200426205 九、發明說明： 【發明所屬之技術領域】 中之研磨製程的 本發明係關於一種用於半導體製造製程 研磨用組合物之製造方法。 【先前技術】 於半導體製造領域中’伴隨著半導體元件之微細化以及 多層化產生之高積體化，半導體層或金屬層之平坦化技術 成為重要之要素技術。於晶圓上形成積體電路時，若未平 坦化因電極配線等造成之凹凸而重疊層時，則落差變大， 且平坦性變為極其不良。又於落差變大之情形時，於光微 影蝕刻法中難以將焦點合併於凹部與凸部之兩方，且無法 實現微細化。因此，有必要於積層中之適當階段進行用以 除去晶圓表面凹凸之平坦化處理。於平坦化處理中存在有 藉由蝕刻除去凹凸部之回蝕法，藉由等離子體CVD(化學 瘵鍍法，Chemical Vapor Deposition)等形成平坦膜之成膜 法’藉由熱處理進行平坦化之流動化法、以及藉由選擇 CVD等進行凹部之填埋之選擇成長法等。 以上之方法存在有因絕緣膜、金屬膜等膜之種類不同而 是否合適或可平坦化之區域極其狹窄之問題。作為可克服 如此問題之平坦化處理技術有藉由CMP之平坦化。 根據CMP之平坦化處理，藉由將懸濁有微細粒子（研磨 粒）之漿料供給至研磨墊表面，並且使已壓接之研磨墊與 石夕晶圓相對移動而研磨表面，可高精度地使廣泛範圍之晶 圓表面平坦化。 200426205 藉由CMP進行平坦化的CMp裝置主要由旋轉定盤部、載 體部、聚料供給部以及修整部所構成。旋轉定盤部以黏著 膠π等將研磨塾貼付於其上面，下面側介由旋轉轴與旋轉 驅動機構連接。載體部藉由支撐材及護圈環將被研磨物即 矽晶圓保持於其下面，並將矽晶圓之加工面壓接於研磨墊 上。上面側介由旋轉軸與旋轉驅動機構連接。 漿料供給部將使氧化矽、氧化鈽以及氧化鋁等之粒子懸 濁於媒質所得之㈣供給至研磨墊表面。修整部具有電附 著有工業用金剛石粒子之薄板，並藉由削除研磨屑等附著 之部分而使研磨特性低落之研磨墊表面再生。 CMP裝置藉由旋轉驅動機構旋轉該旋轉定盤部以及載體 ^並且將漿料供給至研磨墊之大致中央部，藉由相對移 動矽晶圓與研磨墊進行矽晶圓加工面之研磨。 近年，伴隨IC(Integrated Ciixuit)晶片之設計規則微細 化，起因於漿料而於矽晶圓之被研磨面產生之微小劃痕成 為問題。作為微小劃痕之因素，考慮有以懸濁於媒質之研 磨粒之凝聚物或分散不良物而存在之粗大粒子。 於氧化矽漿料之原料中，使用塵狀氧化矽或膠體矽。塵 狀氧化矽與膠體氧化矽相比因純度高故而可生成雜質少之 氧化矽漿料，但凝聚性高且難以實現於媒質中之高分散 化。 於提南塵狀氧化矽之分散穩定性為目的之先前的氧化矽 聚料之製造方法中，有於特許第2935丨25號公報、特許第 2949633號公報、以及特開2〇〇1-26771號公報中所揭示之 91070 W0426205 方法。關於任一方法，藉由規定剪切條件以及氧化 等以實現穩定之分散性。 辰又 實際上，以上述特許文獻中所揭示之製造方法製作以塵 狀氧化矽為原料之氧化矽漿料時，氧化矽之分散性能不充 刀’且漿料中存在較多凝聚物。 【發明内容】 本發明之目的係提供一種分散穩定性優良、凝聚粒子少 之研磨用組合物之製造方法。 人本發明係一種研磨用組合物之製造方法，其特徵在於包 含：調製酸性之塵狀氧化矽分散液之第丨步驟； 於為使與前述塵狀氧化矽分散液混合終了後獲得之研磨 併、&物成為特疋之pH值及二氧化矽濃度而調製之驗性物 質水溶液中，添加前述塵狀氧化矽分散液並進行混合之第 2步驟。 、本發月之特徵在於·為使前述研磨用組合物之pH值成 為8 12，氧化矽濃度成為1〇〜3〇重量％而調製前述鹼性物 質水溶液。 又本發明之特徵在於··前述塵狀氧化石夕之比表面積為 50〜200 m2/g 0 又，發明中4前述驗性物質水溶液，其特徵在於：至少 知3氫氧化知、氫氧化鈉、氫氧化卸、氫氧化詞、以及氣 氧化鋇或氫氧化鎂中之任一種。 二艮據本發明’首先於第1步驟中調製酸性之塵狀氧化矽 刀散液Μ，較好使用之塵狀氧化石夕之比表面積為 200426205 50〜200 m2/g 〇 其次於第2步驟中，調製鹼性物質水溶液。鹼性物質水 溶液之濃度以及體積藉由與於第丨步驟中調整之塵狀氧化 夕刀政液的扣5，為使作為目的之研磨用組合物之值成 為8〜12，氧化矽濃度成為1〇〜3〇重量％而調製^再者，鹼 性物質水溶液至少包含氫氧化錢、氯氧化納、氯氧化卸、 氫氧化鈣、以及氫氧化鋇或氫氧化鎂中之任一種。 根據先前之製造方法，係於塵狀氧化矽分散液中，添加 驗性物質水溶液，但本發明中則於已調製之驗性物質水溶 液中添加塵狀氧化矽分散液。 塵狀乳化石夕分散液之投入初期，因驗性物質水溶液過 剩，故而混合液呈強驗性，產生pH值衝擊。然而，因氧化 石夕濃度非常低’故而可抑制凝聚之產生。若繼續投入，則 混合液之氧化石夕濃度上升’但藉由塵狀氧化石夕分散液之投 :’混合液之鹼性變弱’故而pH值衝擊減弱，且可抑制凝 聚產生。 猎此，可獲得分散穩定性優良、凝聚粒子少之研磨用組 合物。 ' 又本發明中之刖述第i步驟，其特徵在於包含： 為使初期氧化石夕濃度成為46〜54重量％，將塵狀 投入至將PH值調製社〇〜2· 烟制庙处紅 卫伢、、、口同剪切力而 ^ 塵狀氣化;5夕分散液之步驟；及 為使氧化矽濃度成為45〜53重量 u, ^ , 將水添加至前述塵 狀乳化矽分散液之步驟；以及 200426205 為使氧化矽濃度成為33 、七庙此一 更里/〇，進一步添加水至前 述塵狀氧化石夕分散液之步驟。 根據本發明，首养盘#、# — 0/ i先為使初期氧化矽濃度成為46〜54重量 %而將塵狀氧化矽投至制& )4更里 一 /仅主將pH值調製為1〇〜27之水 給咼剪切力而調芻鹿处笛儿 ’、 狀虱化矽分散液。藉由將PH值調製為 a可^效供給高剪切力，並可提高分散性。 :、為使氧化矽’辰度成為45〜53重量％ ’將水添加至塵 狀氧化石夕分散液。藉由添加少量水，可使研磨用組合物之 黏度降低。 最後為使氧化石夕濃度成為33〜44重量％，進一步添加 水。藉由設定氧化石夕》農度為33〜44重量％而可抑制凝聚物 產生。 么又=發明中之前述第2步驟，其特徵在於：於5小時以内 、、止則述塵狀氧化石夕分散液與冑述驗性物質水溶液之混 合0 根據本發明’於5小時以内終止前述塵狀氧化碎分散液 與則述鹼性物質水溶液之混合。藉由於5小時以内終止混 口，可使混合液之pH值迅速降低，且可縮短造成塵狀氧化 矽易於凝聚之pH值條件之時間並可抑制凝聚產生。 又本發明之特徵在於：進一步包含對前述第2步驟中獲 侍之研磨用組合物，使用過濾精度為丨〜4 μιη之過濾器進行 過濾處理之第3步驟。 根據本發明，於第3步驟中，對於第2步驟中獲得之研磨 用、及合物’使用過濾精度為1〜4 μηι之過濾器進行過濾處 91070 -10· 200426205 理。 如上所述’第2步驟中獲得之研磨用組合物因凝聚物產 生較少’故而藉由使用過濾精度為1〜4 μηι之過濾器，可有 效除去凝聚物。 【實施方式】 本&月之目的、特色、以及優點根據下述之詳細說明以 及圖式可更加明確。 參考以下圖式詳細說明適合本發明之實施例。 氧化石夕水料之製造方法大致可分為2個步驟。第1步驟係 製成^性氧化矽分散液之步驟，第2步驟係混合氧化矽分 散液與鹼性物質之水溶液的步驟。 於第1步驟中，將鹽酸等之酸添加至超純水而成為酸 ^例如ΡΗ 2，對其供給剪切力並且投入塵狀氧化矽而製 成分散液。 々於第2步驟中’攪拌氧化矽分散液，並且滴入氫氧化鉀 等之鹼性水溶液而進行混合。 於第2步驟中，藉由氧切分散液之ΡΗ值自酸性變化至 驗性時之ΡΗ值衝擊’產生氧化料聚物。特別是，氧化石夕 分散液之狀態為高濃度氧化石夕，故而更加易於產生凝聚。 根據本發明’藉由改良氧化㈣散液之製程條件以及氧 化：分散液與鹼性水溶液之混合條件，故而可製造出分散 穩定性優良之氧化矽漿料。 圖1係本發明一實施方式之流程圖。 首先，對第i步驟進行詳細說明。心步驟中包含更细微 200426205 的步驟。 於步驟卜1中，將超純水之pH值調製為1.0〜2 7，以言剪 切分散裝置供給剪切力，並且投人具有比表面積為5〇1〇 :/g之塵狀礼化矽粉末直至初期氧化矽濃度成為％〜Μ重 量％，並以高剪切分散裝置供給剪切力1〜5小時。 於步驟1-2中，為使氧化矽濃度成為45〜53重量％，添加 乂里之超純水至氧化矽分散液中並供給剪切力⑺〜4〇分 鐘0200426205 IX. Description of the invention: [Technical field to which the invention belongs] The polishing process of the present invention relates to a method for manufacturing a polishing composition for a semiconductor manufacturing process. [Prior art] In the field of semiconductor manufacturing, along with the miniaturization of semiconductor elements and the increase in the accumulation of layers, the planarization technology of semiconductor layers or metal layers has become an important element technology. When the integrated circuit is formed on the wafer, if the layers are not flattened due to the unevenness caused by the electrode wiring or the like, the gap becomes large and the flatness becomes extremely poor. When the step becomes larger, it is difficult to combine the focal point on both the concave portion and the convex portion in the photolithographic etching method, and it is not possible to achieve miniaturization. Therefore, it is necessary to perform a flattening process to remove unevenness on the surface of the wafer at an appropriate stage in the lamination. In the flattening process, there are an etch-back method in which uneven portions are removed by etching, and a film-forming method such as plasma CVD (Chemical Vapor Deposition) to form a flat film. Chemical conversion method, selective growth method such as selective CVD, and so on. The above method has a problem of whether the area suitable for or flattenable is extremely narrow depending on the types of films such as insulating films and metal films. As a planarization technique that can overcome such a problem, there is planarization by CMP. According to the flattening treatment of CMP, by supplying the slurry with fine particles (abrasive particles) suspended on the surface of the polishing pad, and moving the pressure-bonded polishing pad and the Shixi wafer relatively, the surface can be polished with high accuracy. To flatten a wide range of wafer surfaces. 200426205 The CMP device for flattening by CMP is mainly composed of a rotating plate portion, a carrier portion, a polymer supply portion, and a trimming portion. The rotating plate part is attached to the upper surface with an adhesive π or the like, and the lower side is connected to the rotation driving mechanism via a rotating shaft. The carrier part holds the silicon wafer to be polished under the support material and the retaining ring, and presses the processed surface of the silicon wafer onto the polishing pad. The upper side is connected to the rotation driving mechanism via a rotation shaft. The slurry supply unit supplies the particles obtained by suspending particles of silicon oxide, hafnium oxide, and alumina in the medium to the surface of the polishing pad. The trimming section has a thin plate electrically attached with industrial diamond particles, and regenerates the surface of the polishing pad with reduced polishing characteristics by removing the adhered portions such as abrasive dust. The CMP device rotates the rotary platen and the carrier by a rotation driving mechanism, and supplies the slurry to a substantially central portion of the polishing pad. The silicon wafer and the polishing pad are relatively moved to perform polishing on the silicon wafer processing surface. In recent years, with the miniaturization of IC (Integrated Ciixuit) chip design rules, micro-scratches on the polished surface of silicon wafers caused by slurry have become a problem. As a factor of minute scratches, it is considered that coarse particles exist as agglomerates or poorly dispersed