Berry/〇. In Comparative Example 42, a bismuth dioxide disperser having a primary particle diameter of 5% by mass of 5% by mass was dispersed in a pure money, and the total amount was 95% by mass. Then, the test compound was added until the desired pH was obtained. The remaining portion was blended with pure water to make it 100% by mass in total. Further, in Comparative Example 42, no ls2,4_triazole was added. In the same manner as in Example 37, Comparative Example 4 was carried out. - pH measurement of each of the polishing liquids for semiconductors of Comparative Example 42 and measurement of polishing rate and surface roughness when polishing the silicon wafer using the polishing liquids of Comparative Examples 4 to Comparative Examples 42. The measurement results are shown. In Table 16.

83 201042019 /pii [表 16] 比較例 40 41 42 研磨粒子一次粒徑（nm) 36 7 17 添加量（wt%) 0.5 0.5 0.5 水溶性聚合物聚合物種類 - - - 添加量 (Wt% ) - - 1,2,4-三°坐添加量（\¥1%) 0.5 0.5 - 驗性化合物氫氧化鉀氫氧化鉀氫氧化鉀研磨液pH 11 11 11 覆面研磨速度（nm/min) 482 550 284 最大高度Rt (nm) 研磨前 (Rt〇) 1087 1080 1065 研磨後 (Rt.) 197 1077 171 L (nm) 1258 基本為0 1153 L/ ( Rt〇-Rti) 1.41 - 1.29 於實例37〜實例44中，與比較例40〜比較例42相比，相對於研磨量L之研削痕的消除效率優異，且研磨後之研削痕深度Rtl較小。即，可確認可以較少之研磨量消除凹凸。關於實例37與比較例40之研磨液，為了對研磨量L 與研削痕消除性方面進行更詳細之研究，重新實施研磨（分別為實例45、比較例43)。對預先具有1000 nm前後深度之研削痕的矽晶圓分7次進行研磨，分別測定各研磨量L 中之自晶圓中心起0 mm之部分（Center，中心）、自晶圓中心起60 mm之部分（Middle，中部）、自晶圓中心起120 mm之部分（Edgel，邊緣1 )及自晶圓中心起140 mm之部分（Edge2，邊緣2)的最大高度Rt而進行評價。將評 84 201042019 價結果示於表17和表18以及圖11和圖12中。 [表 17] 實' f列45 研磨次數（次） 0 1 2 3 4 5 6 7 研磨後之晶圓厚度（μιη) 760.917 760.547 760.11 759.684 759.313 758.937 758.53 758.226 L (nm) 0 371 808 1233 1604 1981 2388 2692 最大1¾ 度Rt (nm) 中心 907 205 63 43 41 41 37 39 中部 996 660 78 36 35 32 31 35 邊緣1 1060 401 140 90 76 75 72 93 邊緣2 1370 752 87 110 95 78 76 55 [表 18] 比較y ί列43 研磨次數（次） 0 1 2 3 4 5 6 7 研磨後之晶圓厚度（μιη) 752.834 752.446 751.638 750.38 748.685 746.592 744.066 741.115 L (nm) 0 388 808 1258 1695 2093 2526 2951 最大南度Rt (nm) 中心 882 370 205 181 132 62 83 51 中部 1022 697 360 283 140 55 52 53 邊緣1 1005 620 278 130 160 88 55 49 邊緣2 1440 792 260 192 180 112 66 88 可知於實例45中，與比較例43相比，相對於研磨量 L之最大高度Rt在較早的階段變低，研削痕之消除效率優異。雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍内，當可作些許之更動與潤飾，因此本發明之保護 85 201042019 範圍當視後附之中請專補_界定者為準。【圖式簡單說明】比調製實例1〜實例4及先前例（比較例1 車)之各研磨液的時間點開始起24小時後各研磨液之pH變化量的圖表。巧4』呀後各研㈣圖實/n〜實例4及先前例(比較例1〜比較例11)之各研磨液的調整之後的研磨速度、 =液之時間關始起24小時後各研餘之研磨速度的圖表。圖3是表示各研磨液中之研磨粒（二氧化石夕）之添加量、與自調製各研磨液之時間闕始起24 磨之pH變化量之關係的圖表。圖4是表示實例9之階差/表面粗糖度/微細形狀測定裝置之測定結果。圖5是表示比較例2〇之階差/表面粗链度/微細形定裝置之測定結果。 ' 圖6是表示實例11〜實例14與先前例（比較例21〜比較例24)之研磨液的PH與研磨速度之圖表。圖7是表示實例19之階差/表面粗糙度/微細形狀測定裝置之測定結果。 ^ 圖8是表示比較例33之階差/表面粗糙度/微細形狀測定裝置之測定結果。圖9是表示比較例34之階差/表面粗糙度/微細形狀測定裝置之測定結果。 ' 86 201042019 χ--- 圖1〇是表示比較例35 測定裝置之測定結果。之階差味岭財/微細形狀83 201042019 /pii [Table 16] Comparative Example 40 41 42 Abrasive particles Primary particle diameter (nm) 36 7 17 Adding amount (wt%) 0.5 0.5 0.5 Water-soluble polymer polymer type - - - Adding amount (Wt%) - - 1,2,4-three-degree sitting amount (\¥1%) 0.5 0.5 - Test compound potassium hydroxide potassium hydroxide potassium hydroxide slurry pH 11 11 11 Cover grinding speed (nm/min) 482 550 284 Maximum height Rt (nm) Before grinding (Rt〇) 1087 1080 1065 After grinding (Rt.) 197 1077 171 L (nm) 1258 Basically 0 1153 L/( Rt〇-Rti) 1.41 - 1.29 In Example 37 to Example 44 In the comparison with Comparative Example 40 to Comparative Example 42, the polishing efficiency of the polishing marks L was excellent, and the grinding depth Rtl after polishing was small. That is, it was confirmed that the unevenness can be eliminated with a small amount of polishing. With respect to the polishing liquids of Example 37 and Comparative Example 40, in order to examine the polishing amount L and the grinding mark eliminating property in more detail, the polishing was repeated (Examples 45 and Comparative Examples 43, respectively). The tantalum wafer with a depth of 1000 nm before and after the grinding is polished 7 times, and the part of each grinding amount L from the center of the wafer is 0 mm (Center), 60 mm from the center of the wafer. The portion (Middle, middle), the 120 mm portion (Edgel, edge 1) from the center of the wafer, and the maximum height Rt of the 140 mm portion (Edge 2, edge 2) from the center of the wafer were evaluated. The results of the evaluation of 84 201042019 are shown in Tables 17 and 18 and Figures 11 and 12. [Table 17] Real 'f column 45 Number of grinding times (times) 0 1 2 3 4 5 6 7 Wafer thickness after grinding (μιη) 760.917 760.547 760.11 759.684 759.313 758.937 758.53 758.226 L (nm) 0 371 808 1233 1604 1981 2388 2692 Maximum 13⁄4 degrees Rt (nm) Center 907 205 63 43 41 41 37 39 Middle 996 660 78 36 35 32 31 35 Edge 1 1060 401 140 90 76 75 72 93 Edge 2 1370 752 87 110 95 78 76 55 [Table 18] Compare y ί column 43 Number of grinding times (times) 0 1 2 3 4 5 6 7 Wafer thickness after grinding (μιη) 752.834 752.446 751.638 750.38 748.685 746.592 744.066 741.115 L (nm) 0 388 808 1258 1695 2093 2526 2951 Maximum South Rt (nm) Center 882 370 205 181 132 62 83 51 Central 1022 697 360 283 140 55 52 53 Edge 1 1005 620 278 130 160 88 55 49 Edge 2 1440 792 260 192 180 112 66 88 Known in Example 45, and compared In the case of Example 43, the maximum height Rt with respect to the polishing amount L became lower at an earlier stage, and the removal efficiency of the grinding marks was excellent. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. Protection 85 201042019 Scope is subject to the _ defined as the standard. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the amount of change in pH of each grinding fluid after 24 hours from the start of the time of the polishing liquid of each of the polishing examples 1 to 4 and the previous example (comparative example 1). After the adjustment of the polishing liquid after the adjustment of each of the polishing liquids of the example 4 and the previous examples (Comparative Example 1 to Comparative Example 11), the grinding speed and the time of the liquid are turned off 24 hours later. A chart of the grinding speed. Fig. 3 is a graph showing the relationship between the amount of the abrasive grains (cerium dioxide) added to each polishing liquid and the amount of change in pH of the 24 grinding time from the time of preparation of each polishing liquid. Fig. 4 is a graph showing the measurement results of the step/surface roughness/fine shape measuring apparatus of Example 9. Fig. 5 is a graph showing the measurement results of the step/surface coarse chain/fine shape device of Comparative Example 2; Fig. 6 is a graph showing the pH and polishing rate of the polishing liquids of Examples 11 to 14 and the previous examples (Comparative Examples 21 to 24). Fig. 7 is a graph showing the measurement results of the step/surface roughness/fine shape measuring apparatus of Example 19. Fig. 8 is a graph showing the measurement results of the step/surface roughness/fine shape measuring device of Comparative Example 33. Fig. 9 is a graph showing the measurement results of the step/surface roughness/fine shape measuring device of Comparative Example 34. ' 86 201042019 χ--- Fig. 1A shows the measurement results of the measuring device of Comparative Example 35. The difference of the taste of the ridge / fine shape

Rt之關圖11是表示實例45之研磨量L與最大高度係的圖表。 ° & 圖12是表示比較例43之研磨量L與最大高度扮之關係的圖表。Rt Off Figure 11 is a graph showing the amount of polishing L and the maximum height of Example 45. ° & Fig. 12 is a graph showing the relationship between the polishing amount L and the maximum height of Comparative Example 43.