particles of abrasive particles suspended in a medium. In the raw material of silicon oxide slurry, use dusty silicon oxide or colloidal silicon. Compared with colloidal silica, dusty silica has higher purity and can produce silica slurry with less impurities. However, it has high cohesiveness and it is difficult to achieve high dispersion in the medium. Conventional methods for producing silicon oxide aggregates for the purpose of dispersing and stabilizing silicon dioxide in Tinan are disclosed in Japanese Patent Publication No. 2935 丨 25, Japanese Patent Publication No. 2949633, and Japanese Patent Application Laid-Open No. 20001-26771. The method disclosed in Bulletin 91070 W0426205. In either method, stable dispersibility is achieved by specifying shear conditions and oxidation. In fact, when using the manufacturing method disclosed in the above-mentioned patent document to make a silicon oxide slurry using dusty silicon oxide as a raw material, the dispersion performance of the silicon oxide is not sufficient, and there are many aggregates in the slurry. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polishing composition having excellent dispersion stability and few agglomerated particles. The present invention relates to a method for producing a polishing composition, comprising: a first step of preparing an acidic dusty silicon oxide dispersion; and grinding and obtaining the powder after mixing with the dusty silicon oxide dispersion. The second step is to add the above-mentioned dusty silica dispersion to an aqueous solution of a test substance prepared by the pH value and the silica concentration. This month is characterized in that the alkaline substance aqueous solution is prepared so that the pH of the polishing composition is 8 12 and the silicon oxide concentration is 10 to 30% by weight. The present invention is characterized in that the specific surface area of the dusty oxidized stone is 50 to 200 m2 / g 0. In the invention, the aqueous solution of the above-mentioned test substance is characterized in that at least 3 hydroxides and sodium hydroxide are known. , Hydroxide discharge, hydroxide word, and any of barium oxide or magnesium hydroxide. According to the present invention, the acidic dust-like silicon oxide knife powder M is first prepared in the first step, and the specific surface area of the dust-like oxide stone that is preferably used is 200426205 50 ~ 200 m2 / g. ○ Secondly in the second step In addition, an alkaline substance aqueous solution was prepared. The concentration and volume of the alkaline substance aqueous solution are adjusted by the step 5 in the dusty state of the oxidized liquid solution of the knife, in order to make the value of the polishing composition for the purpose 8 to 12, and the silicon oxide concentration 1 0 to 30% by weight. Furthermore, the alkaline substance aqueous solution contains at least one of sodium hydroxide, sodium oxychloride, oxychloride, calcium hydroxide, and barium hydroxide or magnesium hydroxide. According to the previous manufacturing method, the test substance aqueous solution is added to the dusty silica dispersion, but in the present invention, the dusty silica dispersion is added to the prepared test substance aqueous solution. In the initial stage of the introduction of the dust-like emulsified Shixue dispersion liquid, there was an excess of aqueous test substance solution, so the mixed liquid showed strong testing and produced a pH shock. However, because the concentration of the oxidized stone is very low ', generation of aggregation can be suppressed. If it is continuously added, the concentration of the oxidized stone in the mixed solution will increase ', but by the addition of the dusty oxidized stone in the dispersion:' The alkaline of the mixed solution becomes weaker ', the impact of the pH value will be weakened, and agglomeration can be suppressed. By doing so, a polishing composition having excellent dispersion stability and few agglomerated particles can be obtained. 'Also described in the present invention is the i-th step, which comprises: in order to make the initial concentration of the oxidized stone to be 46 to 54% by weight, the dust is injected into the PH-adjusting agency 0 ~ 2 · Tobacco Temple Red伢 ,,, and the same mouth with the shear force ^ dusty gasification; the step of the 5th dispersion; and in order to make the concentration of silicon oxide to 45 ~ 53 weight u, ^, water is added to the aforementioned dusty emulsified silicon dispersion And steps of 200426205 to increase the concentration of silicon oxide to 33, Qimiao, and further add water to the aforementioned dusty oxidized stone dispersion. According to the present invention, the first raising plate #, # — 0 / i is first cast dusty silicon oxide into the system in order to make the initial silicon oxide concentration to 46 to 54% by weight. 4) More / only the pH value is adjusted to The water of 10 ~ 27 gives shearing force to the tadpoles, and tunes the deer's stalk disperse liquid. By adjusting the pH value to a, high shear force can be effectively supplied, and dispersibility can be improved. : To add silica to the dusty oxidized silica dispersion to increase the degree of silica to 45 to 53% by weight. By adding a small amount of water, the viscosity of the polishing composition can be reduced. Finally, water was added to make the concentration of oxidized stones 33 to 44% by weight. It is possible to suppress the generation of agglomerates by setting the fertility of Oxidation Stone to 33 to 44% by weight. What is the second step in the invention, which is characterized in that the mixing of the dust-like oxidized stone dispersion and the test substance aqueous solution is completed within 5 hours. 0 According to the present invention, the termination is completed within 5 hours. The dusty oxidized crushed dispersion is mixed with the alkaline substance aqueous solution. By stopping the mixing within 5 hours, the pH value of the mixed solution can be rapidly reduced, and the time of the pH conditions that cause dusty silica to easily aggregate can be shortened, and the generation of aggregate can be suppressed. The present invention is further characterized in that it further includes a third step of filtering the polishing composition obtained in the second step, using a filter having a filtration accuracy of ˜4 μm. According to the present invention, in the third step, the grinding and blends obtained in the second step are filtered using a filter having a filtration accuracy of 1 to 4 μm. 91070-10 · 200426205. As described above, 'the polishing composition obtained in the second step is less likely to produce aggregates', and by using a filter having a filtration accuracy of 1 to 4 μm, the aggregates can be effectively removed. [Embodiment] The purpose, features, and advantages of this month will be made clearer by the following detailed description and drawings. Embodiments suitable for the present invention will be described in detail with reference to the following drawings. The manufacturing method of the oxidized stone material can be roughly divided into two steps. The first step is a step of preparing a silica dispersion, and the second step is a step of mixing the silica dispersion and an aqueous solution of an alkaline substance. In the first step, an acid such as hydrochloric acid is added to ultrapure water to form an acid, for example, PZ2, a shearing force is applied thereto, and dust-like silica is added to prepare a dispersion. In step 2 ', the silicon oxide dispersion liquid is stirred, and an alkaline aqueous solution such as potassium hydroxide is added dropwise and mixed. In the second step, the oxidized polymer is produced by changing the pH value of the oxygen-cutting dispersion from acidity to a pH value impact at the time of test. In particular, the state of the oxidized oxidized dispersion is high-concentrated oxidized oxidized, so that aggregation is more likely to occur. According to the present invention ', by improving the process conditions of the hafnium oxide powder and the oxidation: mixing conditions of the dispersion and the alkaline aqueous solution, a silicon oxide slurry having excellent dispersion stability can be produced. FIG. 1 is a flowchart of an embodiment of the present invention. First, the i-th step will be described in detail. The heart step contains more subtle steps of 200426205. In step B1, the pH value of the ultrapure water is adjusted to 1.0 to 27. In other words, a shearing and dispersing device is used to supply a shearing force, and the person has a dusty etiquette with a specific surface area of 501: / g. The silicon powder has an initial silicon oxide concentration of% to M% by weight, and is supplied with a shearing force by a high-shear dispersing device for 1 to 5 hours. In step 1-2, in order to make the concentration of silicon oxide to be 45 to 53% by weight, add ultrapure water of 乂 to the silicon oxide dispersion liquid and supply a shear force of ⑺ ~ 40 minutes.
於步驟1:3中，為使氧化矽濃度成為^〜料重量％，添加 超純水至二氧化石夕分散液中並供給剪切力G · 5〜4小時。 如上所述，於第1步驟中，藉由供給高剪切力，並且於 步驟Μ中添加超純水，可充分降低氧切分散液之黏 度。 其次，對第2步驟進行說明。 於步驟2-1中，#於為使混合後之pH值成為8〜12，氧化 矽濃度成為10〜30重量％而調製之鹼性物質水溶液中，投 入氧化矽分散液。與先前之混合不同，藉由將氧化矽分散 液杈入至鹼性物質水溶液中而可抑制混合時之凝聚物產 生。其理由如下。 氧化矽分散液投入初期，因鹼性物質水溶液過剩，故而 此合液之pH值呈12〜14之強鹼性，且產生1)11值衝擊。但 疋，因氧化矽濃度非常低，故而可抑制凝聚產生。若繼續 杈入，則混合液之氧化矽濃度上升，但藉由氧化矽分散液 之投入而混合液之pH值成為8〜12之弱鹼性，故而pH值衝 -12- 200426205 擊減弱’並可抑制凝聚產生。 再者，吾人期望於5小時以内投入全部之氧化石夕 液。驗性物質水溶液之PH值為12〜14，且為塵狀氧化石夕之 表面溶出之PH值區域。藉此，藉由迅速投入氧切分散液In step 1: 3, in order to make the concentration of silicon oxide to 5% to 5% by weight, ultrapure water is added to the SiO2 dispersion and a shearing force G is applied for 5 to 4 hours. As described above, in the first step, the viscosity of the oxygen-cutting dispersion can be sufficiently reduced by supplying a high shear force and adding ultrapure water in step M. Next, the second step will be described. In step 2-1, # is poured into an aqueous solution of an alkaline substance prepared so that the pH after mixing is 8 to 12, and the concentration of silicon oxide is 10 to 30% by weight, and the silicon oxide dispersion is added. Unlike the previous mixing, the generation of agglomerates during mixing can be suppressed by mixing the silica dispersion liquid into an alkaline substance aqueous solution. The reason is as follows. At the initial stage of the silicon oxide dispersion, since the alkaline substance aqueous solution is excessive, the pH value of the combined solution is strongly alkaline from 12 to 14, and a shock of 11) is generated. However, since the concentration of silicon oxide is very low, the generation of aggregation can be suppressed. If it continues to be added, the silicon oxide concentration of the mixed solution will increase, but the pH value of the mixed solution will become weakly alkaline from 8 to 12 by the addition of the silicon oxide dispersion liquid, so the pH value will decrease -12- 200426205. Can inhibit the generation of aggregation. In addition, I expect to put in all the oxidized stone liquid within 5 hours. The pH value of the aqueous solution of the test substance is 12 ~ 14, and it is the pH value range of the surface of the dusty oxidized stone. With this, by rapidly feeding the oxygen-cutting dispersion
而可迅速使PH偏移至氧化石夕粒子之分散穩定 8〜12 。 P 如上所述，於第2步驟中藉由將氧化石夕分散液投入至鹼 性物質水溶液中，可抑制混合時之㈣物產生。 經由第i以及第2步驟獲得之氧化石夕漿料，因凝聚物少，· 且黏度低，故而可藉由過濾器有效除去凝聚物。 於步驟3-1中’使用過渡精度為卜4㈣之過遽器進行過 濾。藉此，可以流速2〜10升/分鐘進行處理，且可保持充 分的處理流量，並可除去粗大粒子。 以下，關於各步驟條件的討論結果進行說明。 (1)關於氧化碎分散液之pH值 關於步驟1-1中之pH值，於#值分別為2、3、7之條件 _ 下製成氧化石夕_。再者’ pH值以外之條件全部相同。 圖2係表示PH值對於凝聚粒子成長率影響的圖表。縱轴 表示凝聚粒子之成長率，橫軸表示振盪時間。 · 為檢查氧化矽漿料之分散穩定性進行振盪實驗。振盪實 · 驗為：將已製成之20 ml氧化矽漿料放至容量5〇 ml之振盪 · 管令’ a5：置於縱型振盪機内，並以振盪速度31〇 spm(stroke per minute)、振盪衝程4〇 mm進行振盪，經過 既疋時間後取出振盪管，並使用粒度分佈測定裝置 91070 -13- 200426205 (HORIBA製造··型號LA-910)測定氧化矽漿料之中間 (median)粒子直徑。凝聚粒子之成長率以（振盪後之中間粒 子直徑一振蘯前之中間粒子直徑）/振盪前之中間粒子直徑 χ100(%)而算出。 折線11表示pH 2之情形，折線12表示pH 3之情形，折線 13表示pH 7之情形。於pH 2之情形時，可知即使振盪⑺天 粒子直徑亦無變化，且具有較高之分散穩定性。於pH 3之 情形時，可知10天後成長率約為18%; MpH 7之情形時， 可知10天幾成長率約為88%並皆產生凝聚。考慮到其係因 為塵狀氧化矽之等電點位於pH 2附近，故而於pH 2時粒子 表面成為電氣中性，且易於施加高剪切力。 藉由以上情形，可知較好氧化矽分散液之pH值為 1 〜2 · 7。 * (2)關於氧化矽分散液之初期氧化矽濃度 關於步驟卜1中之初期氧切濃度，^初期氧化石夕濃产 分別以45重量％、50重量％、55重量％、以及6〇重量%之： 件製成氧切㈣。再者，初期氧切濃度以外 部相同。 圖3係表示氧切分散液之_氧 漿料粒度分佈又卞乳化石夕 古/_ 縱軸表不頻率，橫轴表示粒子 ^。曲線14表示初期氧切漠度為45重量%之情形，曲 線15表示初期氧切濃度為重量％之情形，曲線16表示 初期氧化矽濃度為55重量〇/() t _ 、 度為6。重量%之情形之情形’曲線17表示氧切濃 91070 14 200426205 二=示可知，初期氧化_越高則氧 粒度刀佈越向左移位，故而初期氧化 水枓之 越高。於初期氧切濃度低為45重量二 因高勢切分散裝置之剪切力無法充分傳達考慮到 低。又，於55重量％以及6〇重θ〇/ 故而分散性 里里/。以及60重3；%之情形時， 分傳達故而分髓高，但氧切分散液之料上升，1 大對於分散機之負擔故而不適合。於初期氧加 ㈣時，可減小對於分散機之負擔，且分散 南0 藉由以上㈣’可知較好氧切分散液之 度為46〜54重量％。 Λ虱化矽/辰 分別以添加之情形以及 再者，添加超純水以 (3)關於添加少量之超純水 關於步驟1_2中之超純水添加， 未添加情形之條件製成氧化矽漿料 外之條件全部相同。 於未添加少量之超純水之情形時，氧切聚料之中間粒 子直徑與已添加之情形相比變大。又，氧化矽濃度越高剪 切力越易於傳達，故而未添加之情形之分散性低，且氧化 石夕毁料之黏度上升約4〇/〇。 藉由以上情形’可知較好是添加少量之超純水至氧化石夕 分散液中，且氧化矽濃度設定為45〜53重量〇/0。 (4)關於氧化矽分散液之氧化矽濃度 ，於步驟1-3中之氧化矽濃度，分別以氧化矽濃度為32 重量/〇 40重量％、45重量％以及49重量％(未添加超純水） 91070 -15- 200426205 之條件製成氧切聚料。再者，氧切濃度以外之條件全 部相同。 圖4係表示氧化碎濃度對於氧化㈣料中之粗大粒子數 之影響圖表。縱軸表示粗大粒子數’橫軸表示粒子直捏。 曲線18表示氧切濃度為32重量％之情形，曲線19表示 氧化=濃度為40重量％之情形，曲線2Q表示氧化妙濃度為 45重量％之情开)，曲線21表示氧化矽濃度為49重量❶，。之情 形。將粒子直徑大於G.5叫之粒子作為粗大粒子計算含 有各粒子直徑之粒子數。 ,與軋化矽濃度為32重量％、45重量％以及49重量％之情 形相比較，氧切濃度⑽重量％之情形時之粗大粒子數 2 °可認為其係因為4G重量％時之黏度可最有效地施加 分散機之剪切力。因此’可認為氧化碎濃度㈣重量％之 情：時黏度低’於45重量％、49重量％時黏度過高。 糟由以上情形’可知較好二氧化石夕分散液之氧化石夕濃度 為3 3〜44重量％。 (5)關於氧化矽分散液與鹼性物質水溶液之混合條件 人關於步心1中之氧化碎分散液與驗性物質水溶液之混 合中，分別以將鹼性物質水溶液投入至氧化石夕分散液之情 =(第1混合條件），以及將氧切分散液投入至驗性物質水 溶液之情形（第2混合條件）的條件，製成氧化0料。作為 鹼性物質’使用氫氧化鉀。再者，混合條件以外之條件全 部相同。 圖5係表示混合條件對於氧化矽漿料之粒度分佈之影響 -16- 200426205 圖表。縱轴表示頻率，橫轴表示粒子直徑。曲線22a、22b 表不第1混合條养之借报 ^ ^ 。 7 ’曲線23表示第2混合條件之情 形。 、匕γ斤述第U匕合條件之情形時pH值衝擊變大，並易產 生婕聚物。實際上’於粒度分佈中可見在⑺叫附近凝聚 物產生之學值。相對地，根據第2混合條件，可見粒子直 U於G.1陶附近突現之峰值，且可知分散性得以提高。 又，亦對氧化石夕漿料之中間粒子直徑進行測定。混合前之 分缺之中間粒子直料UG⑽。以P混合條件 ,氧化發刀散液與氫氧化卸水溶液時之氧化⑦漿料之中 間粒子直徑成為議2 nm’並存在有非常大之凝聚物。對 此二可知以第2混合條件混合時之氧化石夕漿料之中間粒子 直徑維持為11〇nm則幾乎無凝聚產生。 