圖13(小圖13(15)、圖13((〇是表示本發明之一實施形態之半導體基板的研磨方法的概略剖面圖。圖Η是表示通常的矽晶圓的加工步驟的流程表。圖 15 (a)、圖 15 (b)、圖 15 (c)、圖 15 (d)是表示通常的矽晶圓的研磨步驟的模式圖。圖16(a)是表示矽晶圓之通常的再生步驟的流程表，圖16 (b)是表示使用本發明之一實施形態之半導體基板的研磨方法之情形時的矽晶圓之再生步驟的流程表。圖17是表示第三半導體基板用研磨液〜第五半導體基板用研磨液中的1，2,4-三唑及水溶性高分子之含量的圖表。【主要元件符號說明】 1 :半導體基板 2:配線用金屬 3:矽損傷層 87Fig. 13 (Fig. 13 (15) and Fig. 13 ((b) is a schematic cross-sectional view showing a method of polishing a semiconductor substrate according to an embodiment of the present invention. Fig. Η is a flow chart showing a processing procedure of a normal germanium wafer. Fig. 15 (a), Fig. 15 (b), Fig. 15 (c), and Fig. 15 (d) are schematic views showing a polishing process of a normal ruthenium wafer. Fig. 16 (a) shows a general 矽 wafer. Fig. 16 (b) is a flow chart showing a process of reproducing a germanium wafer in a case where a polishing method for a semiconductor substrate according to an embodiment of the present invention is used. Fig. 17 is a view showing polishing of a third semiconductor substrate. A graph of the content of 1,2,4-triazole and a water-soluble polymer in the polishing liquid for the liquid to the fifth semiconductor substrate. [Description of main component symbols] 1 : Semiconductor substrate 2: Metal for wiring 3: 矽 damage layer 87

Claims

201042019 /pn VII. Patent application scope: 1. A polishing liquid for a semiconductor substrate, which comprises abrasive particles, 1,2,4-three spit, and an inspective compound, wherein the test compound is a nitrogen-containing test compound or an inorganic test. The content of the test compound is 0.1% by mass or more, and the pH is 9 or more and 12 or less. 2. The polishing liquid for a semiconductor substrate according to claim 1, wherein the nitrogen-containing test compound contains hydrogen peroxide or tetradecyl ammonium hydroxide. 3. The polishing liquid for a semiconductor substrate according to claim 1 or 2, wherein the inorganic test compound contains potassium hydroxide or sodium hydroxide. A polishing liquid for a semiconductor substrate comprising modified cerium oxide or an inorganic basic compound whose surface is modified with an aluminate, wherein the content of the modified cerium oxide is 〇.〇1 mass% or more and 1.5 mass Below 0.01%, the pH is 9 or more and 12 or less. 5. The polishing liquid for a semiconductor substrate according to claim 4, wherein the modified silica dioxide has a primary particle diameter of 7 nm to 50 nm. 6. The polishing liquid for a semiconductor substrate according to Item 4 or 5, wherein the inorganic basic compound according to 88 201042019 contains potassium hydroxide or sodium hydroxide. The polishing liquid for a semiconductor substrate according to any one of the items 4 to 6, further comprising 1,2,4-trimium. 8. A method of polishing a semi-conducting plate, which is a method of polishing a semiconductor substrate of a rib-forming electrode, comprising: a step of forming a recess on one of the faces of the crucible substrate; Ο G embedding a metal into the recess a step of back grinding the other surface of the pheno-substrate; and a polishing step of exposing the metal described in the above two items to the polishing liquid for a semiconductor substrate as disclosed in the scope of the invention. A method of polishing the i2 semiconductor substrate, such as: a step of preparing a rough wafer; etching the 矽SS circle, using a semiconductor substrate material as claimed in the patent application, The term described in any of the items. a method for researching a semiconductor substrate of a rough polishing step of polishing the tertiary wafer, which is a step of performing a wet rhyme for reusing a wafer; and a polishing liquid for a semiconductor substrate, as described in any one of item 7 The grinding process of the grinding and polishing of the stone etched 89. A polishing liquid for a semiconductor substrate comprising: abrasive particles, 1,2,4-diazole, a water-soluble polymer, and a basic compound, and having a pH of 9 or more and 12 or less. The polishing liquid for a semiconductor substrate according to claim 11, wherein the content of the water-soluble polymer is relative to that of the semi-conducting plate polishing liquid, and the amount of the mussel is 〇. % or more and 1% by mass or less. 13. The polishing liquid for a semiconductor substrate according to claim 11, wherein the content of 1,2,4·three slaves is relative to the semiconductor substrate, and the heart is 〇'〇 1% by mass or more and ίο% by mass or less. "14.