猎由以上情形，混合氧化石夕分散液與驗性物質水溶液之And it can quickly shift the pH to the dispersion and stability of the oxidized stone particles 8 ~ 12. P As described above, in the second step, by adding the oxidized stone oxide dispersion to an aqueous solution of an alkaline substance, it is possible to suppress the occurrence of tritium during mixing. The oxidized stone slurry obtained through the i-th and second steps has a small amount of aggregates and a low viscosity, so the aggregates can be effectively removed by a filter. In step 3-1 ', a filter with a transition accuracy of 4 ° is used for filtering. Thereby, processing can be performed at a flow rate of 2 to 10 liters / minute, and a sufficient processing flow rate can be maintained, and coarse particles can be removed. The results of the discussion of the conditions of each step will be described below. (1) About the pH value of the oxidized crushed dispersion liquid About the pH value in step 1-1, an oxide stone was prepared under the condition that the # values were 2, 3, and 7 respectively. The conditions other than the 'pH value are all the same. FIG. 2 is a graph showing the effect of pH on the growth rate of aggregated particles. The vertical axis represents the growth rate of the agglomerated particles, and the horizontal axis represents the oscillation time. · In order to check the dispersion stability of the silicon oxide slurry, carry out an oscillation experiment. The shaking test is as follows: Put the prepared 20 ml silicon oxide slurry into a shaking 50 ml capacity. • Tube order 'a5: Place it in a vertical shaker and shake at 31 ° spm (stroke per minute). The oscillating stroke was 40mm, and the oscillating tube was taken out after the elapsed time, and the particle size distribution measuring device 91070 -13- 200426205 (model LA-910 manufactured by HORIBA) was used to measure the median particles of the silicon oxide slurry. diameter. The growth rate of the agglomerated particles is calculated as (the diameter of the intermediate particles after the oscillation and the diameter of the intermediate particles before the oscillation) / the diameter of the intermediate particles before the oscillation x 100 (%). The broken line 11 indicates the case of pH 2, the broken line 12 indicates the case of pH 3, and the broken line 13 indicates the case of pH 7. In the case of pH 2, it can be seen that the particle diameter does not change even if it is shaken, and it has high dispersion stability. In the case of pH 3, it is known that the growth rate is about 18% after 10 days; in the case of MpH 7, it is known that the growth rate is about 88% in 10 days and all of them are agglomerated. Considering that the isoelectric point of the dusty silica is near pH 2, the particle surface becomes electrically neutral at pH 2 and it is easy to apply high shear force. From the above, it can be seen that the pH value of a good silica dispersion is 1 to 2 · 7. * (2) About the initial silicon oxide concentration of the silicon oxide dispersion. Regarding the initial oxygen cutting concentration in step B1, the initial concentration of the initial stone oxide is 45%, 50%, 55%, and 60% by weight. % Of: The pieces are made of oxygen cuts. In addition, the initial oxygen cutting concentration is the same outside. Figure 3 shows the oxygen-cutting dispersion of the _ oxygen slurry particle size distribution and emulsified stone Xiguo / _ vertical axis represents frequency, horizontal axis represents particles ^. A curve 14 shows a case where the initial oxygen cutting degree is 45% by weight, a curve 15 shows a case where the initial oxygen cutting concentration is 4% by weight, and a curve 16 shows a preliminary silicon oxide concentration of 55% by weight 0 / () t _ and a degree of 6. In the case of "% by weight" curve 17 indicates that the oxygen cut concentration is 91070 14 200426205 2 = It can be seen that the higher the initial oxidation, the more the oxygen particle size knife cloth shifts to the left, so the higher the initial oxidation leech. The initial oxygen cutting concentration was as low as 45% by weight. Because the shear force of the high-potential shear dispersing device could not be sufficiently communicated, the low oxygen cutting concentration was considered. In addition, at 55% by weight and 60% by weight θ〇 /, it is dispersible. And when the weight is 60% and 3;%, the distribution is high, but the material of the oxygen-cutting dispersion rises, and 1 is not suitable for the burden of the disperser. In the initial oxygen addition of krypton, the burden on the dispersing machine can be reduced, and the dispersion degree is 0. From the above krypton, it can be seen that the degree of a good oxygen-cutting dispersion is 46 to 54% by weight.虱 虱 化 矽 辰 / 矽 were added in the case of adding and ultra-pure water (3) about adding a small amount of ultra-pure water about adding ultra-pure water in step 1_2, without adding the conditions to make a silicon oxide slurry The conditions beyond the expectations are all the same. In the case where a small amount of ultrapure water is not added, the intermediate particle diameter of the oxygen-cutting polymer becomes larger compared to the case where it has been added. In addition, the higher the silicon oxide concentration, the easier it is to transmit the shear force, so the dispersibility in the case where it is not added is low, and the viscosity of the stone oxide material is increased by about 40%. From the above situation ', it can be seen that it is preferable to add a small amount of ultrapure water to the oxidized silica dispersion, and the silica concentration is set to 45 to 53% by weight / 0. (4) Regarding the silicon oxide concentration of the silicon oxide dispersion, the silicon oxide concentration in steps 1-3 was based on the silicon oxide concentration of 32% / 40% by weight, 45% by weight, and 49% by weight (without the addition of ultrapure Water) 91070 -15- 200426205 conditions to make oxygen cut polymer. The conditions other than the oxygen cutting concentration are all the same. Fig. 4 is a graph showing the effect of oxidized crushing concentration on the number of coarse particles in the oxidized aggregate. The vertical axis represents the number of coarse particles. The horizontal axis represents the particles being pinched. Curve 18 shows the case where the oxygen cutting concentration is 32% by weight, curve 19 shows the case where oxidation = concentration is 40% by weight, curve 2Q shows the concentration of oxidation oxide is 45% by weight), and curve 21 shows that the silicon oxide concentration is 49% Alas, Love situation. Calculate the number of particles containing each particle diameter by using particles larger than G.5 as coarse particles. Compared with the case where the rolled silicon concentration is 32% by weight, 45% by weight, and 49% by weight, the number of coarse particles when the oxygen cutting concentration is ⑽% by weight is 2 °, which is considered to be due to the viscosity at 4G% by weight. The most effective application of the shear force of the disperser. Therefore, it can be considered that when the oxidized crushing concentration is ㈣wt%: when the viscosity is low, the viscosity is too high at 45% by weight and 49% by weight. In addition, from the above situation, it can be seen that the concentration of the oxidized stone of the preferred diaperous oxide dispersion is 3 to 44% by weight. (5) About the mixing conditions of the silica dispersion and the alkaline substance aqueous solution. About the mixing of the oxidized crushed dispersion and the test substance aqueous solution in Buxin 1, the alkaline substance aqueous solution was put into the oxide oxide dispersion respectively. Feelings = (1st mixing condition), and the conditions in the case where the oxygen-cutting dispersion is put into the aqueous solution of the test substance (2nd mixing condition). As the alkaline substance, potassium hydroxide was used. The conditions other than the mixing conditions are all the same. Figure 5 is a graph showing the effect of mixing conditions on the particle size distribution of the silicon oxide slurry. The vertical axis represents frequency, and the horizontal axis represents particle diameter. The curves 22a and 22b indicate the borrowing of the first mixed article. ^ ^ The 7 'curve 23 shows the case of the second mixing condition. In the case of the U combination conditions, the pH impact becomes large, and it is easy to produce agglomerates. In fact, 'the particle size distribution shows the academic value of the agglomerates produced near the howling. On the other hand, according to the second mixing condition, it can be seen that the peak of the particle U emerges near the G.1 ceramic, and it can be seen that the dispersion is improved. In addition, the diameter of the intermediate particles of the oxidized stone slurry was also measured. The missing intermediate particles before mixing are straight UG⑽. Under the P mixing conditions, the diameter of the intermediate particles of the osmium oxide slurry when the oxidized hair powder and the hydroxide solution were dehydrated became 2 nm 'and there were very large aggregates. From these two results, it can be seen that when the diameter of the intermediate particles of the oxidized stone slurry when mixed under the second mixing condition is maintained at 110 nm, almost no agglomeration occurs. According to the above situation, the mixed solution of the oxidized stone and the test substance aqueous solution
If $時’可知將氧化石夕分散液投入至驗性物質水溶液中較 佳。 (6)關於氧化矽分散液之投入時間 主關於步驟2-1中於驗性物質水溶液投入氧化石夕分散液之 ”別以於5小時投入全部之氧化矽分散液之情形、 以及㈣分鐘投人之情形的條件，製成氧切漿料 驗性物質，使用氫氧化鉀。再者，投人時間以外之條件2 部相同。 圖6係表示氧化石夕分散液投入時間對於氧化石夕衆料之粒 度分佈之影響圖表。縱軸表示頻率，橫轴表示粒子直徑。 91070 -17- 200426205 曲線24表示投入時間為5小時之情形，曲線25表示投入日士 間為20分鐘之情形。 ^ 若長時間投入氧化石夕分散液，則因氫氧化鉀水溶液為強 鹼11故而因pH值衝擊產生凝聚物。藉由縮短投入時間， * 混合液之pH值可迅速降低至氧化石夕穩定區域，即阳^以 下，故而可抑制凝聚物產生。 ' 藉由以上情形，可知於鹼性物質水溶液投入氧化矽分散 液，較好是於5小時以内終止。 圖7係表不氧化石夕分散液投入速度對於混合液之值之鲁 影響圖表。縱軸表示混合液之pH值，橫軸表示氧化矽分散 液之投入時間。曲線26表示投入速度為25升/分鐘之情 形，曲線27表示投入速度為12.5升/分鐘之情形，曲線“表 示投入速度為5升/分鐘之情形。 如此，藉由加快投入速度，可迅速將混合液之pH值降低 至氧化矽穩定區域，即pH 12以下。 (7)關於過濾器之過濾精度以及處理流速 _ 首先’關於步驟3 -1中之過渡器之過渡精度，分別以過 渡精度為1 μιη、3 μιη、5 μτη、7 μιη以及10 之條件進行 過濾。至於過濾器，使用壓力損失小並可獲得大流量之深 · 度型過濾器。 ^ ψ 圖8係表示過濾器過濾精度對於粗大粒子之除去性能之 · 影響圖。縱軸表示氧化矽漿料中之粗大粒子數，圖中表示 過遽處理前之粗大粒子數、以及過滤處理後之粗大粒子 數。直線29表示過濾精度為1 μπι之情形時之粒子數變化， 91070 -18- 直線3 0表示過清倍 愿猜度為3 μπι之情形時之粒子數變化，直線 一 °慮精度為5 4历之情形時之粒子數變化，直線32表 =濾精度為7陶之情形時之粒子數變化，直線33表示過 應精度為1 〇 n m + g ^ + μιη之情形時之粒子數變化。 Μ精度為5 μΐη、7 、10 μηι之情形時，因過濾精度 “ ^粗大粒+之粒子直#，故而過濾、處理後之粗大粒子數 乎…、交化，且無法獲得充分之過濾性能。對此，過濾精 又為1 μηι、3 μηΐ2情形時，過濾處理後之粗大粒子數大幅 度減少。 其次’關於步驟^中之過濾器之處理流量，以與上述 同樣之條件進行過濾。 圖9係表示過濾器過濾精度對於處理流速之影響圖。縱 軸表不過濾處理之處理流速，圖中表示針對於各過濾精度 處里他速。符號74表示過渡精度為1 μιη之情形時之流 速，符唬75表示過濾精度為3 μπι之情形時之流速，符號％ 表不過濾精度為5 μιη之情形時之流速，符號77表示過濾精 度為7 μιη之情形時之流速，符號78表示過濾精度為1〇 之情形時之流速。 由圖可知，過濾精度越小則流速亦越小。考慮到實際之 製造步驟之情形時’若流速為2升/分鐘以上則可經得起實 用’故而過渡精度為1 μπι之情形時亦可能實用。 若考慮粗大粒子之除去性能以及處理流速，可知使用過 渡精度為1〜4 μιη之過濾器即可。此時之處理流速成為Li 〇 升/分鐘。 91070 -19- 200426205 其次，關於基於先前技術而製成之先前氧化石夕衆料、與 基於本發明而製成之氧化石夕衆料（以下稱為「實施们」）的 崎結果進行說明。第i個先前氧化㈣料（以下稱為「比 較例1」）係基於特許第2935125號公報所揭示之製造方法 製成，第2個先前氧化石夕漿料（以下稱為「比較例2」）製造 成氧化石夕濃度比第㈣先前氧化石夕聚料低，且與基於本發 明製成之氧化矽漿料有同等程度之黏度。 實施例1係根據以下步驟製成。 ⑷將超純水置入至高剪切分散裝置中，添加鹽酸將PH 值調整為2。 ⑻供給高剪切力，並且投人塵狀氧切直至初期氧化 矽濃度成為50重量％。 (c) 杈入塵狀氧化矽後，對二氧化矽分散液供給高剪切力 2小時30分鐘。 (d) 為使氧化矽分散液之濃度成為的重量％，添加少量之 超純水並連續供給高剪切力30分鐘。 (e) 為使氧化矽分散液之氧化矽濃度成為40重量％，添加 超純水並供給高剪切力1小時。 (〇為使最終產品之氧化矽漿料之pH值為11，氧化矽濃 度為25重量％，而將氧化矽分散液投入至調整氫氧化鉀濃 度之氫氧化钾水溶液中。 (g)再者’使用過濾精度為3 μηι之深度型過濾器，除去 粗大粒子。 圖丨〇係表示比較例1以及2、實施例i中所含之粗大粒子 91070 -20- 200426205 數的圖表。縱軸表示粗大粒子數，橫軸表示粒子直徑。曲 線39表示實施例1，曲線4〇表示比較例1，曲線41表示比較 例2 〇 可知實施例1之粗大粒子數與比較例1以及2相比大幅度 減少。關於粗大粒子數以及其他之物性值，表1中表示3種 氧化矽漿料之比較結果。 [表1] 氧化矽濃度 [重量％] PH[-] 黏度[cP] 中間粒子 直徑[nm] 粗大粒子數 (>0.5 μπι) [粒子/ 0.5 ml] 粗大粒子數 (>1 μπι) [粒子/ 0.5 ml] 實施例1 25.7 11.0 3.7 112 100,000 2,000 比較例1 25.7 10.9 6.6 125 9,000,000 160,000 比較例2 20.7 11.0 3.7 125 500,000 25,000 如表1所示，實施例1中儘管中間粒子直徑小，二氧化矽 濃度高，但黏度仍降低。 再者，使用該等氧化矽漿料實際進行矽晶圓之研磨。 圖11係表示CMP裝置100之概要外觀圖。CMP裝置1〇〇由 研磨墊101、旋轉定盤部121、載體部122、漿料供給部123 以及修整部124所構成。研磨墊1〇1與保持於CMP裝置1〇〇 之載體部122之石夕晶圓壓接，並藉由與石夕晶圓相對移動而 研磨矽晶圓表面。 旋轉定盤部121係包含將研磨墊1 〇 1以黏著膠帶等在上面 大致前面處貼付並支持之定盤102、以及介由設置於該定 盤102之下面側的旋轉軸而連接之旋轉驅動機構103的支持 200426205 手段。藉由旋轉驅動機構1 〇3產生之旋轉驅動力通過旋轉 軸傳達至定盤102,定盤102與研磨墊1〇1一同以特定旋轉 數以垂直方向軸線附近旋轉。旋轉數可自由設定，並可藉 由欲研磨對象之晶圓種類或膜之種類、以及研磨墊1 〇 1之 種類等選擇適當的旋轉數。 載體部122如圖12之剖面圖所示，係包含載體本體丨〇4、 支撐材105、護圈環1 〇·6以及旋轉驅動機構丨〇7，並保持被 研磨物即矽晶圓1 〇8，於研磨墊1 〇丨與矽晶圓1 〇8壓接之狀 悲下進行旋轉之保持手段。對矽晶圓1〇8之載體本體1〇4之 固定，係使支撐材105濕潤，並藉由水之表面張力進行吸 著。再者為防止於研磨處理中矽晶圓1〇8脫落，藉由護圈 壤106保持矽晶圓1〇8之外周部。旋轉驅動機構ι〇7係介由 灰轉軸連接至載體本體1 〇4之上面側。藉由旋轉驅動機構 107產生之旋轉驅動力通過旋轉軸傳達至載體本體1〇4，且 載體本體104與矽晶圓108一同以特定之旋轉數於垂直方向 轴線附近旋轉。旋轉數可自由設定，並與旋轉定盤部121 同樣’可藉由欲研磨對象的晶圓種類或膜之種類、以及研 磨塾101之種類等選擇適當之旋轉數。又載體部122係於接 近旋轉定盤部121之方向，垂直向下加壓，並壓接研磨墊 101以及石夕晶圓108。載體部122之加壓可由旋轉驅動機構 107施加’亦可使用其他加壓機構。 衆料*供給部123係包含喷嘴109、漿料供給管110以及漿 料槽111之供給手段。 藉由果等將儲留於漿料槽111之氧化矽漿料，流入漿料 91070 -22· 200426205 仏、、’5笞110内，並自設置於旋轉定盤部丨21之上部且大致中 央部之喷嘴109對於研磨墊1〇1表面以特定之流量進行供 給。至於該供給之氧化矽漿料，使用實施例丨以及比較例 1、2之漿料。 伴隨研磨之進行，於研磨墊1〇1之研磨面附近之微細孔 中堵塞研磨屑或研磨粒等，且研磨率等之研磨特性降低。 修整部124係由電附著有調節器即工業用金剛石粒子之薄 板112、以及介由旋轉軸與薄板112連接之旋轉驅動機構 113所構成之再生手段。於修整時，藉由旋轉驅動機構113 使薄板112旋轉，且將研磨墊1〇1之研磨面與金剛石粒子接 觸’並去除堵塞部分，藉此使研磨墊1〇1再生之研磨特 性。 關於研磨處理時之各部分之運作，載體部122垂直向下 加壓，於壓接研磨墊101以及矽晶圓108之狀態下，漿料供 給部123供給氧化夕漿料。供給之氧化碎漿料浸透至研磨 墊1 〇 1與矽晶圓108之間，並旋轉且相對移動旋轉定盤部 121與載體部122，藉此藉由媒質之化學作用與研磨粒之機 械作用以高精度研磨矽晶圓1〇8之表面。 關於旋轉定盤部121與載體部122之相對移動存在有如下 多種方式。 (1)如圖所示，配置載體部122以使載體部122之中心位 於自旋轉定盤部12 1之旋轉中心半徑方向上大約1 /2之位 置，且僅以旋轉定盤部121與載體部122之自轉進行研磨處 200426205 (2) 於研磨墊1〇1半徑與矽晶圓1〇8半徑間的差相差不太 大時則⑴亦可’但於研磨塾1〇1半徑大於石夕晶圓9之粒子直 徑時，存在有研磨墊1〇1表面未與矽晶圓1〇8接觸之部分， 故而為能使用研磨墊101之全部表面，除（1)之旋轉定盤部 . 121與載體部122之自轉以外，載體部122於旋轉定盤部i2i 之半徑方向上來回移動。 (3) 除（1)之旋轉定盤部121與載體部122之自轉以外，載 體部122於旋轉定盤部121之中心周圍旋轉移動。 鲁 (4) 與（2)相同，於研磨墊1〇1半徑大於矽晶圓半徑 時’將半控方向上來回移動與旋轉定盤部12丨之中心周圍 旋轉移動予以組合。例如，於旋轉定盤部121之中心周圍 有如描繪螺旋執道般移動載體部122即可。 再者，旋轉定盤部121以及載體部丨22之自轉旋轉方向亦 可相同，亦可不同。又，旋轉定盤部121以及載體部122之 自轉旋轉速度亦可相同，亦可不同。 - 修整部124之修整時期，存在有於研磨處理i或複數個矽 _ 晶圓後進行之情形、以及於研磨處理中進行之情形。修整 部124之金剛石薄板112之半徑小於研磨墊1 〇 1之半徑之情 形較多，故而於研磨處理後進行修整之情形時，與上述之 ， 旋轉定盤部121與載體部122之相對移動之方式（2)以及（4) * 大致相同進行即可。於研磨處理中進行之情形時，如圖所 · 不’挾住旋轉定盤部121之中心而配置於載體部ι22相反 側’並與相對移動之方式（2)大致同樣進行即可。 使用如以上之CMP裝置1〇〇進行研磨處理。 91070 -24- 200426205 作為被研磨物，使用TEOS晶圓，作為研磨墊丨〇 i，使用 IC1400 K-Gr00ve(R〇del Nitta公司製造）。旋轉定盤部 121 之旋轉速度設定為60 rpm，且氧化矽漿料以1〇〇 ml/min之 速度供給。進行丨分鐘研磨處理後，使用日立電子技術公 司製造之晶圓表面檢查裝置（LS6600)並計算晶圓表面之劃 痕數（大小為0.2 μιη以上）。 圖1 3係表示使用實施例1以及比較例1、2之研磨處理結 果的圖。縱軸表示每1個晶圓之劃痕數。分別關於實施例i 以及比較例1、2進行3次研磨處理。 比較例1之劃痕數為261〜399(平均322) ’比較例2之劃痕 數為103〜154(平均123)，實施例丨之劃痕數大幅度減少至 28〜63(平均40)。 如此，基於本發明而製成之氧化矽漿料因具有高分散 性，且粗大凝聚粒子數少，故而於研磨處理中可減少晶圓 表面之劃痕數。 