- A polishing liquid for a semiconductor substrate containing abrasive particles, 1,2,4-diazole, a water-soluble polymer, a basic compound, and (4) the total amount of the three slaves relative to the semiconductor substrate contact liquid In the case of 0.05% by mass or more and 5% by mass or less, the content of the 蛐:===================================================================== the following. 15. A method for polishing a semiconductor substrate, a composite of seven dead. After slicing and rubbing the germanium single crystal ingot, the crucible wafer of the workpiece is ground or polished, and then the wafer is performed on the wafer side. Preparing a rough grinding step for coarse-graining the coarse wafer / using the 201042019 step-by-pass wafer into the semi-conductive L6-based board / method of the method, which is a step of performing a wet method for reusing the attached stone wafer; using a coarse grinding step for grinding; Ο - step after performing the fine grinding step of grinding A polishing liquid is used which contains abrasive particles, a sex-like molecule, and a basic compound, and the 1,2,4-trimium umbrella is on the field, and the total mass is . .2 mass center: quantity = total of the polishing liquid for the substrate = the total amount of the polishing liquid for the (four) body substrate, and I S and . A semi-conducting method, the money test re-uses the step of preparing the rough wafer by grinding the stone 夕二曰曰 circle with the attached matter: after the engraving, the use of the patent Scope of the 夕对该The method of grinding the liquid according to the method of the invention, wherein the grinding process of the rough wafer is set in the coarse grinding step, wherein the grinding amount of the rough wafer is set to be 0.1=19. L (nm), when the initial step of the rough wafer is set to Rt0 (rnn) and the step of coarsely grinding the coarse wafer is set to % (nm), the Rto^L^Rt is satisfied. 〇xi.3 and when grinding the rough wafer only L (nm), it satisfies both L/(Rt(rRu) g 3 and ~' 1〇〇(leg). 〇·If the patent scope is item μ or item 19 The research and development method of the semiconductor substrate further includes: a finishing polishing step of grinding the coarse wafer after the coarse grinding step using a polishing liquid, and the polishing liquid contains abrasive particles, 1, 2 4, a triple saliva, a water-soluble polymer, a basic compound, and a pH of 9 or more and 12 or less. 21. The half as described in claim 18 or 19. The method for polishing a plate further comprises: a finishing polishing step of grinding the coarse wafer after the coarse grinding step by the polishing liquid of the body 7 , and the researching green of the grinding machine contains the research and training, 1, 2, 4 _Three saliva, water-soluble high eight, basic compound, H. sylvestre I, 2, 4 · triazole content relative to the semiconductor substrate polishing solution ~, mass 1 is 0.05% by mass or more and 〇 5 mass% In the following, the content of the polishing liquid for the semiconductor substrate is 0. 00 or more and 0. 1 mass 〇 / 〇 or less, and the pH is 9 or more and 12 or less. 92 201042019 22. The polishing liquid for a semiconductor substrate according to any one of the preceding claims, wherein the water-soluble polymer is a nonionic polymer. The polishing liquid for a semiconductor substrate, wherein the nonionic molecule is at least one selected from the group consisting of polyethylene copolymers such as hydrazine and polyvinylpyrrolidone. 〇24. Patent Application No. 11 to 14 Item, item π, item 22 or item 23 The polishing liquid for a semiconductor substrate, wherein the water-soluble polymer is a mixture containing at least one selected from the group consisting of polyethylene α-pyrrolidone and polyethylene acetonitrile. The polishing liquid for a semiconductor substrate according to any one of the items of the present invention, wherein the semiconductor substrate to be diced is Shi Xi or on the substrate constitutes a package 93