本發明在未脫離其精神或主要特徵之下，彳以其他各種 方式進行實施。因此’前述之實施方式僅為所有重點之單 純例不’本發明之範圍係表示於申請專利範圍，並不限於 說明書本文中。再者’屬於申請專利範圍的變形或變化均 屬本發明之範圍。 產業上之可利用性 4據本發明，對於經調製之鹼性物質水溶液中，藉 由添加塵狀氧化石夕分散液，可獲得分散穩定性優良，且凝 聚粒子少之研磨用組合物。 91070 -25· 200426205 又根據本發明，可有效供給高剪切力，並提高分散性。 又根據本發明，藉由添加少量水而可降低研磨用組合物 之黏度。 又根據本發明，藉由於5小時以内終止混合而可迅速降 低混合液之pH值，縮短造成塵狀氧化矽易凝聚之ρίί條件 的時間並可抑制凝聚產生。 又根據本發明，於第2步驟中獲得之研磨用組合物因凝 聚物之產生少，故而藉由過濾處理可有效除去凝聚物。If "if", it is found that it is better to add the oxidized stone dispersion to the test substance aqueous solution. (6) About the time of putting the silicon oxide dispersion liquid, the main point is about the situation of putting the silicon oxide dispersion liquid into the aqueous solution of the test substance in step 2-1. The conditions of the human situation are to make an oxygen-cutting paste qualitative substance, and potassium hydroxide is used. In addition, the conditions other than the investment time are the same in two parts. The graph of the influence of the particle size distribution of the material. The vertical axis represents the frequency and the horizontal axis represents the particle diameter. 91070 -17- 200426205 Curve 24 represents the case where the input time is 5 hours, and curve 25 represents the case where the input time is 20 minutes. ^ If For a long period of time, when the dispersion solution of oxidized stone is added, the potassium hydroxide aqueous solution is a strong base 11. As a result, agglomerates are generated due to the impact of the pH value. By shortening the input time, the pH value of the mixed solution can be quickly reduced to the stable area of oxidized stone. That is, the formation of agglomerates can be suppressed because it is less than or equal to ^. From the above, it can be seen that the addition of the silica dispersion to the alkaline substance aqueous solution is preferably terminated within 5 hours. Figure 7 is a table The graph of the influence of the rate of the oxidized stone dispersion dispersion on the value of the mixed solution. The vertical axis represents the pH value of the mixed solution, and the horizontal axis represents the time of the silicon oxide dispersion. A curve 27 shows a case where the feeding speed is 12.5 liters / minute, and a curve "shows a case where the feeding speed is 5 liters / minute. In this way, by increasing the feeding speed, the pH value of the mixed solution can be quickly reduced to the stable region of silica, that is, the pH is below 12. (7) About the filtering accuracy and processing flow rate of the filter_ First, 'About the transition accuracy of the transition device in step 3 -1, the filtering is performed with the transition accuracy of 1 μιη, 3 μιη, 5 μτη, 7 μιη, and 10, respectively. . As for the filter, a depth-type filter with a small pressure loss and a large flow rate can be used. ^ ψ Figure 8 is a graph showing the effect of filter accuracy on the removal performance of coarse particles. The vertical axis shows the number of coarse particles in the silicon oxide slurry, and the figure shows the number of coarse particles before the treatment and the number of coarse particles after the filtration treatment. Line 29 indicates the change in the number of particles when the filtering accuracy is 1 μπι, 91070 -18- line 3 0 indicates the change in the number of particles when the clearing degree is expected to be 3 μπι, and the accuracy of the straight line is 5 4 times. The number of particles in the case changes. The straight line 32 indicates the change in the number of particles in the case where the filtering accuracy is 7; the straight line 33 indicates the change in the number of particles in the case where the accuracy should be 10 nm + g ^ + μιη. In the case of Μ accuracy of 5 μΐη, 7, 10 μηι, the filtration accuracy is "^ coarse particles + the particles straight #, so the number of coarse particles after filtering and processing is ..., cross, and sufficient filtration performance cannot be obtained. In this regard, when the filter fines are 1 μηι and 3 μηΐ2, the number of coarse particles after the filtering process is greatly reduced. Next, 'about the processing flow of the filter in step ^, the filtering is performed under the same conditions as above. Figure 9 It is a graph showing the influence of filter filtering accuracy on the processing flow rate. The vertical axis shows the processing flow rate of the filtering process, and the figure shows the other speeds for each filtering accuracy. The symbol 74 indicates the flow rate when the transition accuracy is 1 μm. The symbol 75 indicates the flow rate when the filtering accuracy is 3 μπι, and the symbol% indicates the flow rate when the filtering accuracy is 5 μιη, the symbol 77 indicates the flow velocity when the filtering accuracy is 7 μιη, and the symbol 78 indicates the filtering accuracy as The flow rate in the case of 10. As can be seen from the figure, the smaller the filtration accuracy is, the smaller the flow rate is. When considering the actual manufacturing step, 'if the flow rate is 2 liters / minute, The above can withstand practical use, so it may be practical when the transition accuracy is 1 μm. If you consider the removal performance of coarse particles and the processing flow rate, you can know that a filter with a transition accuracy of 1 to 4 μm can be used. At this time The processing flow rate is Li 0 liters / minute. 91070 -19- 200426205 Next, regarding the former oxide stone materials based on the prior art and the oxide stone materials based on the present invention (hereinafter referred to as "implementation ""). The i-th previous oxide scale (hereinafter referred to as "Comparative Example 1") is manufactured based on the manufacturing method disclosed in Patent No. 2935125, and the second previous oxide scale slurry (hereinafter referred to as "Comparative Example 2") ) The concentration of the oxidized stone produced is lower than that of the previous oxidized stone aggregate, and has the same degree of viscosity as the silicon oxide slurry prepared based on the present invention. Example 1 was prepared according to the following steps. ⑷Put ultrapure water into a high-shear dispersing device and adjust the pH value to 2 by adding hydrochloric acid. Rhenium is supplied with a high shearing force, and a dust-like oxygen cut is performed until the initial silicon oxide concentration becomes 50% by weight. (c) After the dusty silica is introduced, a high shear force is applied to the silica dispersion for 2 hours and 30 minutes. (d) In order to make the concentration of the silica dispersion liquid to be% by weight, a small amount of ultrapure water was added and a high shear force was continuously supplied for 30 minutes. (e) To make the silica concentration of the silica dispersion 40% by weight, ultrapure water was added and a high shear force was applied for 1 hour. (0) In order to make the final product's silicon oxide slurry have a pH value of 11 and a silicon oxide concentration of 25% by weight, the silicon oxide dispersion was put into a potassium hydroxide aqueous solution whose potassium hydroxide concentration was adjusted. (G) Further 'Using a depth-type filter with a filtration accuracy of 3 μm removes coarse particles. Figures 〇 are graphs showing the number of coarse particles 91070 -20- 200426205 contained in Comparative Examples 1 and 2, and the vertical axis shows coarseness. The number of particles, the horizontal axis indicates the particle diameter. Curve 39 indicates Example 1, curve 40 indicates Comparative Example 1, and curve 41 indicates Comparative Example 2. It can be seen that the number of coarse particles in Example 1 is greatly reduced compared with Comparative Examples 1 and 2. About the number of coarse particles and other physical property values, Table 1 shows the comparison results of three types of silica slurry. [Table 1] Silicon oxide concentration [wt%] PH [-] Viscosity [cP] Intermediate particle diameter [nm] Number of coarse particles (> 0.5 μπι) [particles / 0.5 ml] Number of coarse particles (> 1 μπι) [particles / 0.5 ml] Example 1 25.7 11.0 3.7 112 100,000 2,000 Comparative Example 1 25.7 10.9 6.6 125 9,000,000 160,000 Comparative Example 2 20.7 11.0 3.7 125 500,00 0 25,000 As shown in Table 1, in Example 1, although the intermediate particle diameter is small and the silicon dioxide concentration is high, the viscosity is still reduced. Furthermore, the silicon wafer is actually polished using these silicon oxide pastes. Figure 11 shows A schematic external view of the CMP apparatus 100. The CMP apparatus 100 is composed of a polishing pad 101, a rotating plate portion 121, a carrier portion 122, a slurry supply portion 123, and a trimming portion 124. The polishing pad 101 is held in the CMP. The Shixi wafer of the carrier portion 122 of the device 100 is crimped, and the surface of the silicon wafer is polished by moving relative to the Shixi wafer. The rotating platen 121 includes a polishing pad 101 and an adhesive tape. The fixed plate 102 attached and supported approximately at the front, and the support 200426205 means of the rotary drive mechanism 103 connected via a rotary shaft provided on the lower side of the fixed plate 102. It is generated by the rotary drive mechanism 103. The rotational driving force is transmitted to the fixed plate 102 through the rotating shaft, and the fixed plate 102 rotates around the vertical axis with a specific number of rotations together with the polishing pad 101. The number of rotations can be freely set and can be determined by the type of wafer to be polished. Or type of membrane And the type of polishing pad 1 〇1, etc., select an appropriate number of rotations. As shown in the cross-sectional view of FIG. 12, the carrier portion 122 includes a carrier body 丨 〇4, a support material 105, a retainer ring 1 〇6, and a rotation drive mechanism.丨 〇7, and holding the object to be polished, that is, the silicon wafer 108, is a holding means for rotating under the condition that the polishing pad 100 and the silicon wafer 108 are crimped. The carrier body 104 of the silicon wafer 108 is fixed by moistening the supporting material 105 and absorbing it by the surface tension of water. Furthermore, in order to prevent the silicon wafer 108 from falling off during the polishing process, the outer periphery of the silicon wafer 108 is held by the retaining ring 106. The rotation drive mechanism ι07 is connected to the upper side of the carrier body 104 via a gray shaft. The rotation driving force generated by the rotation driving mechanism 107 is transmitted to the carrier body 104 through the rotation shaft, and the carrier body 104 and the silicon wafer 108 rotate together with the silicon wafer 108 at a specific rotation number near the vertical axis. The number of rotations can be set freely, and similar to the rotation platen 121 ', an appropriate number of rotations can be selected according to the type of wafer or film to be polished, and the type of the polishing pad 101. In addition, the carrier portion 122 is in a direction close to the rotating plate portion 121, presses vertically downward, and press-contacts the polishing pad 101 and the Shixi wafer 108. The pressurization of the carrier portion 122 may be applied by the rotation driving mechanism 107 'or other pressurizing mechanisms may be used. The crowd supply unit 123 is a supply means including a nozzle 109, a slurry supply pipe 110, and a slurry tank 111. The silicon oxide slurry stored in the slurry tank 111 is poured into the slurry 91070 -22 · 200426205 仏, 笞 5 笞 110 by the fruit and the like, and is provided on the upper part of the rotating plate part 丨 21 and approximately at the center. The nozzle 109 of the part is supplied to the surface of the polishing pad 101 at a specific flow rate. As for the supplied silicon oxide slurry, the slurry of Example 丨 and Comparative Examples 1 and 2 was used. With the progress of polishing, the fine pores near the polishing surface of the polishing pad 101 are blocked with abrasive chips, abrasive particles, and the like, and the polishing characteristics such as polishing rate are reduced. The trimming unit 124 is a regeneration means composed of a thin plate 112 to which a regulator, that is, industrial diamond particles are electrically attached, and a rotation driving mechanism 113 connected to the thin plate 112 via a rotating shaft. During the trimming, the thin plate 112 is rotated by the rotation driving mechanism 113, and the abrasive surface of the polishing pad 101 is brought into contact with the diamond particles' and the clogged portion is removed, thereby regenerating the polishing characteristics of the polishing pad 101. Regarding the operation of each part during the polishing process, the carrier portion 122 is pressed downward vertically, and the slurry supply portion 123 supplies the oxide slurry in a state where the polishing pad 101 and the silicon wafer 108 are pressure-bonded. The supplied oxidized crushed slurry penetrates between the polishing pad 100 and the silicon wafer 108, and rotates and relatively moves the rotating plate portion 121 and the carrier portion 122, thereby utilizing the chemical action of the medium and the mechanical action of the abrasive particles. Polish the surface of the silicon wafer 108 with high precision. There are various methods for the relative movement of the rotating plate part 121 and the carrier part 122 as follows. (1) As shown in the figure, the carrier portion 122 is arranged such that the center of the carrier portion 122 is located at a position about 1/2 in the radial direction of the rotation center of the spin fixing plate portion 121, and only the rotation fixing plate portion 121 and the carrier The rotation of the part 122 is carried out at the polishing place 200426205. (2) When the difference between the radius of the pad 101 and the radius of the silicon wafer 108 is not too large, it is not allowed. When the particle diameter of the wafer 9 exists, there is a portion where the surface of the polishing pad 101 is not in contact with the silicon wafer 108, so that the entire surface of the polishing pad 101 can be used, except for the rotating plate portion of (1). 121 Except for the rotation of the carrier portion 122, the carrier portion 122 moves back and forth in a radial direction of the rotating fixed plate portion i2i. (3) Except for the rotation of the rotating plate portion 121 and the carrier portion 122 of (1), the carrier portion 122 rotates around the center of the rotating plate portion 121. Lu (4) Same as (2), when the radius of the polishing pad 101 is larger than the radius of the silicon wafer ', the semi-controlling direction is moved back and forth with the rotation around the center of the rotating plate portion 12 丨. For example, the carrier portion 122 may be moved around the center of the rotating plate portion 121 like a spiral. In addition, the rotation direction of the rotary fixed plate portion 121 and the carrier portion 22 may be the same or different. In addition, the rotation speeds of the rotary plate portion 121 and the carrier portion 122 may be the same or different. -The trimming period of the trimming unit 124 may be performed after the polishing process i or a plurality of silicon wafers, and may be performed during the polishing process. In some cases, the radius of the diamond sheet 112 of the dressing section 124 is smaller than the radius of the polishing pad 101. Therefore, when the dressing is performed after the polishing process, the relative movement of the rotating plate 121 and the carrier 122 is the same as described above. The methods (2) and (4) * can be performed in approximately the same manner. In the case of performing the polishing process, as shown in the figure, the center of the rotary platen portion 121 is not held, and it is disposed on the opposite side of the carrier portion ι22 ', and may be performed in substantially the same manner as the relative movement method (2). The polishing process was performed using the CMP apparatus 100 as described above. 91070 -24- 200426205 As the object to be polished, a TEOS wafer was used, and as a polishing pad, IC1400 K-Gr00ve (manufactured by Rodel Nitta) was used. The rotation speed of the rotary platen 121 was set to 60 rpm, and the silicon oxide slurry was supplied at a speed of 100 ml / min. After the 丨 minute grinding process, a wafer surface inspection device (LS6600) manufactured by Hitachi Electronics Technology Co., Ltd. was used to calculate the number of scratches on the wafer surface (the size is 0.2 μm or more). Fig. 13 is a view showing the results of polishing treatments using Example 1 and Comparative Examples 1 and 2. Figs. The vertical axis indicates the number of scratches per wafer. The polishing process was performed three times for Example i and Comparative Examples 1 and 2, respectively. The number of scratches in Comparative Example 1 was 261 to 399 (average 322). The number of scratches in Comparative Example 2 was 103 to 154 (average 123). The number of scratches in Example 丨 was greatly reduced to 28 to 63 (average 40). . In this way, the silicon oxide slurry prepared based on the present invention has high dispersibility and has a small number of coarse aggregate particles, so the number of scratches on the surface of the wafer can be reduced during the polishing process. The present invention may be implemented in various other ways without departing from its spirit or main characteristics. Therefore, the foregoing embodiment is merely a pure example of all the important points. The scope of the present invention is shown in the scope of patent application, and is not limited to the description and the text. Furthermore, variations or changes belonging to the scope of patent application are within the scope of the present invention. Industrial Applicability 4 According to the present invention, a polishing composition having excellent dispersion stability and few agglomerated particles can be obtained by adding a dusty oxidized stone dispersion to a prepared alkaline substance aqueous solution. 91070-25 · 200426205 According to the present invention, it can effectively supply high shear force and improve dispersibility. According to the present invention, the viscosity of the polishing composition can be reduced by adding a small amount of water. According to the present invention, by stopping the mixing within 5 hours, the pH value of the mixed solution can be rapidly lowered, the time for the conditions that cause dusty silica to easily aggregate can be shortened, and the occurrence of aggregation can be suppressed. According to the present invention, since the polishing composition obtained in the second step has less generation of agglomerates, the agglomerates can be effectively removed by filtration.
【圖式簡單說明】 圖1係本發明一實施樣態之流程圖。 圖2係表示PH值對於凝聚粒子成長率之影響圖表。 圖3係表示氧化矽分散液的初期氧化矽濃度對於氧化矽 漿料之粒度分佈之影響圖表。 圖4係表示氧化矽濃度對於氧化矽漿料中之粗大粒子數 之影響圖表。[Brief description of the drawings] FIG. 1 is a flowchart of an embodiment of the present invention. Fig. 2 is a graph showing the effect of pH on the growth rate of aggregated particles. Figure 3 is a graph showing the effect of the initial silica concentration of the silica dispersion on the particle size distribution of the silica slurry. Figure 4 is a graph showing the effect of silica concentration on the number of coarse particles in a silica slurry.
圖5係表示混合條件對於氧化矽漿料之粒度分佈之影 圖表。 圖6係表示氧㈣分散液投人時間對於氧切衆料之粒 度分佈之影響圖表。 圖7係表示氧切分散液之投人速度對於混合液之輝 之影響圖表。 圖8係表 影響圖。 示過遽m精度對於粗大粒子之除去性能之 圖9係表示過渡器過濾精度對於處理流速之影響圖 91070 -26- 200426205 圖1 〇係表示比較例1以及2、實施例1所含粗大粒子數的 圖表。 圖11係表示CMP裝置100之概要外觀圖。 圖12係載體部122之剖面圖。 2之研磨處理結 圖13係表示使用實施例1以及比較例^ 果圖。 【主要元件符號說明】 100 CMP裝置 101 研磨墊 102 定盤 103, 107, 113 旋轉驅動機構 104 栽體本體 105 支撐材 106 護圈環 108 石夕晶圓 109 噴嘴 110 渡料供給管 111 漿料槽 112 121 旋轉定盤部 122 .栽體部 123 激料供給部 124 修整部Fig. 5 is a graph showing the influence of mixing conditions on the particle size distribution of the silicon oxide slurry. Fig. 6 is a graph showing the effect of the time of the injection of the oxygen tritium dispersion on the particle size distribution of the oxygen-cutting crowd. Fig. 7 is a graph showing the influence of the rate of injection of the oxygen-cutting dispersion liquid on the brightness of the mixed liquid. Figure 8 is a table of influence diagrams. Figure 9 shows the removal performance of 遽 m accuracy for coarse particles. Figure 9 shows the effect of the filter accuracy of the transitioner on the processing flow rate. Figure 91070 -26- 200426205 Figure 1 shows the number of coarse particles contained in Comparative Examples 1 and 2, Example 1. Chart. FIG. 11 is a schematic external view showing the CMP apparatus 100. FIG. 12 is a cross-sectional view of the carrier portion 122. Polishing treatment result of 2 FIG. 13 is a graph showing the results of using Example 1 and Comparative Example. [Description of main component symbols] 100 CMP device 101 Polishing pad 102 Fixed plate 103, 107, 113 Rotary driving mechanism 104 Plant body 105 Supporting material 106 Retaining ring 108 Shi Xi wafer 109 Nozzle 110 Ferry supply pipe 111 Slurry tank 112 121 Rotating plate part 122. Body part 123 Laser material supply part 124 Trimming part
-27,-27,